Surface-Enhanced Raman Scattering Based Nonfluorescent Probe for Multiplex DNA Detection

PubMed Central

Sun, Lan; Yu, Chenxu; Irudayaraj, Joseph

2008-01-01

To provide rapid and accurate detection of DNA markers in a straightforward, inexpensive and multiplex format, an alternative surface enhanced Raman scattering (SERS) based probe was designed and fabricated to covalently attach both DNA probing sequence and non-fluorescent Raman tags to the surface of gold nanoparticles (DNA-AuP-RTag). The intensity of Raman signal of the probes could be controlled through the surface coverage of the non-fluorescent Raman tags (RTags). Detection sensitivity of these probes could be optimized by fine-tuning the amount of DNA molecules and RTags on the probes. Long-term stability of the DNA-AuP-RTag probes was found to be good (over 3 months). Excellent multiplexing capability of the DNA-AuP-RTag scheme was demonstrated by simultaneous identification of up to eight probes in a mixture. Detection of hybridization of single-stranded DNA (ssDNA) to its complementary targets was successfully accomplished with a long-term goal to use non-fluorescent RTags in a Raman-based DNA microarray platform. PMID:17465531

Bare laser-synthesized Au-based nanoparticles as nondisturbing surface-enhanced Raman scattering probes for bacteria identification.

PubMed

Kögler, Martin; Ryabchikov, Yury V; Uusitalo, Sanna; Popov, Alexey; Popov, Anton; Tselikov, Gleb; Välimaa, Anna-Liisa; Al-Kattan, Ahmed; Hiltunen, Jussi; Laitinen, Riitta; Neubauer, Peter; Meglinski, Igor; Kabashin, Andrei V

2018-02-01

The ability of noble metal-based nanoparticles (NPs) (Au, Ag) to drastically enhance Raman scattering from molecules placed near metal surface, termed as surface-enhanced Raman scattering (SERS), is widely used for identification of trace amounts of biological materials in biomedical, food safety and security applications. However, conventional NPs synthesized by colloidal chemistry are typically contaminated by nonbiocompatible by-products (surfactants, anions), which can have negative impacts on many live objects under examination (cells, bacteria) and thus decrease the precision of bioidentification. In this article, we explore novel ultrapure laser-synthesized Au-based nanomaterials, including Au NPs and AuSi hybrid nanostructures, as mobile SERS probes in tasks of bacteria detection. We show that these Au-based nanomaterials can efficiently enhance Raman signals from model R6G molecules, while the enhancement factor depends on the content of Au in NP composition. Profiting from the observed enhancement and purity of laser-synthesized nanomaterials, we demonstrate successful identification of 2 types of bacteria (Listeria innocua and Escherichia coli). The obtained results promise less disturbing studies of biological systems based on good biocompatibility of contamination-free laser-synthesized nanomaterials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface-enhanced Raman scattering (SERS) detection of multiple viral antigens using magnetic capture of SERS-active nanoparticles

USDA-ARS?s Scientific Manuscript database

A highly sensitive immunoassay based on surface-enhanced Raman scattering (SERS) spectroscopy has been developed for multiplex detection of surface envelope and capsid antigens of the viral zoonotic pathogens West Nile virus (WNV) and Rift Valley fever virus (RVFV). Detection was mediated by antibo...

Optofluidic platforms based on surface-enhanced Raman scattering.

PubMed

Lim, Chaesung; Hong, Jongin; Chung, Bong Geun; deMello, Andrew J; Choo, Jaebum

2010-05-01

We report recent progress in the development of surface-enhanced Raman scattering (SERS)-based optofluidic platforms for the fast and sensitive detection of chemical and biological analytes. In the current context, a SERS-based optofluidic platform is defined as an integrated analytical device composed of a microfluidic element and a sensitive Raman spectrometer. Optofluidic devices for SERS detection normally involve nanocolloid-based microfluidic systems or metal nanostructure-embedded microfluidic systems. In the current review, recent advances in both approaches are surveyed and assessed. Additionally, integrated real-time sensing systems that combine portable Raman spectrometers with microfluidic devices are also reviewed. Such real-time sensing systems have significant utility in environmental monitoring, forensic science and homeland defense applications.

Surface-enhanced Raman scattering from finite arrays of gold nano-patches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vincenti, M. A.; Ceglia, D. de; US Army-Charles M. Bowden Research Laboratory, 35898 Redstone Arsenal, Huntsville, Alabama

We experimentally investigate the surface-enhanced Raman scattering (SERS) response of a 2D-periodic array of square gold nano-patches, functionalized by means of a conjugated, rigid thiol. We measure a Raman signal enhancement up to 200 times more intense compared to other plasmon-based nanostructures functionalized with the same molecule, and show that the enhancement is not strictly correlated to the presence of plasmonic resonances. The agreement between experimental and theoretical results reveals the importance of a full-wave analysis based on the inclusion of the actual scattering cross section of the molecule. The proposed numerical approach may serve not only as a toolmore » to predict the enhancement of Raman signal scattered from strongly resonant nanostructure but also as an effective instrument to engineer SERS platforms that target specific molecules.« less

Differentiation and classification of bacteria using vancomycin functionalized silver nanorods array based surface-enhanced raman spectroscopy an chemometric analysis

USDA-ARS?s Scientific Manuscript database

The intrinsic surface-enhanced Raman scattering (SERS) was used for differentiating and classifying bacterial species with chemometric data analysis. Such differentiation has often been conducted with an insufficient sample population and strong interference from the food matrices. To address these ...

Integrated waveguide and nanostructured sensor platform for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Pearce, Stuart J.; Pollard, Michael E.; Oo, SweZin; Chen, Ruiqi; Kalsi, Sumit; Charlton, Martin D. B.

2014-01-01

Limitations of current sensors include large dimensions, sometimes limited sensitivity and inherent single-parameter measurement capability. Surface-enhanced Raman spectroscopy can be utilized for environment and pharmaceutical applications with the intensity of the Raman scattering enhanced by a factor of 10. By fabricating and characterizing an integrated optical waveguide beneath a nanostructured precious metal coated surface a new surface-enhanced Raman spectroscopy sensing arrangement can be achieved. Nanostructured sensors can provide both multiparameter and high-resolution sensing. Using the slab waveguide core to interrogate the nanostructures at the base allows for the emission to reach discrete sensing areas effectively and should provide ideal parameters for maximum Raman interactions. Thin slab waveguide films of silicon oxynitride were etched and gold coated to create localized nanostructured sensing areas of various pitch, diameter, and shape. These were interrogated using a Ti:Sapphire laser tuned to 785-nm end coupled into the slab waveguide. The nanostructured sensors vertically projected a Raman signal, which was used to actively detect a thin layer of benzyl mercaptan attached to the sensors.

Effect of pH value of probe molecule on the graphene oxide-based surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Cui, Shao-li; Du, Xiao-qing; Zeng, Chao; Li, Lu; Bao, Jun

2017-06-01

The dependence of graphene oxide (GO)-based surface enhanced Raman scattering (SERS) on the pH value of probe molecule was investigated. Water-soluble copper phthalocyanine (TSCuPc) was used as probe molecule and its pH value was adjusted with HCl and NaOH solution. The Raman spectra of TSCuPc with pH equaling 3, 8, and 11 on GO base were tested, respectively. The results show that both Raman enhanced intensity and full width at half maximum (FWHM) of characteristic peaks vary with the pH value of TSCuPc. It is shown that there is no obvious spectral widening of TSCuPc characteristic peaks when TSCuPc is neutral or acidic, and the chemical enhancement intensity of neutral TSCuPc on GO is biggest. In contrast, when TSCuPc is alkaline, the characteristic Raman peaks between 1350 and 1600 cm-1 of TSCuPc on GO are much wider and the intensities of characteristic peaks decrease considerably. The reasons for the pH dependence of GO-based Raman spectra were explored by comparing the wettability of molecule droplet on GO and the absorbance of different pH-adjusted TSCuPc films. It is found that the effect of molecule's pH value on SERS can be contributed to the differences of concentration and distributions on GO surface for varied pH-treated molecule.

Graphene-based textured surface by pulsed laser deposition as a robust platform for surface enhanced Raman scattering applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tite, T.; Donnet, C.; Loir, A.-S.

We have developed a surface enhanced Raman scattering (SERS)-active substrate based on gold nanoparticles-decorated few-layer (fl) graphene grown by pulsed laser deposition. Diamond-Like Carbon film has been converted to fl-graphene after thermal annealing at low temperature. The formation of fl-graphene was confirmed by Raman spectroscopy, and surface morphology was highlighted by scanning electron microscopy. We found that textured fl-graphene film with nanoscale roughness was highly beneficial for SERS detection. Rhodamine 6G and p-aminothiophenol proposed as test molecules were detected with high sensitivity. The detection at low concentration of deltamethrin, an active molecule of a commercial pesticide was further demonstrated.

Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces.

PubMed

Wen, Bao-Ying; Jin, Xi; Li, Yue; Wang, Ya-Hao; Li, Chao-Yu; Liang, Miao-Miao; Panneerselvam, Rajapandiyan; Xu, Qing-Chi; Wu, De-Yin; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2016-06-21

For the first time, we used the electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) technique to in situ characterize the adsorption behaviour of four DNA bases (adenine, guanine, thymine, and cytosine) on atomically flat Au(111) electrode surfaces. The spectroscopic results of the various molecules reveal similar features, such as the adsorption-induced reconstruction of the Au(111) surface and the drastic Raman intensity reduction of the ring breathing modes after the lifting reconstruction. As a preliminary study of the photo-induced charge transfer (PICT) mechanism, the in situ spectroscopic results obtained on single crystal surfaces are excellently illustrated with electrochemical data.

Plasmonic photoluminescence for recovering native chemical information from surface-enhanced Raman scattering

PubMed Central

Lin, Kai-Qiang; Yi, Jun; Zhong, Jin-Hui; Hu, Shu; Liu, Bi-Ju; Liu, Jun-Yang; Zong, Cheng; Lei, Zhi-Chao; Wang, Xiang; Aizpurua, Javier; Esteban, Rubén; Ren, Bin

2017-01-01

Surface-enhanced Raman scattering (SERS) spectroscopy has attracted tremendous interests as a highly sensitive label-free tool. The local field produced by the excitation of localized surface plasmon resonances (LSPRs) dominates the overall enhancement of SERS. Such an electromagnetic enhancement is unfortunately accompanied by a strong modification in the relative intensity of the original Raman spectra, which highly distorts spectral features providing chemical information. Here we propose a robust method to retrieve the fingerprint of intrinsic chemical information from the SERS spectra. The method is established based on the finding that the SERS background originates from the LSPR-modulated photoluminescence, which contains the local field information shared also by SERS. We validate this concept of retrieval of intrinsic fingerprint information in well controlled single metallic nanoantennas of varying aspect ratios. We further demonstrate its unambiguity and generality in more complicated systems of tip-enhanced Raman spectroscopy (TERS) and SERS of silver nanoaggregates. PMID:28348368

Facile synthesis of terminal-alkyne bioorthogonal molecules for live -cell surface-enhanced Raman scattering imaging through Au-core and silver/dopamine-shell nanotags.

PubMed

Chen, Meng; Zhang, Ling; Yang, Bo; Gao, Mingxia; Zhang, Xiangmin

2018-03-01

Alkyne is unique, specific and biocompatible in the Raman-silent region of the cell, but there still remains a challenge to achieve ultrasensitive detection in living systems due to its weak Raman scattering. Herein, a terminal alkyne ((E)-2-[4-(ethynylbenzylidene)amino]ethane-1-thiol (EBAE)) with surface-enhanced Raman scattering is synthesized. The EBAE molecule possesses S- and C-termini, which can be directly bonded to gold nanoparticles and dopamine/silver by forming the Au-S chemical bond and the carbon-metal bond, respectively. The distance between Raman reporter and AuNPs/AgNPs can be reduced, contributing to forming hot-spot-based SERS substrate. The alkyne functionalized nanoparticles are based on Au core and encapsulating polydopamine shell, defined as Au-core and dopamine/Ag-shell (ACDS). The bimetallic ACDS induce strong SERS signals for molecular imaging that arise from the strong electromagnetic field. Furthermore, the EBAE provides a distinct peak in the cellular Raman-silent region with nearly zero background interference. The EBAE Raman signals could be tremendously enhanced when the Raman reporter is located at the middle of the Au-core and dopamine/Ag-shell. Therefore, this work could have huge potential benefits for the highly sensitive detection of intercellular information delivery by connecting the recognition molecules in biomedical diagnostics. Graphical abstract Terminal-alkyne-functionalized Au-core and silver/dopamine-shell nanotags for live-cell surface-enhanced Raman scattering imaging.

Enhanced Raman scattering in porous silicon grating.

PubMed

Wang, Jiajia; Jia, Zhenhong; Lv, Changwu

2018-03-19

The enhancement of Raman signal on monocrystalline silicon gratings with varying groove depths and on porous silicon grating were studied for a highly sensitive surface enhanced Raman scattering (SERS) response. In the experiment conducted, porous silicon gratings were fabricated. Silver nanoparticles (Ag NPs) were then deposited on the porous silicon grating to enhance the Raman signal of the detective objects. Results show that the enhancement of Raman signal on silicon grating improved when groove depth increased. The enhanced performance of Raman signal on porous silicon grating was also further improved. The Rhodamine SERS response based on Ag NPs/ porous silicon grating substrates was enhanced relative to the SERS response on Ag NPs/ porous silicon substrates. Ag NPs / porous silicon grating SERS substrate system achieved a highly sensitive SERS response due to the coupling of various Raman enhancement factors.

Raman and surface enhanced Raman scattering study of the orientation of cruciform 9,10-anthracene thiophene and furan derivatives deposited on a gold colloidal surface

NASA Astrophysics Data System (ADS)

Muñoz-Pérez, J.; Leyton, P.; Paipa, C.; Soto, J. P.; Brunet, J.; Gómez-Jeria, J. S.; Campos-Vallette, M. M.

2016-10-01

The 9,10-di(thiophen-2-yl)anthracene (TAT), 9,10-di(furan-2-yl)anthracene (FAF) and 2-[(10-(thiophen-2-yl)anthracen-9-yl)]furan (TAF) cruciform molecular systems were synthesized using one-step coupling reactions and structurally characterized via Raman, infrared, 1H NMR, 13C NMR and mass spectroscopies. The orientation of the analytes on a gold colloidal surface was inferred from a surface-enhanced Raman scattering (SERS) study. The metal surface interaction was driven by the S and O atoms of the thiophene and furan α-substituents, and the plane of the anthracene fragment remained parallel to the surface. Theoretical calculations based on a simplified molecular model for the analyte-surface interaction provide a good representation of the experimental data.

Effectiveness of surface enhanced Raman spectroscopy of tear fluid with soft substrate for point-of-care therapeutic drug monitoring

NASA Astrophysics Data System (ADS)

Yamada, K.; Endo, T.; Imai, H.; Kido, M.; Jeong, H.; Ohno, Y.

2016-03-01

We have developed the point-of-care therapeutic drug monitoring kit based on Raman Spectroscopy of tear fluid. In this study, we were examined a soft substrate for an optimal lattice based on nanoimprint lithography using cyclo-olefin polymer to improve the sensitivity for measuring drug concentration in tear fluid. This is photonics crystal which is one of the nano-photonics based device was fabricated. Target is Sodium Phenobarbital which is an anticonvulsant agent. We show the effectiveness of Surface Enhanced Raman Spectroscopy of tear fluid with soft substrate for point-of-care therapeutic drug monitoring.

Alizarin Dye based ultrasensitive plasmonic SERS probe for trace level Cadmium detection in drinking water

PubMed Central

Dasary, Samuel S.R.; Zones, Yolanda K.; Barnes, Sandra L.; Ray, P. C.; Singh, Anant K.

2015-01-01

Alizarin functionalized on plasmonic gold nanoparticle displays strong surface enhanced Raman scattering from the various Raman modes of Alizarin, which can be exploited in multiple ways for heavy metal sensing purposes. The present article reports a surface enhanced Raman spectroscopy (SERS) probe for trace level Cadmium in water samples. Alizarin, a highly Raman active dye was functionalized on plasmonic gold surface as a Raman reporter, and then 3-mercaptopropionic acid, 2,6-Pyridinedicarboxylic acid at pH 8.5 was immobilized on the surface of the nanoparticle for the selective coordination of the Cd (II). Upon addition of Cadmium, gold nanoparticle provide an excellent hotspot for Alizarin dye and Raman signal enhancement. This plasmonic SERS assay provided an excellent sensitivity for Cadmium detection from the drinking water samples. We achieved as low as 10 ppt sensitivity from various drinking water sources against other Alkali and heavy metal ions. The developed SERS probe is quite simple and rapid with excellent repeatability and has great potential for prototype scale up for field application. PMID:26770012

Plasmon enhanced Raman scattering effect for an atom near a carbon nanotube

DOE PAGES

Bondarev, I. V.

2015-01-01

Quantum electrodynamics theory of the resonance Raman scattering is developed for an atom in a close proximity to a carbon nanotube. The theory predicts a dramatic enhancement of the Raman intensity in the strong atomic coupling regime to nanotube plasmon near-fields. This resonance scattering is a manifestation of the general electromagnetic surface enhanced Raman scattering effect, and can be used in designing efficient nanotube based optical sensing substrates for single atom detection, precision spontaneous emission control, and manipulation.

Next-generation Surface Enhanced Raman Scattering (SERS) Substrates for Hazard Detection

DTIC Science & Technology

2012-09-01

Next-generation Surface Enhanced Raman Scattering (SERS) Substrates for Hazard Detection by Mikella E. Farrell, Ellen L. Holthoff and Paul M...Surface Enhanced Raman Scattering (SERS) Substrates for Hazard Detection Mikella E. Farrell, Ellen L. Holthoff and Paul M. Pellegrino Sensors and...DD-MM-YYYY) September 2012 2. REPORT TYPE Reprint 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Next-generation Surface Enhanced Raman

Esophageal cancer detection based on tissue surface-enhanced Raman spectroscopy and multivariate analysis

NASA Astrophysics Data System (ADS)

Feng, Shangyuan; Lin, Juqiang; Huang, Zufang; Chen, Guannan; Chen, Weisheng; Wang, Yue; Chen, Rong; Zeng, Haishan

2013-01-01

The capability of using silver nanoparticle based near-infrared surface enhanced Raman scattering (SERS) spectroscopy combined with principal component analysis (PCA) and linear discriminate analysis (LDA) to differentiate esophageal cancer tissue from normal tissue was presented. Significant differences in Raman intensities of prominent SERS bands were observed between normal and cancer tissues. PCA-LDA multivariate analysis of the measured tissue SERS spectra achieved diagnostic sensitivity of 90.9% and specificity of 97.8%. This exploratory study demonstrated great potential for developing label-free tissue SERS analysis into a clinical tool for esophageal cancer detection.

Surface-enhanced Raman spectroscopy of double-shell hollow nanoparticles: electromagnetic and chemical enhancements.

PubMed

Mahmoud, Mahmoud A

2013-05-28

Enhancements of the Raman signal by the newly prepared gold-palladium and gold-platinum double-shell hollow nanoparticles were examined and compared with those using gold nanocages (AuNCs). The surface-enhanced Raman spectra (SERS) of thiophenol adsorbed on the surface of AuNCs assembled into a Langmuir-Blodgett monolayer were 10-fold stronger than AuNCs with an inner Pt or Pd shell. The chemical and electromagnetic enhancement mechanisms for these hollow nanoparticles were further proved by comparing the Raman enhancement of nitrothiophenol and nitrotoulene. Nitrothiophenol binds to the surface of the nanoparticles by covalent interaction, and Raman enhancement by both the two mechanisms is possible, while nitrotoulene does not form any chemical bond with the surface of the nanoparticles and hence no chemical enhancement is expected. Based on discrete dipole approximation (DDA) calculations and the experimental SERS results, AuNCs introduced a high electromagnetic enhancement, while the nanocages with inner Pt or Pd shell have a strong chemical enhancement. The optical measurements of the localized surface plasmon resonance (LSPR) of the nanocages with an outer Au shell and an inner Pt or Pd shell were found, experimentally and theoretically, to be broad compared with AuNCs. The possible reason could be due to the decrease of the coherence time of Au oscillated free electrons and fast damping of the plasmon energy. This agreed well with the fact that a Pt or Pd inner nanoshell decreases the electromagnetic field of the outer Au nanoshell while increasing the SERS chemical enhancement.

Characterization of Next Generation Commercial Surface Enhanced Raman Scattering Substrates with a 633- and 785-nm System

DTIC Science & Technology

2013-04-01

Characterization of Next Generation Commercial Surface Enhanced Raman Scattering Substrates with a 633- and 785-nm System by Mikella E...Surface Enhanced Raman Scattering Substrates with a 633- and 785-nm System Mikella E. Farrell, Dimitra N. Stratis-Cullum, and Paul M. Pellegrino...DATES COVERED (From - To) 4. TITLE AND SUBTITLE Characterization of Next Generation Commercial Surface Enhanced Raman Scattering Substrates with a

Ultrathin diamond-like carbon film coated silver nanoparticles-based substrates for surface-enhanced Raman spectroscopy.

PubMed

Liu, Fanxin; Cao, Zhishen; Tang, Chaojun; Chen, Ling; Wang, Zhenlin

2010-05-25

We have demonstrated that by coating with a thin dielectric layer of tetrahedral amorphous carbon (ta-C), a biocompatible and optical transparent material in the visible range, the Ag nanoparticle-based substrate becomes extremely suitable for surface-enhanced Raman spectroscopy (SERS). Our measurements show that a 10 A or thicker ta-C layer becomes efficient to protect the oxygen-free Ag in air and prevent Ag ionizing in aqueous solutions. Furthermore, the Ag nanoparticles substrate coated with a 10 A ta-C film shows a higher enhancement of Raman signals than the uncoated substrate. These observations are further supported by our numerical simulations. We suggest that biomolecule detections in analytic assays could be easily realized using ta-C-coated Ag-based substrate for SERS especially in the visible range. The coated substrate also has higher mechanical stability, chemical inertness, and technological compliance, and may be useful, for example, to enhance TiO(2) photocatalysis and solar-cell efficiency by the surface plasmons.

Demonstration of surface-enhanced Raman scattering by tunable, plasmonic gallium nanoparticles.

PubMed

Wu, Pae C; Khoury, Christopher G; Kim, Tong-Ho; Yang, Yang; Losurdo, Maria; Bianco, Giuseppe V; Vo-Dinh, Tuan; Brown, April S; Everitt, Henry O

2009-09-02

Size-controlled gallium nanoparticles deposited on sapphire were explored as alternative substrates to enhance Raman spectral signatures. Gallium's resilience following oxidation is inherently advantageous in comparison with silver for practical ex vacuo nonsolution applications. Ga nanoparticles were grown using a simple molecular beam epitaxy-based fabrication protocol, and monitoring their corresponding surface plasmon resonance energy through in situ spectroscopic ellipsometry allowed the nanoparticles to be easily controlled for size. The Raman spectra obtained from cresyl fast violet (CFV) deposited on substrates with differing mean nanoparticle sizes represent the first demonstration of enhanced Raman signals from reproducibly tunable self-assembled Ga nanoparticles. Nonoptimized aggregate enhancement factors of approximately 80 were observed from the substrate with the smallest Ga nanoparticles for CFV dye solutions down to a dilution of 10 ppm.

Demonstration of surface-enhanced Raman scattering by tunable, plasmonic gallium nanoparticles

PubMed Central

Wu, Pae C; Khoury, Christopher G.; Kim, Tong-Ho; Yang, Yang; Losurdo, Maria; Bianco, Giuseppe V.; Vo-Dinh, Tuan; Brown, April S.; Everitt, Henry O.

2009-01-01

Size-controlled gallium nanoparticles deposited on sapphire are explored as alternative substrates to enhance Raman spectral signatures. Gallium’s resilience following oxidation is inherently advantageous compared to silver for practical ex vacuo, non-solution applications. Ga nanoparticles are grown using a simple, molecular beam epitaxy-based fabrication protocol, and by monitoring their corresponding surface plasmon resonance energy through in situ spectroscopic ellipsometry, the nanoparticles are easily controlled for size. Raman spectroscopy performed on cresyl fast violet (CFV) deposited on substrates of differing mean nanoparticle size represents the first demonstration of enhanced Raman signals from reproducibly tunable self-assembled Ga nanoparticles. Non-optimized aggregate enhancement factors of ~80 were observed from the substrate with the smallest Ga nanoparticles for CFV dye solutions down to a dilution of 10 ppm. PMID:19655747

A new aptameric biosensor for cocaine based on surface-enhanced Raman scattering spectroscopy.

PubMed

Chen, Jiwei; Jiang, Jianhui; Gao, Xing; Liu, Guokun; Shen, Guoli; Yu, Ruqin

2008-01-01

The present study reports the proof of principle of a reagentless aptameric sensor based on surface-enhanced Raman scattering (SERS) spectroscopy with "signal-on" architecture using a model target of cocaine. This new aptameric sensor is based on the conformational change of the surface-tethered aptamer on a binding target that draws a certain Raman reporter in close proximity to the SERS substrate, thereby increasing the Raman scattering signal due to the local enhancement effect of SERS. To improve the response performance, the sensor is fabricated from a cocaine-templated mixed self-assembly of a 3'-terminal tetramethylrhodamine (TMR)-labeled DNA aptamer on a silver colloid film by means of an alkanethiol moiety at the 5' end. This immobilization strategy optimizes the orientation of the aptamer on the surface and facilitates the folding on the binding target. Under optimized assay conditions, one can determine cocaine at a concentration of 1 muM, which compares favorably with analogous aptameric sensors based on electrochemical and fluorescence techniques. The sensor can be readily regenerated by being washed with a buffer. These results suggest that the SERS-based transducer might create a new dimension for future development of aptameric sensors for sensitive determination in biochemical and biomedical studies.

Surface-enhanced Raman scattering and DFT investigation of 1,5-diphenylcarbazide and its metal complexes with Ca(II), Mn(II), Fe(III) and Cu(II)

NASA Astrophysics Data System (ADS)

Szabó, László; Herman, Krisztian; Mircescu, Nicoleta Elena; Tódor, István Szabolcs; Simon, Botond Lorand; Boitor, Radu Alex; Leopold, Nicolae; Chiş, Vasile

2014-09-01

In recent years, surface-enhanced Raman scattering (SERS) has become an increasingly viable method for the detection of metal ions, evidenced by the existing studies on metal complexes. In this study, 1,5-diphenylcarbazide (DPC) and its Ca(II), Mn(II), Fe(III) and Cu(II) complexes were investigated by FTIR/ATR, FT-Raman and surface-enhanced Raman spectroscopies. The hybrid B3LYP exchange-correlation functional was used for the molecular geometry optimizations, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculations of the DPC molecule and its complexes. Based on experimental and theoretical data, we were able to accurately identify unique and representative features for each DPC-metal complex, features that enable the detection of said metal complexes in millimolar concentrations.

Surface enhanced Raman scattering spectroscopic waveguide

DOEpatents

Lascola, Robert J; McWhorter, Christopher S; Murph, Simona H

2015-04-14

A waveguide for use with surface-enhanced Raman spectroscopy is provided that includes a base structure with an inner surface that defines a cavity and that has an axis. Multiple molecules of an analyte are capable of being located within the cavity at the same time. A base layer is located on the inner surface of the base structure. The base layer extends in an axial direction along an axial length of an excitation section. Nanoparticles are carried by the base layer and may be uniformly distributed along the entire axial length of the excitation section. A flow cell for introducing analyte and excitation light into the waveguide and a method of applying nanoparticles may also be provided.

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

NASA Astrophysics Data System (ADS)

Valley, Nicholas; Jensen, Lasse; Autschbach, Jochen; Schatz, George C.

2010-08-01

Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman (102-104 versus 101-102). Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

Detection of latent prints by Raman imaging

DOEpatents

Lewis, Linda Anne [Andersonville, TN; Connatser, Raynella Magdalene [Knoxville, TN; Lewis, Sr., Samuel Arthur

2011-01-11

The present invention relates to a method for detecting a print on a surface, the method comprising: (a) contacting the print with a Raman surface-enhancing agent to produce a Raman-enhanced print; and (b) detecting the Raman-enhanced print using a Raman spectroscopic method. The invention is particularly directed to the imaging of latent fingerprints.

Tunable and highly reproducible surface-enhanced Raman scattering substrates made from large-scale nanoparticle arrays based on periodically poled LiNbO3 templates

NASA Astrophysics Data System (ADS)

Liu, Xiaoyan; Kitamura, Kenji; Yu, Qiuming; Xu, Jiajie; Osada, Minoru; Takahiro, Nagata; Li, Jiangyu; Cao, Guozhong

2013-10-01

This work describes novel surface-enhanced Raman scattering (SERS) substrates based on ferroelectric periodically poled LiNbO3 templates. The templates comprise silver nanoparticles (AgNPs), the size and position of which are tailored by ferroelectric lithography. The substrate has uniform and large sampling areas that show SERS effective with excellent signal reproducibility, for which the fabrication protocol is advantageous in its simplicity. We demonstrate ferroelectric-based SERS substrates with particle sizes ranging from 30 to 70 nm and present tunable SERS effect from Raman active 4-mercaptopyridine molecules attached to AgNPs when excited by a laser source at 514 nm.

[Three-dimensional vertically aligned CNTs coated by Ag nanoparticles for surface-enhanced Raman scattering].

PubMed

Zhang, Xiao-Lei; Zhang, Jie; Fan, Tuo; Ren, Wen-Jie; Lai, Chun-Hong

2014-09-01

In order to make surface-enhanced Raman scattering (SERS) substrates contained more "hot spots" in a three-dimensional (3D) focal volume, and can be adsorbed more probe molecules and metal nanoparticles, to obtain stronger Raman spectral signal, a new structure based on vertically aligned carbon nanotubes (CNTs) coated by Ag nanoparticles for surface Raman enhancement is presented. The vertically aligned CNTs are synthesized by chemical vapor deposition (CVD). A silver film is first deposited on the vertically aligned CNTs by magnetron sputtering. The samples are then annealed at different temperature to cause the different size silver nanoparticles to coat on the surface and sidewalls of vertically aligned CNTs. The result of scanning electron microscopy(SEM) shows that Ag nanoparticles are attached onto the sidewalls and tips of the vertically aligned CNTs, as the annealing temperature is different , pitch size, morphology and space between the silver nanoparticles is vary. Rhodamine 6G is served as the probe analyte. Raman spectrum measurement indicates that: the higher the concentration of R6G, the stronger the Raman intensity, but R6G concentration increase with the enhanced Raman intensity varies nonlinearly; when annealing temperature is 450 °C, the average size of silver nanoparticles is about 100 to 120 nm, while annealing temperature is 400 °C, the average size is about 70 nm, and the Raman intensity of 450 °C is superior to the annealing temperature that of 400 °C and 350 °C.

Nanoscale array structures suitable for surface enhanced raman scattering and methods related thereto

DOEpatents

Bond, Tiziana C.; Miles, Robin; Davidson, James C.; Liu, Gang Logan

2014-07-22

Methods for fabricating nanoscale array structures suitable for surface enhanced Raman scattering, structures thus obtained, and methods to characterize the nanoscale array structures suitable for surface enhanced Raman scattering. Nanoscale array structures may comprise nanotrees, nanorecesses and tapered nanopillars.

Nanoscale array structures suitable for surface enhanced raman scattering and methods related thereto

DOEpatents

Bond, Tiziana C.; Miles, Robin; Davidson, James C.; Liu, Gang Logan

2015-07-14

Methods for fabricating nanoscale array structures suitable for surface enhanced Raman scattering, structures thus obtained, and methods to characterize the nanoscale array structures suitable for surface enhanced Raman scattering. Nanoscale array structures may comprise nanotrees, nanorecesses and tapered nanopillars.

Nanoscale array structures suitable for surface enhanced raman scattering and methods related thereto

DOEpatents

Bond, Tiziana C; Miles, Robin; Davidson, James; Liu, Gang Logan

2015-11-03

Methods for fabricating nanoscale array structures suitable for surface enhanced Raman scattering, structures thus obtained, and methods to characterize the nanoscale array structures suitable for surface enhanced Raman scattering. Nanoscale array structures may comprise nanotrees, nanorecesses and tapered nanopillars.

Noninvasive noble metal nanoparticle arrays for surface-enhanced Raman spectroscopy of proteins

NASA Astrophysics Data System (ADS)

Inya-Agha, Obianuju; Forster, Robert J.; Keyes, Tia E.

2007-02-01

Noble metal nanoparticles arrays are well established substrates for surface enhanced Raman spectroscopy (SERS). Their ability to enhance optical fields is based on the interaction of their surface valence electrons with incident electromagnetic radiation. In the array configuration, noble metal nanoparticles have been used to produce SER spectral enhancements of up to 10 8 orders of magnitude, making them useful for the trace analysis of physiologically relevant analytes such as proteins and peptides. Electrostatic interactions between proteins and metal surfaces result in the preferential adsorption of positively charged protein domains onto metal surfaces. This preferential interaction has the effect of disrupting the native conformation of the protein fold, with a concomitant loss of protein function. A major historic advantage of Raman microspectroscopy has been is its non-invasive nature; protein denaturation on the metal surfaces required for SER spectroscopy renders it a much more invasive technique. Further, part of the analytical power of Raman spectroscopy lies in its use as a secondary conformation probe. The protein structural loss which occurs on the metal surface results in secondary conformation readings which are not true to the actual native state of the analyte. This work presents a method for chemical fabrication of noble metal SERS arrays with surface immobilized layers which can protect protein native conformation without excessively mitigating the electromagnetic enhancements of spectra. Peptide analytes are used as model systems for proteins. Raman spectra of alpha lactalbumin on surfaces and when immobilized on these novel arrays are compared. We discuss the ability of the surface layer to protect protein structure whilst improving signal intensity.

The characterization of photographic materials as substrates for surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Vaughan, J.; Hortin, N.; Christie, S.; Kvasnik, F.; Scully, P. J.

2005-06-01

In this study, five types of photographic materials were obtained from commercial sources and characterized for use as substrates for surface enhanced Raman spectroscopy. The substrates are photographic emulsions coated on glass or paper support. The emulsions were developed to maximize the amount of metallic silver aggregated into clusters. The test analyte, Cresyl Violet, was deposited directly onto the substrate surface. The permeable nature of the supporting gelatin matrix enables the interaction between the target analyte and the solid silver clusters. The surface enhanced Raman spectra of a 2.75 × 10-7 M concentration of Cresyl Violet in ethanol were obtained using these photographic substrates. The Raman and resonant Raman enhancement of Cresyl Violet varies from substrate to substrate, as does the ratio of Raman to resonant Raman peak heights.

Aptamer based surface enhanced Raman scattering detection of vasopressin using multilayer nanotube arrays

PubMed Central

Huh, Yun Suk; Erickson, David

2009-01-01

Here we present an optofluidic surface enhanced Raman spectroscopy (SERS) device for on-chip detection of vasopressin using an aptamer based binding assay. To create the SERS-active substrate, densely packed, 200 nm diameter, metal nanotube arrays were fabricated using an anodized alumina nanoporous membrane as a template for shadow evaporation. We explore the use of both single layer Au structures and multilayer Au/Ag/Au structures and also demonstrate a facile technique for integrating the membranes with all polydimethylsiloxane (PDMS) microfluidic devices. Using the integrated device, we demonstrate a linear response in the main detection peak intensity to solution phase concentration and a limit of detection on the order of 5.2 μU/mL. This low limit of detection is obtained with device containing the multilayer SERS substrate which we show exhibits a stronger Raman enhancement while maintaining biocompatibility and ease or surface reactivity with the capture probe. PMID:19857952

Application of silver nanoparticles in the detection of SYBR Green I by surface enhanced Raman and surface-enhanced fluorescence

NASA Astrophysics Data System (ADS)

Guo, Wei; Wu, Jian; Wang, Chunyan; Zhang, Tian; Chen, Tao

2018-05-01

Silver nanomaterials have remarkable application in biomedical detection due to their unique surface plasmon resonance (SPR) characteristics. It can be used for surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). Current research elaborates a technique for improvement of SYBR Green I detection obtained from surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) by silver nanoparticles with the average size about 70 nm. Primarily, SYBR Green I is an important fluorescent dye used in polymerase chain reaction (PCR). It is found that both Raman and fluorescence can be used for detection of this dye. Furthermore, the enhanced efficiency of the Raman and fluorescence by SERS and SEF is observed in this study, the enhancement factor for Raman signals is 3.2 × 103, and the fluorescence intensity bincreased two times by SEF. The quantitative detection of SYBR Green I by SERS and SEF can be achieved. The present work can be used to improve the detection of SYBR Green I by SERS and SEF. It would also be employed for high-sensitive detection of other materials in the future.

Electrostatic interaction based approach to thrombin detection by surface-enhanced Raman spectroscopy.

PubMed

Hu, Juan; Zheng, Peng-Cheng; Jiang, Jian-Hui; Shen, Guo-Li; Yu, Ru-Qin; Liu, Guo-Kun

2009-01-01

We have developed an electrostatic interaction based biosensor for thrombin detection using surface-enhanced Raman spectroscopy (SERS). This method utilized the electrostatic interaction between capture (thrombin aptamer) and probe (crystal violet, CV) molecules. The specific interaction between thrombin and aptamer could weaken the electrostatic barrier effect from the negative charged aptamer SAMs to the diffusion process of the positively charged CV from the bulk solution to the Au nanoparticle surface. Therefore, the more the bound thrombin, the more the CV molecules near the Au nanoparticle surface and the stronger the observed Raman signal of CV, provided the Raman detections were set at the same time point for each case. This procedure presented a highly specific selectivity and a linear detection of thrombin in the range from 0.1 nM to 10 nM with a detection limit of about 20 pM and realized the thrombin detection in human blood serum solution directly. The electrostatic interaction based technique provides an easy and fast-responding optical platform for a "signal-on" detection of proteins, which might be applicable for the real time assay of proteins.

Enhanced Raman scattering of graphene by silver nanoparticles with different densities and locations

NASA Astrophysics Data System (ADS)

Sun, Hai-Bin; Fu, Can; Xia, Yan-Jie; Zhang, Chong-Wu; Du, Jiang-Hui; Yang, Wen-Chao; Guo, Peng-Fei; Xu, Jun-Qi; Wang, Chun-Lei; Jia, Yong-Lei; Liu, Jiang-Feng

2017-02-01

Graphene-metal nanoparticle heterojunctions greatly improve the surface-enhanced Raman scattering (SERS) by strong light-graphene interactions. In this work, to enhance the Raman scattering, Ag nanoparticles (NPs) underneath and on top of the graphene were used. Then, Raman scattering of graphene is significantly enhanced approximately 67-fold, and the enhancement factor of the graphene G peak increases with the Ag NP density at the same location. In addition, an obvious red-shift and broadening of the resonance peak of Ag NPs is presented, which may be correlated to the strength of Raman enhancement, the coupling of the deposited Ag NPs and the graphene. Further, graphene-Ag NP heterojunctions can be used as SERS substrates to obtain the strongest Raman signals of the rhodamine (R6G) molecules and the weakest photoluminescence (PL) background from the Ag NPs. Based on the tunable Raman enhancement, graphene-Ag NPs offer a promising platform for engineering SERS substrates to obtain highly sensitive detection of trace levels of analyte molecules.

Scanning angle Raman spectroscopy: Investigation of Raman scatter enhancement techniques for chemical analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Matthew W.

2013-01-01

This thesis outlines advancements in Raman scatter enhancement techniques by applying evanescent fields, standing-waves (waveguides) and surface enhancements to increase the generated mean square electric field, which is directly related to the intensity of Raman scattering. These techniques are accomplished by employing scanning angle Raman spectroscopy and surface enhanced Raman spectroscopy. A 1064 nm multichannel Raman spectrometer is discussed for chemical analysis of lignin. Extending dispersive multichannel Raman spectroscopy to 1064 nm reduces the fluorescence interference that can mask the weaker Raman scattering. Overall, these techniques help address the major obstacles in Raman spectroscopy for chemical analysis, which include themore » inherently weak Raman cross section and susceptibility to fluorescence interference.« less

Ag-ZnO nanostructure for ANTA explosive molecule detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaik, Ummar Pasha; Sangani, L. D. Varma; Gaur, Anshu

2016-05-23

Ag/ZnO nanostructure for surface enhanced Raman scattering application in the detection of ANTA explosive molecule is demonstrated. A highly rough ZnO microstructure was achieved by rapid thermal annealing of metallic Zn film. Different thickness Ag nanostructures are decorated over these ZnO microstructures by ion beam sputtering technique. Surface enhanced Raman spectroscopic studies carried out over Ag/ZnO substrates have shown three orders higher enhancement compared to bare Ag nanostructure deposited on the same substrate. The reasons behind such huge enhancement are discussed based on the morphology of the sample.

SRS in the single molecule limit (Conference Presentation)

NASA Astrophysics Data System (ADS)

Potma, Eric O.; Crampton, Kevin T.; Fast, Alexander; Apkarian, Vartkess A.

2017-02-01

We present combined surface-enhanced stimulated Raman scattering (SE-SRS) and surface-enhanced coherent anti-Stokes Raman scattering (SE-CARS) measurements on individual plasmonic antennas dressed with bipyridyl-ethylene molecules. By carefully optimizing the conditions for performing SE-SRS experiments, we have obtained stable and reproducible molecular surface-enhanced SRS spectra from single nano-antennas. Using surface-enhanced Raman scattering (SERS) and transmission electron microscopy of the same antennas, we confirm that the observed SE-SRS signals originate from only one or a few molecules. We highlight the physics of surface enhancement in the context of coherent Raman scattering and derive sensitivity parameters under the relevant conditions. The implications of single molecule SRS measurements are discussed.

JPRS Report, Science & Technology, Japan, 4th International Conference on Langmuir-Blodgett Films

DTIC Science & Technology

1989-08-23

Toshiba-cho, Saiwai-ku, Kawasaki, 210 Japan Surface enhanced resonance Raman scattering (SERRS) from a Langmuir-Blodgett monolayer of 4’-n...4000 cm" . These results show that the spectra are affected by the enhancement due to resonance Raman scattering . The dependence of SERRS intensity...enhanced adsorption is one of the surface enhanced processes such as the surface enhanced Raman scattering (SERS) and the enhanced fluorescence. There

Bare and protected sputtered-noble-metal films for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Talaga, David; Bonhommeau, Sébastien

2014-11-01

Sputtered silver and gold films with different surface morphologies have been prepared and coated with a benzenethiol self-assembled monolayer. Rough noble metal films showed strong Raman features assigned to adsorbed benzenethiol molecules upon irradiation over a wide energy range in the visible spectrum, which disclosed the occurrence of a significant surface-enhanced Raman scattering with maximal enhancement factors as high as 6 × 106. In addition, the adsorption of ethanethiol onto silver surfaces hinders their corrosion over days while preserving mostly intact enhancement properties of naked silver. This study may be applied to develop stable and efficient metalized probes for tip-enhanced Raman spectroscopy.

Effect of concentration and pH on the surface-enhanced Raman scattering of captopril on nano-colloidal silver surface

NASA Astrophysics Data System (ADS)

Gao, Junxiang; Gu, Huaimin; Liu, Fangfang; Dong, Xiao; Xie, Min; Hu, Yongjun

2011-07-01

In this report, Raman and surface-enhanced Raman scattering (SERS) spectra of captopril are studied in detail. Herein, the Raman bands are assigned by the density functional theory (DFT) calculations and potential energy distributions (PED) based on internal coordinates of the molecule, which are found to be in good agree with the experimental values. Furthermore, the concentration and pH dependence of the SERS intensity of the molecule is discussed. By analyzing the intensities variation of SERS bands of the different concentrations of captopril solution, it can be concluded that the molecules orientation adsorbed on the silver nanoparticles surface change with the change of the concentrations. The variation of SERS spectra of captopril with the change of pH suggests that the interaction among the adsorbates with Ag cluster depend on the protonated state of the adsorbate and the aggregation of silver nanoparticles.

Proximity-dependent isothermal cycle amplification for small-molecule detection based on surface enhanced Raman scattering.

PubMed

Li, Ying; Zeng, Yan; Mao, Yaning; Lei, Chengcun; Zhang, Shusheng

2014-01-15

A novel proximity-dependent isothermal cycle amplification (PDICA) strategy has been proposed and successfully used for the determination of cocaine coupled with surface enhanced Raman scattering (SERS). For enhancing the SERS signal, Raman dye molecules modified bio-barcode DNA and gold nanoparticles (AuNPs) are used to prepare the Raman probes. Magnetic beads (MBs) are used as the carrier of amplification template and signal output products for circumventing the problem of high background induced by excess bio-barcode DNA. In the presence of target molecules, two label-free proximity probes can hybridize with each other and subsequently opens the hairpin connector-probe to perform the PDICA reaction including the target recycling amplification and strand-displacement amplification. As a result, abundant AuNPs Raman probes can be anchored on the surface of MBs and a low detection limit of 0.1 nM for cocaine is obtained. This assay also exhibits an excellent selectivity and has been successfully performed in human serum, which confirms the reliability and practicality of this protocol. © 2013 Elsevier B.V. All rights reserved.

Surface-enhanced Raman scattering on tunable plasmonic nanoparticle substrates

PubMed Central

Jackson, J. B.; Halas, N. J.

2004-01-01

Au and Ag nanoshells are investigated as substrates for surface-enhanced Raman scattering (SERS). We find that SERS enhancements on nanoshell films are dramatically different from those observed on colloidal aggregates, specifically that the Raman enhancement follows the plasmon resonance of the individual nanoparticles. Comparative finite difference time domain calculations of fields at the surface of smooth and roughened nanoshells reveal that surface roughness contributes only slightly to the total enhancement. SERS enhancements as large as 2.5 × 1010 on Ag nanoshell films for the nonresonant molecule p-mercaptoaniline are measured. PMID:15608058

Bio-sensing with butterfly wings: naturally occurring nano-structures for SERS-based malaria parasite detection.

PubMed

Garrett, Natalie L; Sekine, Ryo; Dixon, Matthew W A; Tilley, Leann; Bambery, Keith R; Wood, Bayden R

2015-09-07

Surface enhanced Raman scattering (SERS) is a powerful tool with great potential to provide improved bio-sensing capabilities. The current 'gold-standard' method for diagnosis of malaria involves visual inspection of blood smears using light microscopy, which is time consuming and can prevent early diagnosis of the disease. We present a novel surface-enhanced Raman spectroscopy substrate based on gold-coated butterfly wings, which enabled detection of malarial hemozoin pigment within lysed blood samples containing 0.005% and 0.0005% infected red blood cells.

Increasing surface enhanced Raman spectroscopy effect of RNA and DNA components by changing the pH of silver colloidal suspensions.

PubMed

Primera-Pedrozo, Oliva M; Rodríguez, Gabriela Del Mar; Castellanos, Jorge; Felix-Rivera, Hilsamar; Resto, Oscar; Hernández-Rivera, Samuel P

2012-02-15

This work focused on establishing the parameters for enhancing the Raman signals of DNA and RNA constituents: nitrogenous bases, nucleosides and nucleotides, using metallic nanoparticles as surface enhanced Raman scattering substrates. Silver nanospheres were synthesized using sodium borohydride as a reducing agent and sodium citrate as a capping agent. The prepared nanoparticles had a surface plasmon band at ∼384nm and an average size of 12±3nm. The nanoparticles' surface charge was manipulated by changing the pH of the Ag colloidal suspensions in the range of 1-13. Low concentrations as 0.7μM were detected under the experimental conditions. The optimum pH values were: 7 for adenine, 9 for AMP, 5 for adenosine, 7 for dAMP and 11 for deoxyadenosine. Copyright © 2011 Elsevier B.V. All rights reserved.

Ultrafast and nonlinear surface-enhanced Raman spectroscopy.

PubMed

Gruenke, Natalie L; Cardinal, M Fernanda; McAnally, Michael O; Frontiera, Renee R; Schatz, George C; Van Duyne, Richard P

2016-04-21

Ultrafast surface-enhanced Raman spectroscopy (SERS) has the potential to study molecular dynamics near plasmonic surfaces to better understand plasmon-mediated chemical reactions such as plasmonically-enhanced photocatalytic or photovoltaic processes. This review discusses the combination of ultrafast Raman spectroscopic techniques with plasmonic substrates for high temporal resolution, high sensitivity, and high spatial resolution vibrational spectroscopy. First, we introduce background information relevant to ultrafast SERS: the mechanisms of surface enhancement in Raman scattering, the characterization of plasmonic materials with ultrafast techniques, and early complementary techniques to study molecule-plasmon interactions. We then discuss recent advances in surface-enhanced Raman spectroscopies with ultrafast pulses with a focus on the study of molecule-plasmon coupling and molecular dynamics with high sensitivity. We also highlight the challenges faced by this field by the potential damage caused by concentrated, highly energetic pulsed fields in plasmonic hotspots, and finally the potential for future ultrafast SERS studies.

Silver nanoparticle based surface enhanced Raman scattering spectroscopy of diabetic and normal rat pancreatic tissue under near-infrared laser excitation

NASA Astrophysics Data System (ADS)

Huang, H.; Shi, H.; Feng, S.; Lin, J.; Chen, W.; Huang, Z.; Li, Y.; Yu, Y.; Lin, D.; Xu, Q.; Chen, R.

2013-04-01

This paper presents the use of high spatial resolution silver nanoparticle based near-infrared surface enhanced Raman scattering (SERS) from rat pancreatic tissue to obtain biochrmical information about the tissue. A high quality SERS signal from a mixture of pancreatic tissues and silver nanoparticles can be obtained within 10 s using a Renishaw micro-Raman system. Prominent SERS bands of pancreatic tissue were assigned to known molecular vibrations, such as the vibrations of DNA bases, RNA bases, proteins and lipids. Different tissue structures of diabetic and normal rat pancreatic tissues have characteristic features in SERS spectra. This exploratory study demonstrated great potential for using SERS imaging to distinguish diabetic and normal pancreatic tissues on frozen sections without using dye labeling of functionalized binding sites.

The synthesis of four-layer gold-silver-polymer-silver core-shell nanomushroom with inbuilt Raman molecule for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Jiang, Tao; Wang, Xiaolong; Zhou, Jun

2017-12-01

A facial two-step reduction method was proposed to synthesize four-layer gold-silver-polymer-silver (Au@Ag@PSPAA@Ag) core-shell nanomushrooms (NMs) with inbuilt Raman molecule. The surface-enhanced Raman scattering (SERS) intensity of 4MBA adhered on the surface of Au core gradually increased with the modification of middle Ag shell and then Ag mushroom cap due to the formation of two kinds of ultra-small interior nanogap. Compared with the initial Au nanoparticles, the SERS enhancement ratio of the Au@Ag@PSPAA@Ag NMs approached to nearly 40. The novel core-shell NMs also exhibited homogeneous SERS signals for only one sample and reproducible signals for 10 different samples, certified by the low relative standard deviation values of less than 10% and 15% for the character peaks of 4-mercaptobenzoic acid, respectively. Such a novel four-layer core-shell nanostructure with reliable SERS performance has great potential application in quantitative SERS-based immunoassay.

Electride Mediated Surface Enhanced Raman Scattering (SERS)

NASA Technical Reports Server (NTRS)

Anderson, Mark S. (Inventor)

2016-01-01

An electride may provide surface enhanced Raman scattering (SERS). The electride, a compound where the electrons serve as anions, may be a ceramic electride, such as a conductive ceramic derived from mayenite, or an organic electride, for example. The textured electride surface or electride particles may strongly enhance the Raman scattering of organic or other Raman active analytes. This may also provide a sensitive method for monitoring the chemistry and electronic environment at the electride surface. The results are evidence of a new class of polariton (i.e., a surface electride-polariton resonance mechanism) that is analogous to the surface plasmon-polariton resonance that mediates conventional SERS.

Surface-enhanced Raman spectroscopy on coupled two-layer nanorings

NASA Astrophysics Data System (ADS)

Hou, Yumin; Xu, Jun; Wang, Pengwei; Yu, Dapeng

2010-05-01

A reproducible quasi-three-dimensional structure, composed of top and bottom concentric nanorings with same periodicity but different widths and no overlapping at the perpendicular direction, is built up by a separation-layer method, which results in huge enhancement of surface-enhanced Raman spectroscopy (SERS) due to the coupling of plasmons. Simulations show plasmonic focusing with "hot arcs" of electromagnetic enhancement meeting the need of quantitative SERS with extremely high sensitivities. In addition, the separation-layer method opens a simple and effective way to adjust the coupling of plasmons among nanostructures which is essential for the fabrication of SERS-based sensors.

Fructose and Pectin Detection in Fruit-Based Food Products by Surface-Enhanced Raman Spectroscopy

PubMed Central

Camerlingo, Carlo; Portaccio, Marianna; Tatè, Rosarita; Lepore, Maria; Delfino, Ines

2017-01-01

Surface-Enhanced Raman Spectroscopy (SERS) enables the investigation of samples with weak specific Raman signals, such as opaque samples, including fruit juices and pulp. In this paper, biological apple juices and apple/pear pulp have been studied in order to evidence the presence of fructose and pectin, which are components of great relevance for quality assessment of these kinds of products. In order to perform SERS measurements a low-cost home-made substrate consisting of a glass slide decorated with 30-nm-sized gold nanoparticles has been designed and used. By employing a conventional micro-Raman spectroscopy set-up and a suitable data treatment based on “wavelet” denoising algorithms and background subtraction, spectra of pectin and fructose with clear Raman features have been obtained. The results have confirmed the potential of SERS in the food industry for product characterization, also considering the low-cost and the relative ease of the fabrication process of the employed SERS substrate. PMID:28398254

Aggregated silver nanoparticles based surface-enhanced Raman scattering enzyme-linked immunosorbent assay for ultrasensitive detection of protein biomarkers and small molecules.

PubMed

Liang, Jiajie; Liu, Hongwu; Huang, Caihong; Yao, Cuize; Fu, Qiangqiang; Li, Xiuqing; Cao, Donglin; Luo, Zhi; Tang, Yong

2015-06-02

Lowering the detection limit is critical to the design of bioassays required for medical diagnostics, environmental monitoring, and food safety regulations. The current sensitivity of standard color-based analyte detection limits the further use of enzyme-linked immunosorbent assays (ELISAs) in research and clinical diagnoses. Here, we demonstrate a novel method that uses the Raman signal as the signal-generating system of an ELISA and combines surface-enhanced Raman scattering (SERS) with silver nanoparticles aggregation for ultrasensitive analyte detection. The enzyme label of the ELISA controls the dissolution of Raman reporter-labeled silver nanoparticles through hydrogen peroxide and generates a strong Raman signal when the analyte is present. Using this assay, prostate-specific antigen (PSA) and the adrenal stimulant ractopamine (Rac) were detected in whole serum and urine at the ultralow concentrations of 10(-9) and 10(-6) ng/mL, respectively. The methodology proposed here could potentially be applied to other molecules detection as well as PSA and Rac.

Adenosine Triphosphate-Encapsulated Liposomes with Plasmonic Nanoparticles for Surface Enhanced Raman Scattering-Based Immunoassays.

PubMed

Pham, Xuan-Hung; Hahm, Eunil; Kim, Tae Han; Kim, Hyung-Mo; Lee, Sang Hun; Lee, Yoon-Sik; Jeong, Dae Hong; Jun, Bong-Hyun

2017-06-23

In this study, we prepared adenosine triphosphate (ATP) encapsulated liposomes, and assessed their applicability for the surface enhanced Raman scattering (SERS)-based assays with gold-silver alloy (Au@Ag)-assembled silica nanoparticles (NPs; SiO₂@Au@Ag). The liposomes were prepared by the thin film hydration method from a mixture of l-α-phosphatidylcholine, cholesterol, and PE-PEG2000 in chloroform; evaporating the solvent, followed by hydration of the resulting thin film with ATP in phosphate-buffered saline (PBS). Upon lysis of the liposome, the SERS intensity of the SiO₂@Au@Ag NPs increased with the logarithm of number of ATP-encapsulated liposomes after lysis in the range of 8 × 10⁶ to 8 × 10 10 . The detection limit of liposome was calculated to be 1.3 × 10 -17 mol. The successful application of ATP-encapsulated liposomes to SiO₂@Au@Ag NPs based SERS analysis has opened a new avenue for Raman label chemical (RCL)-encapsulated liposome-enhanced SERS-based immunoassays.

A simple way to synthesize large-scale Cu2O/Ag nanoflowers for ultrasensitive surface-enhanced Raman scattering detection

NASA Astrophysics Data System (ADS)

Zou, Junyan; Song, Weijia; Xie, Weiguang; Huang, Bo; Yang, Huidong; Luo, Zhi

2018-03-01

Here, we report a simple strategy to prepare highly sensitive surface-enhanced Raman spectroscopy (SERS) substrates based on Ag decorated Cu2O nanoparticles by combining two common techniques, viz, thermal oxidation growth of Cu2O nanoparticles and magnetron sputtering fabrication of a Ag nanoparticle film. Methylene blue is used as the Raman analyte for the SERS study, and the substrates fabricated under optimized conditions have very good sensitivity (analytical enhancement factor ˜108), stability, and reproducibility. A linear dependence of the SERS intensities with the concentration was obtained with an R 2 value >0.9. These excellent properties indicate that the substrate has great potential in the detection of biological and chemical substances.

Surface-enhanced Raman spectroscopy of genomic DNA from in vitro grown tomato (Lycopersicon esculentum Mill.) cultivars before and after plant cryopreservation.

PubMed

Muntean, Cristina M; Leopold, Nicolae; Tripon, Carmen; Coste, Ana; Halmagyi, Adela

2015-06-05

In this work the surface-enhanced Raman scattering (SERS) spectra of five genomic DNAs from non-cryopreserved control tomato plants (Lycopersicon esculentum Mill. cultivars Siriana, Darsirius, Kristin, Pontica and Capriciu) respectively, have been analyzed in the wavenumber range 400-1800 cm(-1). Structural changes induced in genomic DNAs upon cryopreservation were discussed in detail for four of the above mentioned tomato cultivars. The surface-enhanced Raman vibrational modes for each of these cases, spectroscopic band assignments and structural interpretations of genomic DNAs are reported. We have found, that DNA isolated from Siriana cultivar leaf tissues suffers the weakest structural changes upon cryogenic storage of tomato shoot apices. On the contrary, genomic DNA extracted from Pontica cultivar is the most responsive system to cryopreservation process. Particularly, both C2'-endo-anti and C3'-endo-anti conformations have been detected. As a general observation, the wavenumber range 1511-1652 cm(-1), being due to dA, dG and dT residues seems to be influenced by cryopreservation process. These changes could reflect unstacking of DNA bases. However, not significant structural changes of genomic DNAs from Siriana, Darsirius and Kristin have been found upon cryopreservation process of tomato cultivars. Based on this work, specific plant DNA-ligand interactions or accurate local structure of DNA in the proximity of a metallic surface, might be further investigated using surface-enhanced Raman spectroscopy. Copyright © 2015 Elsevier B.V. All rights reserved.

Surface-enhanced Raman spectroscopy of genomic DNA from in vitro grown tomato (Lycopersicon esculentum Mill.) cultivars before and after plant cryopreservation

NASA Astrophysics Data System (ADS)

Muntean, Cristina M.; Leopold, Nicolae; Tripon, Carmen; Coste, Ana; Halmagyi, Adela

2015-06-01

In this work the surface-enhanced Raman scattering (SERS) spectra of five genomic DNAs from non-cryopreserved control tomato plants (Lycopersicon esculentum Mill. cultivars Siriana, Darsirius, Kristin, Pontica and Capriciu) respectively, have been analyzed in the wavenumber range 400-1800 cm-1. Structural changes induced in genomic DNAs upon cryopreservation were discussed in detail for four of the above mentioned tomato cultivars. The surface-enhanced Raman vibrational modes for each of these cases, spectroscopic band assignments and structural interpretations of genomic DNAs are reported. We have found, that DNA isolated from Siriana cultivar leaf tissues suffers the weakest structural changes upon cryogenic storage of tomato shoot apices. On the contrary, genomic DNA extracted from Pontica cultivar is the most responsive system to cryopreservation process. Particularly, both C2‧-endo-anti and C3'-endo-anti conformations have been detected. As a general observation, the wavenumber range 1511-1652 cm-1, being due to dA, dG and dT residues seems to be influenced by cryopreservation process. These changes could reflect unstacking of DNA bases. However, not significant structural changes of genomic DNAs from Siriana, Darsirius and Kristin have been found upon cryopreservation process of tomato cultivars. Based on this work, specific plant DNA-ligand interactions or accurate local structure of DNA in the proximity of a metallic surface, might be further investigated using surface-enhanced Raman spectroscopy.

Two-Dimensional Heterostructure as a Platform for Surface-Enhanced Raman Scattering.

PubMed

Tan, Yang; Ma, Linan; Gao, Zhibin; Chen, Ming; Chen, Feng

2017-04-12

Raman enhancement on a flat nonmetallic surface has attracted increasing attention, ever since the discovery of graphene enhanced Raman scattering. Recently, diverse two-dimensional layered materials have been applied as a flat surface for the Raman enhancement, attributed to different mechanisms. Looking beyond these isolated materials, atomic layers can be reassembled to design a heterostructure stacked layer by layer with an arbitrary chosen sequence, which allows the flow of charge carriers between neighboring layers and offers novel functionalities. Here, we demonstrate the heterostructure as a novel Raman enhancement platform. The WSe 2 (W) monolayer and graphene (G) were stacked together to form a heterostructure with an area of 10 mm × 10 mm. Heterostructures with different stacked structuress are used as platforms for the enhanced Raman scattering, including G/W, W/G, G/W/G/W, and W/G/G/W. On the surface of the heterostructure, the intensity of the Raman scattering is much stronger compared with isolated layers, using the copper phthalocyanine (CuPc) molecule as a probe. It is found that the Raman enhancement effect on heterostructures depends on stacked methods. Phonon modes of CuPc have the strongest enhancement on G/W. W/G and W/G/G/W have a stronger enhancement than that on the isolated WSe 2 monolayer, while lower than the graphene monolayer. The G/W/G/W/substrate demonstrated a comparable Raman enhancement effect than the G/W/substrate. These differences are due to the different interlayer couplings in heterostructures related to electron transition probability rates, which are further proved by first-principle calculations and probe-pump measurements.

Surface Plasmon-Coupled Directional Enhanced Raman Scattering by Means of the Reverse Kretschmann Configuration.

PubMed

Huo, Si-Xin; Liu, Qian; Cao, Shuo-Hui; Cai, Wei-Peng; Meng, Ling-Yan; Xie, Kai-Xin; Zhai, Yan-Yun; Zong, Cheng; Yang, Zhi-Lin; Ren, Bin; Li, Yao-Qun

2015-06-04

Surface-enhanced Raman scattering (SERS) is a unique analytical technique that provides fingerprint spectra, yet facing the obstacle of low collection efficiency. In this study, we demonstrated a simple approach to measure surface plasmon-coupled directional enhanced Raman scattering by means of the reverse Kretschmann configuration (RK-SPCR). Highly directional and p-polarized Raman scattering of 4-aminothiophenol (4-ATP) was observed on a nanoparticle-on-film substrate at 46° through the prism coupler with a sharp angle distribution (full width at half-maximum of ∼3.3°). Because of the improved collection efficiency, the Raman scattering signal was enhanced 30-fold over the conventional SERS mode; this was consistent with finite-difference time-domain simulations. The effect of nanoparticles on the coupling efficiency of propagated surface plasmons was investigated. Possessing straightforward implementation and directional enhancement of Raman scattering, RK-SPCR is anticipated to simplify SERS instruments and to be broadly applicable to biochemical assays.

Highly sensitive surface-enhanced Raman scattering substrate made from superaligned carbon nanotubes.

PubMed

Sun, Yinghui; Liu, Kai; Miao, Jiao; Wang, Zheyao; Tian, Baozhong; Zhang, Lina; Li, Qunqing; Fan, Shoushan; Jiang, Kaili

2010-05-12

Surface-enhanced Raman scattering (SERS) has attracted wide attention because it can enhance normally weak Raman signal by several orders of magnitude and facilitate the sensitive detection of molecules. Conventional SERS substrates are constructed by placing metal nanoparticles on a planar surface. Here we show that, if the planar surface was substituted by a unique nanoporous surface, the enhancement effect can be dramatically improved. The nanoporous surface can be easily fabricated in batches and at low costs by cross stacking superaligned carbon nanotube films. The as-prepared transparent and freestanding SERS substrate is capable of detecting ambient trinitrotoluene vapor, showing much higher Raman enhancement than ordinary planar substrates because of the extremely large surface area and the unique zero-dimensional at one-dimensional nanostructure. These results not only provide a new approach to ultrasensitive SERS substrates, but also are helpful for improving the fundamental understanding of SERS phenomena.

Surface-enhanced Raman scattering (SERS) dosimeter and probe

DOEpatents

Vo-Dinh, Tuan

1995-01-01

A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devises, in probe array devices.

A gold nanohole array based surface-enhanced Raman scattering biosensor for detection of silver(I) and mercury(II) in human saliva†

PubMed Central

Zheng, Peng; Li, Ming; Jurevic, Richard; Cushing, Scott K.; Liu, Yuxin

2015-01-01

A surface-enhanced Raman scattering (SERS) biosensor has been developed by incorporating a gold nanohole array with a SERS probe (a gold nanostar@Raman-reporter@silica sandwich structure) into a single detection platform via DNA hybridization, which circumvents the nanoparticle aggregation and the inefficient Raman scattering issues. Strong plasmonic coupling between the Au nanostar and the Au nanohole array results in a large enhancement of the electromagnetic field, leading to amplification of the SERS signal. The SERS sensor has been used to detect Ag(i) and Hg(ii) ions in human saliva because both the metal ions could be released from dental amalgam fillings. The developed SERS sensor can be adapted as a general detection platform for non-invasive measurements of a wide range of analytes such as metal ions, small molecules, DNA and proteins in body fluids. PMID:26008641

Implementation of molecularly imprinted polymer beads for surface enhanced Raman detection.

PubMed

Kamra, Tripta; Zhou, Tongchang; Montelius, Lars; Schnadt, Joachim; Ye, Lei

2015-01-01

Molecularly imprinted polymers (MIPs) have a predesigned molecular recognition capability that can be used to build robust chemical sensors. MIP-based chemical sensors allow label-free detection and are particularly interesting due to their simple operation. In this work we report the use of thiol-terminated MIP microspheres to construct surfaces for detection of a model organic analyte, nicotine, by surface enhanced Raman scattering (SERS). The nicotine-imprinted microspheres are synthesized by RAFT precipitation polymerization and converted into thiol-terminated microspheres through aminolysis. The thiol groups on the MIP surface allow the microspheres to be immobilized on a gold-coated substrate. Three different strategies are investigated to achieve surface enhanced Raman scattering in the vicinity of the imprinted sites: (1) direct sputtering of gold nanoparticles, (2) immobilization of gold colloids through the MIP's thiol groups, and (3) trapping of the MIP microspheres in a patterned SERS substrate. For the first time we show that large MIP microspheres can be turned into selective SERS surfaces through the three different approaches of assembly. The MIP-based sensing surfaces are used to detect nicotine to demonstrate the proof of concept. As synthesis and surface functionalization of MIP microspheres and nanoparticles are well established, the methods reported in this work are handy and efficient for constructing label-free chemical sensors, in particular for those based on SERS detection.

[Surface-enhanced raman spectra studies on roughened Zn electrode in alkaline solutions].

PubMed

Shen, Xiao-ying; Liu, Guo-kun; Gu, Ren-ao; Tian, Zhong-qun

2005-09-01

Electrochemical oxidation-reduction method was employed to roughen Zn electrode for obtaining SERS, and potential dependent surface enhanced Raman spectra (SERS) of roughened Zn electrode in KOH solution of different concentration wereobserved. The spectra of Zn electrode in various solutions had obvious differences which indicated the concentration of OH- had a great effect on the dissolution and passivation of zinc. Based on our experimental results, the authors attempt to analyse the behavior of zinc in alkaline and give the mechanism of its passivation.

Comparison of time-gated surface-enhanced Raman spectroscopy (TG-SERS) and classical SERS based monitoring of Escherichia coli cultivation samples.

PubMed

Kögler, Martin; Paul, Andrea; Anane, Emmanuel; Birkholz, Mario; Bunker, Alex; Viitala, Tapani; Maiwald, Michael; Junne, Stefan; Neubauer, Peter

2018-06-08

The application of Raman spectroscopy as a monitoring technique for bioprocesses is severely limited by a large background signal originating from fluorescing compounds in the culture media. Here we compare time-gated Raman (TG-Raman)-, continuous wave NIR-process Raman (NIR-Raman) and continuous wave micro-Raman (micro-Raman) approaches in combination with surface enhanced Raman spectroscopy (SERS) for their potential to overcome this limit. For that purpose, we monitored metabolite concentrations of Escherichia coli bioreactor cultivations in cell-free supernatant samples. We investigated concentration transients of glucose, acetate, AMP and cAMP at alternating substrate availability, from deficiency to excess. Raman and SERS signals were compared to off-line metabolite analysis of carbohydrates, carboxylic acids and nucleotides. Results demonstrate that SERS, in almost all cases, led to a higher number of identifiable signals and better resolved spectra. Spectra derived from the TG-Raman were comparable to those of micro-Raman resulting in well-discernable Raman peaks, which allowed for the identification of a higher number of compounds. In contrast, NIR-Raman provided a superior performance for the quantitative evaluation of analytes, both with and without SERS nanoparticles when using multivariate data analysis. This article is protected by copyright. All rights reserved. © 2018 American Institute of Chemical Engineers.

Raman Imaging in Cell Membranes, Lipid-Rich Organelles, and Lipid Bilayers.

PubMed

Syed, Aleem; Smith, Emily A

2017-06-12

Raman-based optical imaging is a promising analytical tool for noninvasive, label-free chemical imaging of lipid bilayers and cellular membranes. Imaging using spontaneous Raman scattering suffers from a low intensity that hinders its use in some cellular applications. However, developments in coherent Raman imaging, surface-enhanced Raman imaging, and tip-enhanced Raman imaging have enabled video-rate imaging, excellent detection limits, and nanometer spatial resolution, respectively. After a brief introduction to these commonly used Raman imaging techniques for cell membrane studies, this review discusses selected applications of these modalities for chemical imaging of membrane proteins and lipids. Finally, recent developments in chemical tags for Raman imaging and their applications in the analysis of selected cell membrane components are summarized. Ongoing developments toward improving the temporal and spatial resolution of Raman imaging and small-molecule tags with strong Raman scattering cross sections continue to expand the utility of Raman imaging for diverse cell membrane studies.

Surface-enhanced hyper-Raman spectroscopy with a picosecond laser: gold and copper colloids

NASA Astrophysics Data System (ADS)

Lipscomb, Leigh Ann; Nie, Shuming; Feng, Sibo; Yu, Nai-Teng

1990-07-01

We have obtained surface-enhanced hyper-Raman scattering (SEHRS) spectra of crystal violet, rhodamine 6G and Ru(trpy) (BPE) 32+ adsorbed on gold and copper colloidal surfaces (where trpy=2,2',2″-terpyridine, BPE=trans-bis(4-pyridyl)ethylene). Our results demonstrate that the SEHRS effect is not intrinsically restricted to a Ag substrate and that surface enhancements at the emitted hyper-Raman photon frequencies are not required for observing SEHRS signals.

Raman Spectroscopy.

ERIC Educational Resources Information Center

Gerrard, Donald L.

1984-01-01

Reviews literature on Raman spectroscopy from late 1981 to late 1983. Topic areas include: instrumentation and sampling; liquids and solutions; gases and matrix isolation; biological molecules; polymers; high-temperature and high-pressure studies; Raman microscopy; thin films and surfaces; resonance-enhanced and surface-enhanced spectroscopy; and…

Tailored Rh surface facilitates, enhancement of Raman scattering in trimetallic AuPt core/Rh shell composites: Experimental and theoretical evidences

NASA Astrophysics Data System (ADS)

Loganathan, B.; Chandraboss, V. L.; Senthilvelan, S.; Karthikeyan, B.

2016-01-01

We present a detailed analysis of surface-enhanced Raman scattering of 7-azaindole and L-cysteine adsorbed on a tailored Rh surface by using experimental and density functional theoretical (DFT) calculations. DFT with the B3LYP/Lanl2DZ basis set was used for the optimization of the ground state geometries and simulation of the surface-enhanced Raman spectrum of probe molecules adsorbed on Rh6 cluster. 7-azaindole and L-cysteine adsorption at the shell interface was ascertained from first-principles. In addition, characterization of synthesized trimetallic AuPt core/Rh shell colloidal nanocomposites has been analyzed by UV-visible spectroscopy, high-resolution transmission and scanning electron microscopy, selected area electron diffraction pattern analysis, energy-dispersive X-ray spectroscopy, atomic force, confocal Raman microscopy, FT-Raman and surface-enhanced Raman spectroscopic analysis. This analysis serves as the first step in gaining an accurate understanding of specific interactions at the interface of organic and biomolecules and to gain knowledge on the surface composition of trimetallic Au/Pt/Rh colloidal nanocomposites.

Surface-enhanced Raman scattering from graphene covered gold nanocap arrays

NASA Astrophysics Data System (ADS)

Long, Kailin; Luo, Xiaoguang; Nan, Haiyan; Du, Deyang; Zhao, Weiwei; Ni, Zhenhua; Qiu, Teng

2013-11-01

This work reports an efficient method to fabricate large-area flexible substrates for surface enhanced Raman scattering (SERS) application. Our technique is based on a single-step direct imprint process via porous anodic alumina stamps. Periodic hexagonal arrangements of porous anodic alumina stamps are transferred to the polyethylene terephthalate substrates by mechanically printing process. Printed nanocaps will turn into "hot spots" for electromagnetic enhancement with a deposited gold film by high vacuum evaporation. The gaps between the nanocaps are controllable with a tight correspondence to the thickness of the deposited gold, which dramatically influence the enhancement factor. After covered with a single-layer graphene sheet, the gold nanocap substrate can be further optimized with an extra enhancement of Raman signals, and it is available for the trace detection of probe molecules. This convenient, simple, and low-cost method of making flexible SERS-active substrates potentially opens a way towards biochemical analysis and disease detection.

Surface-enhanced Raman scattering (SERS) dosimeter and probe

DOEpatents

Vo-Dinh, T.

1995-03-21

A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devices, in probe array devices. 10 figures.

Surface Plasmon Resonance Sensors on Raman and Fluorescence Spectroscopy

PubMed Central

Wang, Jiangcai; Lin, Weihua; Cao, En; Xu, Xuefeng; Liang, Wenjie; Zhang, Xiaofang

2017-01-01

The performance of chemical reactions has been enhanced immensely with surface plasmon resonance (SPR)-based sensors. In this review, the principle and application of SPR sensors are introduced and summarized thoroughly. We introduce the mechanism of the SPR sensors and present a thorough summary about the optical design, including the substrate and excitation modes of the surface plasmons. Additionally, the applications based on SPR sensors are described by the Raman and fluorescence spectroscopy in plasmon-driven surface catalytic reactions and the measurement of refractive index sensing, especially. PMID:29212139

Plasmonic nanostructures for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Jiang, Ruiqian

In the last three decades, a large number of different plasmonic nanostructures have attracted much attention due to their unique optical properties. Those plasmonic nanostructures include nanoparticles, nanoholes and metal nanovoids. They have been widely utilized in optical devices and sensors. When the plasmonic nanostructures interact with the electromagnetic wave and their surface plasmon frequency match with the light frequency, the electrons in plasmonic nanostructures will resonate with the same oscillation as incident light. In this case, the plasmonic nanostructures can absorb light and enhance the light scattering. Therefore, the plasmonic nanostructures can be used as substrate for surface-enhanced Raman spectroscopy to enhance the Raman signal. Using plasmonic nanostructures can significantly enhance Raman scattering of molecules with very low concentrations. In this thesis, two different plasmonic nanostructures Ag dendrites and Au/Ag core-shell nanoparticles are investigated. Simple methods were used to produce these two plasmonic nanostructures. Then, their applications in surface enhanced Raman scattering have been explored. Ag dendrites were produced by galvanic replacement reaction, which was conducted using Ag nitrate aqueous solution and copper metal. Metal copper layer was deposited at the bottom side of anodic aluminum oxide (AAO) membrane. Silver wires formed inside AAO channels connected Ag nitrate on the top of AAO membrane and copper layer at the bottom side of AAO. Silver dendrites were formed on the top side of AAO. The second plasmonic nanostructure is Au/Ag core-shell nanoparticles. They were fabricated by electroless plating (galvanic replacement) reaction in a silver plating solution. First, electrochemically evolved hydrogen bubbles were used as template through electroless deposition to produce hollow Au nanoparticles. Then, the Au nanoparticles were coated with Cu shells in a Cu plating solution. In the following step, a AgCN based plating solution was used to replace Cu shell to form Au/Ag core-shell nanoparticles. These two plasmonic nanostructures were tested as substrates for Raman spectroscopy. It demonstrated that these plasmonic nanostructures could enhance Raman signal from the molecules on their surface. The results indicate that these plasmonic nanostructures could be utilized in many fields, such as such as biological and environmental sensors.

Surface-enhanced Raman scattering from AgNP-graphene-AgNP sandwiched nanostructures

NASA Astrophysics Data System (ADS)

Wu, Jian; Xu, Yijun; Xu, Pengyu; Pan, Zhenghui; Chen, Sheng; Shen, Qishen; Zhan, Li; Zhang, Yuegang; Ni, Weihai

2015-10-01

We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials.We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials. Electronic supplementary information (ESI) available: Additional SEM images, electric field enhancement profiles, Raman scattering spectra, and structure-dependent peak ratios. See DOI: 10.1039/c5nr04500b

Effect of surface density silver nanoplate films toward surface-enhanced Raman scattering enhancement for bisphenol A detection

NASA Astrophysics Data System (ADS)

Bakar, N. A.; Salleh, M. M.; Umar, A. A.; Shapter, J. G.

2018-03-01

This paper reports a study on surface-enhanced Raman scattering (SERS) phenomenon of triangular silver nanoplate (NP) films towards bisphenol A (BPA) detection. The NP films were prepared using self-assembly technique with four different immersion times; 1 hour, 2 hours, 5 hours, and 8 hours. The SERS measurement was studied by observing the changes in Raman spectra of BPA after BPA absorbed on the NP films. It was found that the Raman intensity of BPA peaks was enhanced by using the prepared SERS substrates. This is clearly indicated that these SERS silver substrates are suitable to sense industrial chemical and potentially used as SERS detector. However, the rate of SERS enhancement is depended on the distribution of NP on the substrate surface.

Wavelength modulated surface enhanced (resonance) Raman scattering for background-free detection.

PubMed

Praveen, Bavishna B; Steuwe, Christian; Mazilu, Michael; Dholakia, Kishan; Mahajan, Sumeet

2013-05-21

Spectra in surface-enhanced Raman scattering (SERS) are always accompanied by a continuum emission called the 'background' which complicates analysis and is especially problematic for quantification and automation. Here, we implement a wavelength modulation technique to eliminate the background in SERS and its resonant version, surface-enhanced resonance Raman scattering (SERRS). This is demonstrated on various nanostructured substrates used for SER(R)S. An enhancement in the signal to noise ratio for the Raman bands of the probe molecules is also observed. This technique helps to improve the analytical ability of SERS by alleviating the problem due to the accompanying background and thus making observations substrate independent.

Label-Free Molecular Imaging of Biological Cells and Tissues by Linear and Nonlinear Raman Spectroscopic Approaches.

PubMed

Krafft, Christoph; Schmitt, Michael; Schie, Iwan W; Cialla-May, Dana; Matthäus, Christian; Bocklitz, Thomas; Popp, Jürgen

2017-04-10

Raman spectroscopy is an emerging technique in bioanalysis and imaging of biomaterials owing to its unique capability of generating spectroscopic fingerprints. Imaging cells and tissues by Raman microspectroscopy represents a nondestructive and label-free approach. All components of cells or tissues contribute to the Raman signals, giving rise to complex spectral signatures. Resonance Raman scattering and surface-enhanced Raman scattering can be used to enhance the signals and reduce the spectral complexity. Raman-active labels can be introduced to increase specificity and multimodality. In addition, nonlinear coherent Raman scattering methods offer higher sensitivities, which enable the rapid imaging of larger sampling areas. Finally, fiber-based imaging techniques pave the way towards in vivo applications of Raman spectroscopy. This Review summarizes the basic principles behind medical Raman imaging and its progress since 2012. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical properties of chitin: surface-enhanced Raman scattering substrates based on antireflection structures on cicada wings

NASA Astrophysics Data System (ADS)

Stoddart, P. R.; Cadusch, P. J.; Boyce, T. M.; Erasmus, R. M.; Comins, J. D.

2006-02-01

The transparent wings of some cicada species present ordered arrays of papillary structures with a spacing of approximately 200 nm. These structures serve an antireflection function, with optical transmission peaking at a value of approximately 98% and rising above 90% over a broad band from 450 to 2500 nm. The dimensions of the papillae are comparable to the roughness scale of surface-enhanced Raman scattering (SERS) substrates. SERS measurements performed on silver- and gold-coated wings display enhancement factors of approximately 106 with no apparent background contribution from the wing.

A Look at the Origin and Magnitude of the Chemical Contribution to the Enhancement Mechanism of Surface-Enhanced Raman Spectroscopy (SERS): Theory and Experiment

DTIC Science & Technology

2013-01-01

Mater. Chem. C 2013, 1, 426−431. (20) Pazos -Perez, N.; Ni, W. H.; Schweikart, A .; Alvarez-Puebla, R. A .; Fery, A .; Liz-Marzan, L. M. Highly Uniform... A Look at the Origin and Magnitude of the Chemical Contribution to the Enhancement Mechanism of Surface-Enhanced Raman Spectroscopy (SERS): Theory...Evanston, Illinois 60208-3113, United States *S Supporting Information ABSTRACT: Normal and surface-enhanced Raman spectra for a set of substituted

Ultra-sensitive molecular detection using surface-enhanced Raman scattering on periodic metal-dielectric nanostructures

NASA Astrophysics Data System (ADS)

Nien, Chun; Li, Yi-Hsuan; Su, Vin-Cent; Kuan, Chieh-Hsiung

2017-02-01

Surface-enhanced Raman scattering (SERS) is a powerful technique for trace chemical analysis and single molecule detection in the application of biochemical monitoring and food safety due to its ability to enhance the Raman scattering of molecules near the metallic surface or nanostructures. Here, we present a comprehensive study of the SERS enhancement by the periodically nanostructured surface, where the thin film of silver is deposited onto the surface, except the sidewall of posts, of 1-D lamellar gratings with varying pitch to forming metal-dielectric composite nanostructures. By enhancing the localized and surface-propagating mode in the vicinity of the concaves, the SERS signal can be improved by amplifying the intensity of electric field and increasing the optical path length of the incident light. Experimental investigations show that the enhancement factor can be manipulated by varying the polarization of incident light and the pitch size of gratings. To demonstrate the SERS effects of the proposed structures, thin layers of benzoic acid, which is commonly used as a food preservative, are deposited on the SERS substrates by spin-coating a solution of benzoic acid and dried at room temperature. A Confocal Raman microscope with a 532 nm laser source is used to illuminate light and measure the Raman spectrum of benzoic acid. We demonstrate the Raman signal of benzoic acid can be enhanced on the order of 102 on the SERS substrates.

Surface-enhanced Raman spectroscopy of urine by an ingenious near-infrared Raman spectrometer

NASA Astrophysics Data System (ADS)

Feng, Shangyuan; Chen, Weiwei; Li, Yongzeng; Chen, Guannan; Huang, Zufang; Liao, Xiaohua; Xie, Zhiming; Chen, Rong

2007-11-01

This paper demonstrates the potential of an elaborately devised near-infrared Raman system in analysis of urine. The broad band in the long-wavelength region of the electronic absorption spectra of the sol with added adsorbent at certain concentrations has been explained in terms of the aggregation of the colloidal silver particles. We have reported the surface-enhanced Raman (SERS) spectra of urine, and studied the silver solution enhanced effects on the urine Raman scattering. The Raman bands of human's urine was assigned to certain molecule vibrations. We have found that different donators have dissimilar SERS of urine in different physiological condition. Comparatively few studies have explored the ability of Raman spectroscopy for the analysis of urine acid. In the present report, we investigated the ability of surface enhanced Raman spectroscopy to measure uric acid in the human urine. The results suggested that the present Raman system holds considerable promise for practical use. Practical applications such as the quantitative medical examination of urine metabolites may also be feasible in the near future.

Self-Assembly of Large Gold Nanoparticles for Surface-Enhanced Raman Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Guang; Nanda, Jagjit; Wang, Boya

Performance of portable technologies from mobile phones to electric vehicles is currently limited by the energy density and lifetime of lithium batteries. Expanding the limits of battery technology requires in situ detection of trace components at electrode–electrolyte interphases. Surface-enhance Raman spectroscopy could satisfy this need if a robust and reproducible substrate were available. Gold nanoparticles (Au NPs) larger than 20 nm diameter are expected to greatly enhance Raman intensity if they can be assembled into ordered monolayers. A three-phase self-assembly method is presented that successfully results in ordered Au NP monolayers for particle diameters ranging from 13 to 90 nm.more » The monolayer structure and Raman enhancement factors (EFs) are reported for a model analyte, rhodamine, as well as the best performing polymer electrolyte salt, lithium bis(trifluoromethane)sulfonimide. Experimental EFs for the most part correlate with predictions based on monolayer geometry and with numerical simulations that identify local electromagnetic field enhancements. Lastly, the EFs for the best performing Au NP monolayer are between 10 6 and 10 8 and give quantitative signal response when analyte concentration is changed.« less

Self-Assembly of Large Gold Nanoparticles for Surface-Enhanced Raman Spectroscopy.

PubMed

Yang, Guang; Nanda, Jagjit; Wang, Boya; Chen, Gang; Hallinan, Daniel T

2017-04-19

Performance of portable technologies from mobile phones to electric vehicles is currently limited by the energy density and lifetime of lithium batteries. Expanding the limits of battery technology requires in situ detection of trace components at electrode-electrolyte interphases. Surface-enhance Raman spectroscopy could satisfy this need if a robust and reproducible substrate were available. Gold nanoparticles (Au NPs) larger than 20 nm diameter are expected to greatly enhance Raman intensity if they can be assembled into ordered monolayers. A three-phase self-assembly method is presented that successfully results in ordered Au NP monolayers for particle diameters ranging from 13 to 90 nm. The monolayer structure and Raman enhancement factors (EFs) are reported for a model analyte, rhodamine, as well as the best performing polymer electrolyte salt, lithium bis(trifluoromethane)sulfonimide. Experimental EFs for the most part correlate with predictions based on monolayer geometry and with numerical simulations that identify local electromagnetic field enhancements. The EFs for the best performing Au NP monolayer are between 10 6 and 10 8 and give quantitative signal response when analyte concentration is changed.

Self-Assembly of Large Gold Nanoparticles for Surface-Enhanced Raman Spectroscopy

DOE PAGES

Yang, Guang; Nanda, Jagjit; Wang, Boya; ...

2017-04-04

Performance of portable technologies from mobile phones to electric vehicles is currently limited by the energy density and lifetime of lithium batteries. Expanding the limits of battery technology requires in situ detection of trace components at electrode–electrolyte interphases. Surface-enhance Raman spectroscopy could satisfy this need if a robust and reproducible substrate were available. Gold nanoparticles (Au NPs) larger than 20 nm diameter are expected to greatly enhance Raman intensity if they can be assembled into ordered monolayers. A three-phase self-assembly method is presented that successfully results in ordered Au NP monolayers for particle diameters ranging from 13 to 90 nm.more » The monolayer structure and Raman enhancement factors (EFs) are reported for a model analyte, rhodamine, as well as the best performing polymer electrolyte salt, lithium bis(trifluoromethane)sulfonimide. Experimental EFs for the most part correlate with predictions based on monolayer geometry and with numerical simulations that identify local electromagnetic field enhancements. Lastly, the EFs for the best performing Au NP monolayer are between 10 6 and 10 8 and give quantitative signal response when analyte concentration is changed.« less

Three-dimensional hybrid silicon nanostructures for surface enhanced Raman spectroscopy based molecular detection

NASA Astrophysics Data System (ADS)

Vendamani, V. S.; Nageswara Rao, S. V. S.; Venugopal Rao, S.; Kanjilal, D.; Pathak, A. P.

2018-01-01

Three-dimensional silver nanoparticles decorated vertically aligned Si nanowires (Si NWs) are effective surface-enhanced Raman spectroscopy (SERS) substrates for molecular detection at low concentration levels. The length of Si NWs prepared by silver assisted electroless etching is increased with an increase in etching time, which resulted in the reduced optical reflection in the visible region. These substrates were tested and optimized by measuring the Raman spectrum of standard dye Rhodamine 6G (R6G) of 10 nM concentration. Further, effective SERS enhancements of ˜105 and ˜104 were observed for the cytosine protein (concentration of 50 μM) and ammonium perchlorate (oxidizer used in explosives composition with a concentration of 10 μM), respectively. It is established that these three-dimensional SERS substrates yielded considerably higher enhancement factors for the detection of R6G when compared to previous reports. The sensitivity can further be increased and optimized since the Raman enhancement was found to increase with an increase in the density of silver nanoparticles decorated on the walls of Si NWs.

Review of Recent Progress of Plasmonic Materials and Nano-Structures for Surface-Enhanced Raman Scattering

PubMed Central

Wang, Alan X.; Kong, Xianming

2015-01-01

Surface-enhanced Raman scattering (SERS) has demonstrated single-molecule sensitivity and is becoming intensively investigated due to its significant potential in chemical and biomedical applications. SERS sensing is highly dependent on the substrate, where excitation of the localized surface plasmons (LSPs) enhances the Raman scattering signals of proximate analyte molecules. This paper reviews research progress of SERS substrates based on both plasmonic materials and nano-photonic structures. We first discuss basic plasmonic materials, such as metallic nanoparticles and nano-rods prepared by conventional bottom-up chemical synthesis processes. Then, we review rationally-designed plasmonic nano-structures created by top-down approaches or fine-controlled synthesis with high-density hot-spots to provide large SERS enhancement factors (EFs). Finally, we discuss the research progress of hybrid SERS substrates through the integration of plasmonic nano-structures with other nano-photonic devices, such as photonic crystals, bio-enabled nanomaterials, guided-wave systems, micro-fluidics and graphene. PMID:26900428

Monolayer graphene on nanostructured Ag for enhancement of surface-enhanced Raman scattering stable platform

NASA Astrophysics Data System (ADS)

Dai, Zhigao; Mei, Fei; Xiao, Xiangheng; Liao, Lei; Wu, Wei; Zhang, Yupeng; Ying, Jianjian; Wang, Lingbo; Ren, Feng; Jiang, Changzhong

2015-03-01

We have reported that the Ag nanostructure-based substrate is particularly suitable for surface-enhanced Raman scattering when it is coated with monolayer graphene, an optically transparent and chemistry-inertness material in the visible range. Ag bowtie nanoantenna arrays and Ag nanogrids were fabricated using plasma-assisted nanosphere lithography. Our measurements show that atmospheric sulfur containing compounds are powerless to break in the monolayer graphene to vulcanize the surfaces of the Ag bowtie nanoantenna arrays and Ag nanogrids by various means, including scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). Furthermore, the Ag nanostructure substrate coated with the monolayer graphene film shows a larger enhancement of Raman activity and the electromagnetic field than the uncoated substrate. Compared with those of bare Ag nanostructures, the averaged EFs of graphene-film-coated Ag nanostructures were estimated to be about 21 and 5 for Ag bowtie nanoantenna arrays and nanogrids after one month later in air, respectively. These observations are further supported by theoretical calculations.

Review of Recent Progress of Plasmonic Materials and Nano-Structures for Surface-Enhanced Raman Scattering.

PubMed

Wang, Alan X; Kong, Xianming

2015-06-01

Surface-enhanced Raman scattering (SERS) has demonstrated single-molecule sensitivity and is becoming intensively investigated due to its significant potential in chemical and biomedical applications. SERS sensing is highly dependent on the substrate, where excitation of the localized surface plasmons (LSPs) enhances the Raman scattering signals of proximate analyte molecules. This paper reviews research progress of SERS substrates based on both plasmonic materials and nano-photonic structures. We first discuss basic plasmonic materials, such as metallic nanoparticles and nano-rods prepared by conventional bottom-up chemical synthesis processes. Then, we review rationally-designed plasmonic nano-structures created by top-down approaches or fine-controlled synthesis with high-density hot-spots to provide large SERS enhancement factors (EFs). Finally, we discuss the research progress of hybrid SERS substrates through the integration of plasmonic nano-structures with other nano-photonic devices, such as photonic crystals, bio-enabled nanomaterials, guided-wave systems, micro-fluidics and graphene.

Exploring the chemical enhancement for surface-enhanced Raman scattering with Au bowtie nanoantennas

PubMed Central

Fromm, David P.; Kinkhabwala, Anika; Schuck, P. James; Moerner, W. E.; Sundaramurthy, Arvind; Kino, Gordon S.

2006-01-01

Single metallic bowtie nanoantennas provide a controllable environment for surface-enhanced Raman scattering (SERS) of adsorbed molecules. Bowties have experimentally measured electromagnetic enhancements, enabling estimation of chemical enhancement for both the bulk and the few-molecule regime. Strong fluctuations of selected Raman lines imply that a small number of p-mercaptoaniline molecules on a single bowtie show chemical enhancement >107, much larger than previously believed, likely due to charge transfer between the Au surface and the molecule. This chemical sensitivity of SERS has significant implications for ultra-sensitive detection of single molecules. PMID:16483189

Quantitative and Sensitive Detection of Chloramphenicol by Surface-Enhanced Raman Scattering

PubMed Central

Ding, Yufeng; Yin, Hongjun; Meng, Qingyun; Zhao, Yongmei; Liu, Luo; Wu, Zhenglong; Xu, Haijun

2017-01-01

We used surface-enhanced Raman scattering (SERS) for the quantitative and sensitive detection of chloramphenicol (CAP). Using 30 nm colloidal Au nanoparticles (NPs), a low detection limit for CAP of 10−8 M was obtained. The characteristic Raman peak of CAP centered at 1344 cm−1 was used for the rapid quantitative detection of CAP in three different types of CAP eye drops, and the accuracy of the measurement result was verified by high-performance liquid chromatography (HPLC). The experimental results reveal that the SERS technique based on colloidal Au NPs is accurate and sensitive, and can be used for the rapid detection of various antibiotics. PMID:29261161

Surface enhanced Raman spectroscopy of fullerene C60 drop-deposited on the silvered porous silicon

NASA Astrophysics Data System (ADS)

Khinevich, N.; Girel, K.; Bandarenka, H.; Salo, V.; Mosunov, A.

2017-11-01

Surface enhanced Raman spectroscopy (SERS) of fullerene C60 drop-deposited from the 1.4·10-4 M aqueous solutions on the silvered porous silicon (Ag/PS) is reported for the first time. The used concentration is found to be not detected by the ordinary Raman spectroscopy. It is shown that SERS-spectrum of the fullerene deposited from the air-aged solution are characterized by less intensity than that of the fullerene solution kept out of the air. This indicates degradation of the fullerene solution due to oxidation. The results are prospective for the fast qualitative and quantitative analysis of the fullerene-based materials.

Enhancing Raman signals through electromagnetic hot zones induced by magnetic dipole resonance of metal-free nanoparticles

NASA Astrophysics Data System (ADS)

Tseng, Yi-Chuan; Lee, Yang-Chun; Chang, Sih-Wei; Lin, Tzu-Yao; Ma, Dai-Liang; Lin, Bo-Cheng; Chen, Hsuen-Li

2017-11-01

In this study, we found that the large area of electromagnetic field hot zone induced through magnetic dipole resonance of metal-free structures can greatly enhance Raman scattering signals. The magnetic resonant nanocavities, based on high-refractive-index silicon nanoparticles (SiNPs), were designed to resonate at the wavelength of the excitation laser of the Raman system. The well-dispersed SiNPs that were not closely packed displayed significant magnetic dipole resonance and gave a Raman enhancement per unit volume of 59 347. The hot zones of intense electric field were generated not only within the nonmetallic NPs but also around them, even within the underlying substrate. We observed experimentally that gallium nitride (GaN) and silicon carbide (SiC) surfaces presenting very few SiNPs (coverage: <0.3%) could display significantly enhanced (>50%) Raman signals. In contrast, the Raman signals of the underlying substrates were not enhanced by gold nanoparticles (AuNPs), even though these NPs displayed a localized surface plasmon resonance (LSPR) phenomenon. A comparison of the areas of the electric field hot zones (E 2 > 10) generated by SiNPs undergoing magnetic dipole resonance with the electric field hot spots (E 2 > 10) generated by AuNPs undergoing LSPR revealed that the former was approximately 70 times that of the latter. More noteworthily, the electromagnetic field hot zone generated from the SiNP is able to extend into the surrounding and underlying media. Relative to metallic NPs undergoing LSPR, these nonmetallic NPs displaying magnetic dipole resonance were more effective at enhancing the Raman scattering signals from analytes that were underlying, or even far away from, them. This application of magnetic dipole resonance in metal-free structures appears to have great potential for use in developing next-generation techniques for Raman enhancement.

Unveiling NIR Aza-Boron-Dipyrromethene (BODIPY) Dyes as Raman Probes: Surface-Enhanced Raman Scattering (SERS)-Guided Selective Detection and Imaging of Human Cancer Cells.

PubMed

Adarsh, Nagappanpillai; Ramya, Adukkadan N; Maiti, Kaustabh Kumar; Ramaiah, Danaboyina

2017-10-12

The development of new Raman reporters has attracted immense attention in diagnostic research based on surface enhanced Raman scattering (SERS) techniques, which is a well established method for ultrasensitive detection through molecular fingerprinting and imaging. Herein, for the first time, we report the unique and efficient Raman active features of the selected aza-BODIPY dyes 1-6. These distinctive attributes could be extended at the molecular level to allow detection through SERS upon adsorption onto nano-roughened gold surface. Among the newly revealed Raman reporters, the amino substituted derivative 4 showed high signal intensity at very low concentrations (ca. 0.4 μm for 4-Au). Interestingly, an efficient nanoprobe has been constructed by using gold nanoparticles as SERS substrate, and 4 as the Raman reporter (4-Au@PEG), which unexpectedly showed efficient recognition of three human cancer cells (lung: A549, cervical: HeLa, Fibrosarcoma: HT-1080) without any specific surface marker. We observed well reflected and resolved Raman mapping and characteristic signature peaks whereas, such recognition was not observed in normal fibroblast (3T3L1) cells. To confirm these findings, a SERS nanoprobe was conjugated with a specific tumour targeting marker, EGFR (Epidermal Growth Factor Receptor), a well known targeted agent for Human Fibrosarcoma (HT1080). This nanoprobe efficiently targeted the surface marker of HT1080 cells, threreby demonstrating its use as an ultrasensitive Raman probe for detection and targeted imaging, leaving normal cells unaffected. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Raman Spectroscopy and Surface-Enhanced Raman Scattering to Identify Colorants in Art: An Experiment for an Upper-Division Chemistry Laboratory

ERIC Educational Resources Information Center

Mayhew, Hannah E.; Frano, Kristen A.; Svoboda, Shelley A.; Wustholz, Kristin L.

2015-01-01

Surface-enhanced Raman scattering (SERS) studies of art represent an attractive way to introduce undergraduate students to concepts in nanoscience, vibrational spectroscopy, and instrumental analysis. Here, we present an undergraduate analytical or physical chemistry laboratory wherein a combination of normal Raman and SERS spectroscopy is used to…

Surface enhanced Raman optical activity of molecules on orientationally averaged substrates: theory of electromagnetic effects.

PubMed

Janesko, Benjamin G; Scuseria, Gustavo E

2006-09-28

We present a model for electromagnetic enhancements in surface enhanced Raman optical activity (SEROA) spectroscopy. The model extends previous treatments of SEROA to substrates, such as metal nanoparticles in solution, that are orientationally averaged with respect to the laboratory frame. Our theoretical treatment combines analytical expressions for unenhanced Raman optical activity with molecular polarizability tensors that are dressed by the substrate's electromagnetic enhancements. We evaluate enhancements from model substrates to determine preliminary scaling laws and selection rules for SEROA. We find that dipolar substrates enhance Raman optical activity (ROA) scattering less than Raman scattering. Evanescent gradient contributions to orientationally averaged ROA scale to first or higher orders in the gradient of the incident plane-wave field. These evanescent gradient contributions may be large for substrates with quadrupolar responses to the plane-wave field gradient. Some substrates may also show a ROA contribution that depends only on the molecular electric dipole-electric dipole polarizability. These conclusions are illustrated via numerical calculations of surface enhanced Raman and ROA spectra from (R)-(-)-bromochlorofluoromethane on various model substrates.

Synthesis and characterization of mixed monolayer protected gold nanorods and their Raman activities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mlambo, Mbuso; Nanotechnology Innovation Centre, Advanced Materials Division, Mintek, Private Bag X3015, Randburg 2125; Mdluli, Phumlani S.

2013-10-15

Graphical abstract: Gold nanorods surface functionalization. - Highlights: • Mixed monolayer protected gold nanorods. • Surface enhanced Raman spectroscopy. • HS-(CH{sub 2}){sub 11}-NHCO-coumarin as a Raman active compound. - Abstract: The cetyltrimethylammonium bromide (CTAB) gold nanorods (AuNRs) were prepared by seed-mediated route followed by the addition of a Raman active compound (HS-(CH{sub 2}){sub 11}-NHCO-coumarin) on the gold nanorods surfaces. Different stoichiometric mixtures of HS-(CH{sub 2}){sub 11}-NHCO-coumarin and HS-PEG-(CH{sub 2}){sub 11}COOH were evaluated for their Raman activities. The lowest stoichiometric ratio HS-(CH{sub 2}){sub 11}-NHCO-coumarin adsorbed on gold nanorods surface was detected and enhanced by Raman spectroscopy. The produced mixed monolayer protectedmore » gold nanorods were characterized by UV-vis spectrometer for optical properties, transmission electron microscope (TEM) for structural properties (shape and aspect ratio) and their zeta potentials (charges) were obtained from ZetaSizer to determine the stability of the produced mixed monolayer protected gold nanorods. The Raman results showed a surface enhanced Raman scattering (SERS) enhancement at the lowest stoichiometric ratio of 1% HS-(CH{sub 2}){sub 11}-NHCO-coumarin compared to high ratio of 50% HS-(CH{sub 2}){sub 11}-NHCO-coumarin on the surface of gold nanorods.« less

Optical absorption of suspended graphene based metal plasmonic grating in the visible range

NASA Astrophysics Data System (ADS)

Han, Y. X.; Chen, B. B.; Yang, J. B.; He, X.; Huang, J.; Zhang, J. J.; Zhang, Z. J.

2018-05-01

We employ finite-difference time-domain ( FDTD) method and Raman spectroscopy to study the properties of graphene, which is suspended on a gold/SiO2/Si grating structure with different trench depth of SiO2 layer. The absorption enhancement of suspended graphene and plasmonic resonance of metal grating are investigated in the visible range using 2D FDTD method. Moreover, it is found that the intensity of the Raman features depends very sensitively on the trench depth of SiO2 layer. Raman enhancement in our experiments is attributed to the enhanced optical absorption of graphene by near-field coupling based metal plasmonic grating. The enhanced absorption of suspended graphene modulated by localized surface plasmon resonance (LSPR) offers a potential application for opto-electromechanical devices.

Magnetic separation of heavy metal ions and evaluation based on surface-enhanced Raman spectroscopy: copper(II) ions as a case study.

PubMed

Yan, Xue; Zhang, Xue-Jiao; Yuan, Ya-Xian; Han, San-Yang; Xu, Min-Min; Gu, Ren'ao; Yao, Jian-Lin

2013-11-01

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p-Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface-enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface-enhanced Raman spectroscopy bands from p-mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface-Enhanced Raman Spectroscopy Study of 4-ATP on Gold Nanoparticles for Basal Cell Carcinoma Fingerprint Detection

NASA Astrophysics Data System (ADS)

Quynh, Luu Manh; Nam, Nguyen Hoang; Kong, K.; Nhung, Nguyen Thi; Notingher, I.; Henini, M.; Luong, Nguyen Hoang

2016-05-01

The surface-enhanced Raman signals of 4-aminothiophenol (4-ATP) attached to the surface of colloidal gold nanoparticles with size distribution of 2 to 5 nm were used as a labeling agent to detect basal cell carcinoma (BCC) of the skin. The enhanced Raman band at 1075 cm-1 corresponding to the C-S stretching vibration in 4-ATP was observed during attachment to the surface of the gold nanoparticles. The frequency and intensity of this band did not change when the colloids were conjugated with BerEP4 antibody, which specifically binds to BCC. We show the feasibility of imaging BCC by surface-enhanced Raman spectroscopy, scanning the 1075 cm-1 band to detect the distribution of 4-ATP-coated gold nanoparticles attached to skin tissue ex vivo.

Widefield quantitative multiplex surface enhanced Raman scattering imaging in vivo

NASA Astrophysics Data System (ADS)

McVeigh, Patrick Z.; Mallia, Rupananda J.; Veilleux, Israel; Wilson, Brian C.

2013-04-01

In recent years numerous studies have shown the potential advantages of molecular imaging in vitro and in vivo using contrast agents based on surface enhanced Raman scattering (SERS), however the low throughput of traditional point-scanned imaging methodologies have limited their use in biological imaging. In this work we demonstrate that direct widefield Raman imaging based on a tunable filter is capable of quantitative multiplex SERS imaging in vivo, and that this imaging is possible with acquisition times which are orders of magnitude lower than achievable with comparable point-scanned methodologies. The system, designed for small animal imaging, has a linear response from (0.01 to 100 pM), acquires typical in vivo images in <10 s, and with suitable SERS reporter molecules is capable of multiplex imaging without compensation for spectral overlap. To demonstrate the utility of widefield Raman imaging in biological applications, we show quantitative imaging of four simultaneous SERS reporter molecules in vivo with resulting probe quantification that is in excellent agreement with known quantities (R2>0.98).

Ultrasensitive Raman sensor based on a highly scattering porous structure

NASA Astrophysics Data System (ADS)

Yakovlev, V. V.

2010-02-01

Analytical methods capable of in situ monitoring of water quality have been in high demand for environmental safety, the identification of minute impurities and fundamental understanding of potential risks of these molecular species. Raman spectroscopy, which provides 'fingerprint' information about molecular species in the excitation volume, is a powerful tool for in vivo diagnostics. However, due to a relatively weak Raman signal (~ 1 out of 1014 incident photons produces the useful signal) there is a need to significantly (by many orders of magnitude) enhance this signal, to raise the detection sensitivity of this technique. Traditionally, surface enhanced Raman spectroscopy is employed to dramatically increase the local field intensity and substantially improve the efficiency of Raman scattering. However, the above enhancement occurs only in "hot spots", which represent only a small percent of the total surface are of the substrate. Plasmonic nanostructures are also found to be hard to manufacture in large quantities with the desired degree of reproducibility and to be unable to handle high laser power. We propose and experimentally demonstrate a new type of approach for ultrasensitive Raman sensing. It is based on manufacturing a random porous structure of high-index material, such as GaP, and use the effect of light localization to help improving the detection sensitivity of such sensor. The desired structure was manufactured using electrochemical etching of GaP wafers. The observed Raman signal amplitudes are favorably compared to the best known plasmonic substrates.

Probing the interaction of ionic liquids with graphene using surface-enhanced Raman spectroscopy

DOE PAGES

Mahurin, Shannon Mark; Dai, Sheng; Surwade, Sumedh P.; ...

2015-12-17

We report an in situ measurement of the interaction of an imidazolium-based room temperature ionic liquid with both pure silver and a graphene-over-silver electrode under an applied electrochemical potential. At a negative applied potential, overall signal intensity increased indicating enhanced ionic liquid concentration at both silver and graphene electrodes. Vibrational modes associated with the imidazolium ring exhibited greater intensity enhancements and larger peak shifts compared with the anion indicating that the cation adsorbs with the ring and alkyl chain parallel to the electrode surface for both silver and graphene. In contrast to the silver, the surface enhanced Raman spectra ofmore » the ionic liquid near graphene showed shifts in the cation peaks even at no applied potential because of the strong π–π interaction between the ionic liquid and the graphene. Furthermore, the intensity of the graphene peak decreased in the presence of ionic liquid possibly due to the interaction between the ionic liquid and graphene. In conclusion, these results illustrate the effectiveness of surface-enhanced Raman spectroscopy to investigate electrolyte interactions with graphene at the liquid/electrode interface.« less

Enhancement of Fluorescence and Raman Scattering in Cyanine-Dye Molecules on the Surface of Silicon-Coated Silver Nanoparticles

NASA Astrophysics Data System (ADS)

Kamalieva, A. N.; Toropov, N. A.; Bogdanov, K. V.; Vartanyan, T. A.

2018-03-01

A method of formation of a composite structure based on silver nanoparticles and a thin protective silicon film (Ag NPs/Si) is developed. Enhancement of the fluorescence and Raman scattering in cyaninedye molecules deposited onto the formed nanostructure is observed. The optical properties and morphology stability of particles that are in contact with cyanine-dye solutions in organic solvents are studied. It is shown that the Ag NPs/Si composite structure can be multiply used as an SERS-active surface.

Active control of silver nanoparticles spacing using dielectrophoresis for surface-enhanced Raman scattering.

PubMed

Chrimes, Adam F; Khoshmanesh, Khashayar; Stoddart, Paul R; Kayani, Aminuddin A; Mitchell, Arnan; Daima, Hemant; Bansal, Vipul; Kalantar-zadeh, Kourosh

2012-05-01

We demonstrate an active microfluidic platform that integrates dielectrophoresis for the control of silver nanoparticles spacing, as they flow in a liquid channel. By careful control of the nanoparticles spacing, we can effectively increase the surface-enhanced Raman scattering (SERS) signal intensity based on augmenting the number of SERS-active hot-spots, while avoiding irreversible aggregation of the particles. The system is benchmarked using dipicolinate (2,6-pyridinedicarboxylic acid) (DPA), which is a biomarker of Bacillus anthracis. The validity of the results is discussed using several complementing characterization scenarios.

[Detection of single-walled carbon nanotube bundles by tip-enhanced Raman spectroscopy].

PubMed

Wu, Xiao-Bin; Wang, Jia; Wang, Rui; Xu, Ji-Ying; Tian, Qian; Yu, Jian-Yuan

2009-10-01

Raman spectroscopy is a powerful technique in the characterization of carbon nanotubes (CNTs). However, this spectral method is subject to two obstacles. One is spatial resolution, namely the diffraction limits of light, and the other is its inherent small Raman cross section and weak signal. To resolve these problems, a new approach has been developed, denoted tip-enhanced Raman spectroscopy (TERS). TERS has been demonstrated to be a powerful spectroscopic and microscopic technique to characterize nanomaterial or nanostructures. Excited by a focused laser beam, an enhanced electric field is generated in the vicinity of a metallic tip because of the surface plasmon polariton (SPP) and lightening rod effect. Consequently, Raman signal from the sample area illuminated by the enhanced field nearby the tip is enhanced. At the same time, the topography is obtained in the nanometer scale. The exact corresponding relationship between the localized Raman and the topography makes the Raman identification at the nanometer scale to be feasible. In the present paper, based on an inverted microscope and a metallic AFM tip, a tip-enhanced Raman system was set up. The radius of the Au-coated metallic tip is about 30 nm. The 532 nm laser passes through a high numerical objective (NA0.95) from the bottom to illuminate the tip to excite the enhanced electric field. Corresponding with the AFM image, the tip-enhanced near-field Raman of a 100 nm diameter single-walled carbon nanotube (SWNT) bundles was obtained. The SWNTs were prepared by arc method. Furthermore, the near-field Raman of about 3 SWNTs of the bundles was received with the spatial resolution beyond the diffraction limit. Compared with the far-field Raman, the enhancement factor of the tip-enhanced Raman is more than 230. With the super-diffraction spatial resolution and the tip-enhanced Raman ability, tip-enhanced Raman spectroscopy will play an important role in the nano-material and nano-structure characterization.

Near-infrared surface-enhanced-Raman-scattering (SERS) mediated detection of single optically trapped bacterial spores

NASA Astrophysics Data System (ADS)

Alexander, Troy A.; Pellegrino, Paul M.; Gillespie, James B.

2003-08-01

A novel methodology has been developed for the investigation of bacterial spores. Specifically, this method has been used to probe the spore coat composition of two different Bacillus stearothermophilus variants. This technique may be useful in many applications; most notably, development of novel detection schemes toward potentially harmful bacteria. This method would also be useful as an ancillary environmental monitoring system where sterility is of importance (i.e., food preparation areas as well as invasive and minimally invasive medical applications). This unique detection scheme is based on the near-infrared (NIR) Surface-Enhanced-Raman-Scattering (SERS) from single, optically trapped, bacterial spores. The SERS spectra of bacterial spores in aqueous media have been measured using SERS substrates based on ~60-nm diameter gold colloids bound to 3-Aminopropyltriethoxysilane derivatized glass. The light from a 787-nm laser diode was used to trap/manipulate as well as simultaneously excite the SERS of an individual bacterial spore. The collected SERS spectra were examined for uniqueness and the applicability of this technique for the strain discrimination of Bacillus stearothermophilus spores. Comparison of normal Raman and SERS spectra reveal not only an enhancement of the normal Raman spectral features but also the appearance of spectral features absent in the normal Raman spectrum.

Near-infrared Surface-Enhanced-Raman-Scattering (SERS) mediated discrimination of single optically trapped bacterial spores

NASA Astrophysics Data System (ADS)

Alexander, Troy A.; Pellegrino, Paul M.; Gillespie, James B.

2004-03-01

A novel methodology has been developed for the investigation of bacterial spores. Specifically, this method has been used to probe the spore coat composition of two different Bacillus stearothermophilus variants. This technique may be useful in many applications; most notably, development of novel detection schemes toward potentially harmful bacteria. This method would also be useful as an ancillary environmental monitoring system where sterility is of importance (i.e., food preparation areas as well as invasive and minimally invasive medical applications). This unique detection scheme is based on the near-infrared (NIR) Surface-Enhanced-Raman- Scattering (SERS) from single, optically trapped, bacterial spores. The SERS spectra of bacterial spores in aqueous media have been measured using SERS substrates based on ~60-nm diameter gold colloids bound to 3-Aminopropyltriethoxysilane derivatized glass. The light from a 787-nm laser diode was used to trap/manipulate as well as simultaneously excite the SERS of an individual bacterial spore. The collected SERS spectra were examined for uniqueness and the applicability of this technique for the strain discrimination of Bacillus stearothermophilus spores. Comparison of normal Raman and SERS spectra reveal not only an enhancement of the normal Raman spectral features but also the appearance of spectral features absent in the normal Raman spectrum.

Surface-Enhanced Raman and Surface-Enhanced Hyper-Raman Scattering of Thiol-Functionalized Carotene

PubMed Central

2016-01-01

A thiol-modified carotene, 7′-apo-7′-(4-mercaptomethylphenyl)-β-carotene, was used to obtain nonresonant surface-enhanced Raman scattering (SERS) spectra of carotene at an excitation wavelength of 1064 nm, which were compared with resonant SERS spectra at an excitation wavelength of 532 nm. These spectra and surface-enhanced hyper-Raman scattering (SEHRS) spectra of the functionalized carotene were compared with the spectra of nonmodified β-carotene. Using SERS, normal Raman, and SEHRS spectra, all obtained for the resonant case, the interaction of the carotene molecules with silver nanoparticles, as well as the influence of the resonance enhancement and the SERS enhancement on the spectra, were investigated. The interaction with the silver surface occurs for both functionalized and nonfunctionalized β-carotene, but only the stronger functionalization-induced interaction enables the acquisition of nonresonant SERS spectra of β-carotene at low concentrations. The resonant SEHRS and SERS spectra are very similar. Nevertheless, the SEHRS spectra contain additional bands of infrared-active modes of carotene. Increased contributions from bands that experience low resonance enhancement point to a strong interaction between silver nanoparticles and electronic levels of the molecules, thereby giving rise to a decrease in the resonance enhancement in SERS and SEHRS. PMID:28077983

Challenge of false alarms in nitroaromatic explosive detection--a detection device based on surface-enhanced Raman spectroscopy.

PubMed

Wackerbarth, Hainer; Gundrum, Lars; Salb, Christian; Christou, Konstantin; Viöl, Wolfgang

2010-08-10

A challenge in the detection of explosives is the differentiation between explosives and contaminants. Synthetic musk-containing perfumes can cause false alarms, as these perfumes are nitroaromatic compounds, which can be mistaken for trinitro toluene (TNT) by some detectors. We present a detection principle based on surface-enhanced Raman scattering (SERS). A stream of the airborne compounds is focused and resublimated on a cooled nanostructured gold surface. We recorded high-resolution SERS spectra of TNT, musk xylene, and musk ketone. The nitroaromatic compounds can be identified unambiguously by their SERS spectra. Even the dominant bands containing nitro-group scissoring and symmetric stretching modes are significantly shifted by the difference in molecular structure.

Low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy combined with molecular beam epitaxy for in situ two-dimensional materials' studies

NASA Astrophysics Data System (ADS)

Sheng, Shaoxiang; Li, Wenbin; Gou, Jian; Cheng, Peng; Chen, Lan; Wu, Kehui

2018-05-01

Tip-enhanced Raman spectroscopy (TERS), which combines scanning probe microscopy with the Raman spectroscopy, is capable to access the local structure and chemical information simultaneously. However, the application of ambient TERS is limited by the unstable and poorly controllable experimental conditions. Here, we designed a high performance TERS system based on a low-temperature ultrahigh-vacuum scanning tunneling microscope (LT-UHV-STM) and combined with a molecular beam epitaxy (MBE) system. It can be used for growing two-dimensional (2D) materials and for in situ STM and TERS characterization. Using a 2D silicene sheet on the Ag(111) surface as a model system, we achieved an unprecedented 109 Raman single enhancement factor in combination with a TERS spatial resolution down to 0.5 nm. The results show that TERS combined with a MBE system can be a powerful tool to study low dimensional materials and surface science.

Toehold-mediated DNA displacement-based surface-enhanced Raman scattering DNA sensor utilizing an Au-Ag bimetallic nanodendrite substrate.

PubMed

Kim, Saetbyeol; Tran Ngoc, Huan; Kim, Joohoon; Yoo, So Young; Chung, Hoeil

2015-07-23

A simple and sensitive surface enhanced Raman scattering (SERS)-based DNA sensor that utilizes the toehold-mediated DNA displacement reaction as a target-capturing scheme has been demonstrated. For a SERS substrate, Au-Ag bimetallic nanodendrites were electrochemically synthesized and used as a sensor platform. The incorporation of both Ag and Au was employed to simultaneously secure high sensitivity and stability of the substrate. An optimal composition of Ag and Au that satisfied these needs was determined. A double-strand composed of 'a probe DNA (pDNA)' complementary to 'a target DNA (tDNA)' and 'an indicator DNA tagged with a Raman reporter (iDNA)' was conjugated on the substrate. The conjugation made the reporter molecule close to the surface and induced generation of the Raman signal. The tDNA released the pre-hybridized iDNA from the pDNA via toehold-mediated displacement, and the displacement of the iDNA resulted in the decrease of Raman intensity. The variation of percent intensity change was sensitive and linear in the concentration range from 200fM to 20nM, and the achieved limit of detection (LOD) was 96.3fM, superior to those reported in previous studies that adopted different signal taggings based on such as fluorescence and electrochemistry. Copyright © 2015 Elsevier B.V. All rights reserved.

Tip enhanced Raman spectroscopy, DFT and PED calculations of 4″-trimethylsilylethylsulfanyl-4,4‧-di(phenyleneethynylene)benzene thiol adsorbed on silver

NASA Astrophysics Data System (ADS)

Fletcher, Melissa C.; Alexson, Dimitri M.; Moore, Martin M.; Prokes, S. M.; Glembocki, Orest; Vivoni, Alberto; McCoy, Rhonda; Mishra, Soni; Tandon, Poonam; Hosten, Charles M.

2015-11-01

Monolayers of α,ω-dithiol oligo(phenyleneethynlene) molecules are critical to the field of molecular electronics because of their abilities to form bonds with many metallic surfaces and rectify current. In this study Fourier Transformation-Raman, surface-enhanced Raman scattering (SERS) spectroscopy and Tip-enhanced Raman Spectroscopy (TERS) were used to characterize a selectively oriented self-assembled monolayer of 4″-trimethylsilylethylsulfanyl-4,4‧-bis-(phenyleneethynylene)benzenethiol (OPE‧) on silver coated nanospheres. Selective orientation was achieved by synthesizing 4″-trimethylsilylethylsulfanyl-4,4‧-bis-(phenyleneethynylene)benzene disulfide, which undergoes oxidative dissociation and covalently bonds to the metal surface. The Ag coated nanosphere surfaces were characterized by scanning electron microscopy (SEM), which showed a large area of surface charging. The SERS and TERS spectra show similar results; however, a greater enhancement was achieved with the TERS relative to the SERS spectra. Assignments of vibrational bands were based on DFT calculations performed at the B3LYP level with good agreement between theoretical and experimental values. An average percent difference of 2.5 cm-1 was obtained for the non-CH stretching frequencies and a scaling factor was not applied to theoretically generated frequencies. A red shift of the ν(C-S) peak at 1087 cm-1 was observed when OPE‧ was adsorbed on a Ag surface. Vibrations specific to the trimethylsilylethyl (TMSE) group were visible in the TERS spectra, and disappear upon deprotection.

Surface-enhanced Raman spectroscopy detection of polybrominated diphenylethers using a portable Raman spectrometer.

PubMed

Jiang, Xiaohong; Lai, Yongchao; Wang, Wei; Jiang, Wei; Zhan, Jinhua

2013-11-15

Polybrominated diphenylethers (PBDEs), one of the most common brominated flame retardants, are toxic and persistent, generally detected by the chromatographic method. In this work, qualitative and quantitative detection of PBDEs were explored based on surface-enhanced Raman spectroscopy (SERS) technique using a portable Raman spectrometer. Alkanethiol modified silver nanoparticle aggregates were used as the substrate and PBDEs could be pre-concentrated close to the substrate surface through their hydrophobic interactions with alkanethiol. The effect of alkanethiols with different chain length on the SERS detection of PBDEs was evaluated. It was shown that 1-hexanethiol (HT) modified substrate has higher sensitivity, good stability and reusability. Qualitative and quantitative SERS detection of PBDEs in real sea water was accomplished, with the measured detection limits at 1.2×10(2) μg L(-1). These results illustrate SERS could be used as an effective method for the detection of PBDEs. Copyright © 2013 Elsevier B.V. All rights reserved.

Biological sensing with surface-enhanced Raman spectroscopy (SERS) using a facile and rapid silver colloid-based synthesis technique

NASA Astrophysics Data System (ADS)

Smyth, C.; Mehigan, S.; Rakovich, Y. P.; Bell, S. E. J.; McCabe, E. M.

2011-03-01

Optical techniques towards the realisation of sensitive and selective biosensing platforms have received a considerable amount of attention in recent times. Techniques based on interferometry, surface plasmon resonance, field-effect transistors and waveguides have all proved popular, and in particular, spectroscopy offers a large range of options. Raman spectroscopy has always been viewed as an information rich technique in which the vibrational frequencies reveal a lot about the structure of a compound. The issue with Raman spectroscopy has traditionally been that its rather low cross section leads to poor limits-of-detection. In response to this problem, Surface-enhanced Raman Scattering (SERS), which increases sensitivity by bringing the sample in contact with many types of enhanceing substrates, has been developed. Here we discuss a facile and rapid technique for the detection of pterins using colloidal silver suspensions. Pteridine compounds are a family of biochemicals, heterocyclic in structure, and employed in nature as components of colour pigmentation and also as facilitators for many metabolic pathways, particularly those relating to the amino acid hydroxylases. In this work, xanthopterin, isoxanthopterin and 7,8- dihydrobiopterin have been examined whilst absorbed to SERS-active silver colloids. SERS, while far more sensitive than regular Raman spectroscopy, has its own issues relating to the reproducibility of substrates. In order to obtain quantitative data for the pteridine compounds mentioned above, exploratory studies of methods for introducing an internal standard for normalisation of the signals have been carried out.e

Surface-enhanced Raman scattering (SERS) imaging of alkyne-tagged small molecule drug in live cells with endocytosed gold nanoparticles

NASA Astrophysics Data System (ADS)

Ando, Jun; Sekiya, Takumasa; Ka, Den; Yamakoshi, Hiroyuki; Dodo, Kosuke; Sodeoka, Mikiko; Kawata, Satoshi; Fujita, Katsumasa

2017-02-01

We propose the combination of alkyne-tag and surface-enhanced Raman scattering (SERS) spectroscopy to perform highly-sensitive and selective drug imaging in live cells. Gold nanoparticles are introduced in lysosomes through endocytosis as SERS agents, and the alkyne-tagged drugs are subsequently administered in cells. Raman microscopic observation reveals the arrival of drug in lysosome through enhanced Raman signal of alkyne. Since the peak of alkyne appears in Raman-silent region of biomolecules, selective detection of drugs is possible without background signal of endogenous molecules. From endocytosed gold nanoparticles in living HeLa cells, we observed distinct Raman signal from alkyne-tagged inhibitor of lysosomal enzyme.

Surface enhanced Raman scattering of aged graphene: Effects of annealing in vacuum

NASA Astrophysics Data System (ADS)

Wang, Yingying; Ni, Zhenhua; Li, Aizhi; Zafar, Zainab; Zhang, Yan; Ni, Zhonghua; Qu, Shiliang; Qiu, Teng; Yu, Ting; Xiang Shen, Ze

2011-12-01

In this paper, we report a simple method to recover the surface enhanced Raman scattering activity of aged graphene. The Raman signals of Rhodamine molecules absorbed on aged graphene are dramatically increased after vacuum annealing and comparable to those on fresh graphene. Atomic force microscopy measurements indicate that residues on aged graphene surface can efficiently be removed by vacuum annealing, which makes target molecule closely contact with graphene. We also find that the hole doping in graphene will facilitate charge transfer between graphene and molecule. These results confirm the strong Raman enhancement of target molecule absorbed on graphene is due to the charge transfer mechanism.

Detecting Chemically Modified DNA Bases Using Surface Enhanced Raman Spectroscopy

PubMed Central

Barhoumi, Aoune; Halas, Naomi J.

2013-01-01

Post-translational modifications of DNA- changes in the chemical structure of individual bases that occur without changes in the DNA sequence- are known to alter gene expression. They are believed to result in frequently deleterious phenotypic changes, such as cancer. Methylation of adenine, methylation and hydroxymethylation of cytosine, and guanine oxidation are the primary DNA base modifications identified to date. Here we show it is possible to use surface enhanced Raman spectroscopy (SERS) to detect these primary DNA base modifications. SERS detection of modified DNA bases is label-free and requires minimal additional sample preparation, reducing the possibility of additional chemical modifications induced prior to measurement. This approach shows the feasibility of DNA base modification assessment as a potentially routine analysis that may be further developed for clinical diagnostics. PMID:24427449

Detecting Chemically Modified DNA Bases Using Surface Enhanced Raman Spectroscopy.

PubMed

Barhoumi, Aoune; Halas, Naomi J

2011-12-15

Post-translational modifications of DNA- changes in the chemical structure of individual bases that occur without changes in the DNA sequence- are known to alter gene expression. They are believed to result in frequently deleterious phenotypic changes, such as cancer. Methylation of adenine, methylation and hydroxymethylation of cytosine, and guanine oxidation are the primary DNA base modifications identified to date. Here we show it is possible to use surface enhanced Raman spectroscopy (SERS) to detect these primary DNA base modifications. SERS detection of modified DNA bases is label-free and requires minimal additional sample preparation, reducing the possibility of additional chemical modifications induced prior to measurement. This approach shows the feasibility of DNA base modification assessment as a potentially routine analysis that may be further developed for clinical diagnostics.

Functionalized gold nanostars for label-free detection of PKA phosphorylation using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

He, Shuai; Kah, James C. Y.

2017-04-01

Protein phosphorylation controls fundamental biological processes. Dysregulation of protein kinase is associated with a series of human diseases including cancer. Protein kinase A (PKA) activity has been reported to serve as a potential prognostic marker for cancer. To this end, we developed a non-radioactive, rapid, cheap and robust scheme based on surface-enhanced Raman spectroscopy (SERS) for label-free detection of PKA phosphorylation using gold nanostars (AuNS) functionalized with BSA-kemptide. While bovine serum albumin (BSA) proteins stabilized the AuNS, kemptide, which is a high affinity substrate peptide specific for PKA, were phosphorylated in vitro to generate Raman signals that were identified by performing principal component analysis (PCA) on the acquired SERS spectra.

Sensitive Detection of Biomolecules by Surface Enhanced Raman Scattering using Plant Leaves as Natural Substrates

NASA Astrophysics Data System (ADS)

Sharma, Vipul; Krishnan, Venkata

2017-03-01

Detection of biomolecules is highly important for biomedical and other biological applications. Although several methods exist for the detection of biomolecules, surface enhanced Raman scattering (SERS) has a unique role in greatly enhancing the sensitivity. In this work, we have demonstrated the use of natural plant leaves as facile, low cost and eco-friendly SERS substrates for the sensitive detection of biomolecules. Specifically, we have investigated the influence of surface topography of five different plant leaf based substrates, deposited with Au, on the SERS performance by using L-cysteine as a model biomolecule. In addition, we have also compared the effect of sputter deposition of Au thin film with dropcast deposition of Au nanoparticles on the leaf substrates. Our results indicate that L-cysteine could be detected with high sensitivity using these plant leaf based substrates and the leaf possessing hierarchical micro/nanostructures on its surface shows higher SERS enhancement compared to a leaf having a nearplanar surface. Furthermore, leaves with drop-casted Au nanoparticle clusters performed better than the leaves sputter deposited with a thin Au film.

Characterization method for relative Raman enhancement for surface-enhanced Raman spectroscopy using gold nanoparticle dimer array

NASA Astrophysics Data System (ADS)

Sugano, Koji; Ikegami, Kohei; Isono, Yoshitada

2017-06-01

In this paper, a characterization method for Raman enhancement for highly sensitive and quantitative surface-enhanced Raman spectroscopy (SERS) is reported. A particle dimer shows a marked electromagnetic enhancement when the particle connection direction is matched to the polarization direction of incident light. In this study, dimers were arrayed by nanotrench-guided self-assembly for a marked total Raman enhancement. By measuring acetonedicarboxylic acid, the fabricated structures were characterized for SERS depending on the polarization angle against the particle connection direction. This indicates that the fabricated structures cause an effective SERS enhancement, which is dominated by the electromagnetic enhancement. Then, we measured 4,4‧-bipyridine, which is a pesticide material, for quantitative analysis. In advance, we evaluated the enhancement of the particle structure by the Raman measurement of acetonedicarboxylic acid. Finally, we compared the Raman intensities of acetonedicarboxylic acid and 4,4‧-bipyridine. Their intensities showed good correlation. The advantage of this method for previously evaluating the enhancement of the substrate was demonstrated. This developed SERS characterization method is expected to be applied to various quantitative trace analyses of molecules with high sensitivity.

A study of surface enhanced Raman scattering for furfural adsorbed on silver surface

NASA Astrophysics Data System (ADS)

Jia, Ting-jian; Li, Peng-wei; Shang, Zhi-guo; Zhang, Ling; He, Ting-chao; Mo, Yu-jun

2008-02-01

The normal Raman spectrum (NRS) and the surface enhanced Raman scattering (SERS) spectrum of furfural in silver colloid were recorded and analyzed in this paper. The assignment of these bands to furfural molecules was performed by density functional theory (DFT) calculation. The data of the SERS by comparing with the one of NRS show that furfural molecules are adsorbed on the silver surface via the nonbonding electrons of the carbonyl oxygen.

Raman Enhancement Effect on Thin GaSe Flake and Its Thickness Dependence

NASA Astrophysics Data System (ADS)

Quan, Lin; Song, Yuqing; Zhang, Guanghui; Wu, Yukun; Jin, Ke; Ding, Huaiyi; Pan, Nan; Luo, Yi; Wang, Xiaoping

Chemical enhancement is one of the important mechanisms in surface-enhanced Raman spectroscopy, however, its origin is still under debate. Two dimensional (2D) layered material is thought to be a strong candidate to investigate the chemical mechanism of Raman enhancement because it has flat surface, well defined structure and without the interference of electromagnetic enhancement. Herein we report the systematic studies of Raman enhancement effect on the gallium selenide (GaSe) flake by using copper phthalocyanine (CuPc) molecule as a probe. It is found that the Raman signal of CuPc on the monolayer GaSe can be significantly increased by one order of magnitude than that on the SiO2/Si substrate. Meanwhile, the enhancement effect is found to decrease with increasing the thickness of GaSe flake. The origin of the Raman enhancement is attributed to the chemical mechanism resulted from the charge transfer between the GaSe flake and the detected molecules. The supposition is further verified by the investigation of Raman enhancement effect of CuPc with different thicknesses on the GaSe flake. Our work will shed more light on the understanding of the chemical mechanism for Raman enhancement and expand more practical applications of GaSe.

Chemical analysis of acoustically levitated drops by Raman spectroscopy.

PubMed

Tuckermann, Rudolf; Puskar, Ljiljana; Zavabeti, Mahta; Sekine, Ryo; McNaughton, Don

2009-07-01

An experimental apparatus combining Raman spectroscopy with acoustic levitation, Raman acoustic levitation spectroscopy (RALS), is investigated in the field of physical and chemical analytics. Whereas acoustic levitation enables the contactless handling of microsized samples, Raman spectroscopy offers the advantage of a noninvasive method without complex sample preparation. After carrying out some systematic tests to probe the sensitivity of the technique to drop size, shape, and position, RALS has been successfully applied in monitoring sample dilution and preconcentration, evaporation, crystallization, an acid-base reaction, and analytes in a surface-enhanced Raman spectroscopy colloidal suspension.

PCR-free Quantification of Multiple Splice Variants in Cancer Gene by Surface Enhanced Raman Spectroscopy

PubMed Central

Sun, Lan; Irudayaraj, Joseph

2009-01-01

We demonstrate a surface enhanced Raman spectroscopy (SERS) based array platform to monitor gene expression in cancer cells in a multiplex and quantitative format without amplification steps. A strategy comprising of DNA/RNA hybridization, S1 nuclease digestion, and alkaline hydrolysis was adopted to obtain DNA targets specific to two splice junction variants Δ(9, 10) and Δ(5) of the breast cancer susceptibility gene 1 (BRCA1) from MCF-7 and MDA-MB-231 breast cancer cell lines. These two targets were identified simultaneously and their absolute quantities were estimated by a SERS strategy utilizing the inherent plasmon-phonon Raman mode of gold nanoparticle probes as a self-referencing standard to correct for variability in surface enhancement. Results were then validated by reverse transcription PCR (RT-PCR). Our proposed methodology could be expanded to a higher level of multiplexing for quantitative gene expression analysis of any gene without any amplification steps. PMID:19780515

Detection of Scopolamine Hydrobromide via Surface-enhanced Raman Spectroscopy.

PubMed

Bao, Lin; Sha, Xuan-Yu; Zhao, Hang; Han, Si-Qin-Gao-Wa; Hasi, Wu-Li-Ji

2017-01-01

Surface-enhanced Raman spectroscopy (SERS) was used to measure scopolamine hydrobromide. First, the Raman characteristic peaks of scopolamine hydrobromide were assigned, and the characteristic peaks were determined. The optimal aggregation agent was potassium iodide based on a comparative experimental study. Finally, the SERS spectrum of scopolamine hydrobromide was detected in aqueous solution, and the semi-quantitative analysis and the recovery rate were determined via a linear fitting. The detection limit of scopolamine hydrobromide in aqueous solution was 0.5 μg/mL. From 0 - 10 μg/mL, the curve of the intensity of the Raman characteristic peak of scopolamine hydrobromide at 1002 cm -1 is y = 4017.76 + 642.47x. The correlation coefficient was R 2 = 0.983, the recovery was 98.5 - 109.7%, and the relative standard deviation (RSD) was about 5.5%. This method is fast, accurate, non-destructive and simple for the detection of scopolamine hydrobromide.

Surface enhanced Raman spectroscopy: A review of recent applications in forensic science

NASA Astrophysics Data System (ADS)

Fikiet, Marisia A.; Khandasammy, Shelby R.; Mistek, Ewelina; Ahmed, Yasmine; Halámková, Lenka; Bueno, Justin; Lednev, Igor K.

2018-05-01

Surface enhanced Raman spectroscopy has many advantages over its parent technique of Raman spectroscopy. Some of these advantages such as increased sensitivity and selectivity and therefore the possibility of small sample sizes and detection of small concentrations are invaluable in the field of forensics. A variety of new SERS surfaces and novel approaches are presented here on a wide range of forensically relevant topics.

Nanoporous Substrate with Mixed Nanoclusters for Surface Enhanced Raman Scattering.

NASA Astrophysics Data System (ADS)

Chang, Sehoon; Ko, Hyunhyub; Singamaneni, Srikanth; Gunawidjaja, Ray; Tsukruk, Vladimir

2009-03-01

Rapid detection of plastic and liquid explosives is an urgent need due to various societal and technological reasons. We employed a novel design of surface enhanced Raman scattering (SERS)-active substrate based on porous alumina membranes decorated with mixed nanoclusters of gold nanorods and nanoparticles. We demonstrated trace level detection of several important explosives such as dinitrotolene (DNT), trinitrotoluene (TNT), and hexamethylenetriperoxidediamine (HMTD) by fast, sensitive, reliable Raman spectroscopic method. We achieved near molecular-level detection (about 15˜ 30 molecules) of DNT and TNT utilizing the SERS substrate. However, trace level detection is challenging due to the lack of common optical signatures (fluorescence, absorption in UV-vis range) or chemical functionality of peroxide-based explosives such as HMTD. To overcome this, we employed photochemical decomposition approach and analyzed chemical fragments using SERS. We suggest that tailored polymer coating, mixed nanoclusters, and laser-induced photocatalytic decomposition are all critical for achieving this unprecedented sensitivity level..

Surface Enhanced Raman Scattering studies of L-amino acids adsorbed on silver nanoclusters

NASA Astrophysics Data System (ADS)

Botta, Raju; Rajanikanth, A.; Bansal, C.

2015-01-01

Silver nanocluster films were prepared using plasma inert gas phase condensation technique. These were used as Raman active substrates for Surface Enhanced Raman Scattering (SERS) studies of 19 standard L-amino acids adsorbed on the surface of Ag nanoclusters via Agsbnd N bonds. A detailed study of two essential aromatic amino acids viz. L-Phenylalanine and L-Tryptophan showed a correlation between the Raman intensity of the characteristic lines of phenol and indole side chains and their molar concentrations in the range 1 μM-1 mM. This indicates that Raman studies can be used for quantitative determination of the amino acids in proteins.

Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules.

PubMed

Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin; Huang, Yingzhou

2017-08-02

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-M x (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-M x complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS.

Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules

PubMed Central

Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin

2017-01-01

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-Mx (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-Mx complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS. PMID:28767053

SERS imaging of cell-surface biomolecules metabolically labeled with bioorthogonal Raman reporters.

PubMed

Xiao, Ming; Lin, Liang; Li, Zefan; Liu, Jie; Hong, Senlian; Li, Yaya; Zheng, Meiling; Duan, Xuanming; Chen, Xing

2014-08-01

Live imaging of biomolecules with high specificity and sensitivity as well as minimal perturbation is essential for studying cellular processes. Here, we report the development of a bioorthogonal surface-enhanced Raman scattering (SERS) imaging approach that exploits small Raman reporters for visualizing cell-surface biomolecules. The cells were cultured and imaged by SERS microscopy on arrays of Raman-enhancing nanoparticles coated on silicon wafers or glass slides. The Raman reporters including azides, alkynes, and carbondeuterium bonds are small in size and spectroscopically bioorthogonal (background-free). We demonstrated that various cell-surface biomolecules including proteins, glycans, and lipids were metabolically incorporated with the corresponding precursors bearing a Raman reporter and visualized by SERS microscopy. The coupling of SERS microscopy with bioorthogonal Raman reporters expands the capabilities of live-cell microscopy beyond the modalities of fluorescence and label-free imaging. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of Surface-Enhanced Raman Spectroscopy in Inorganic Syntheses for an Upper-Level Exploratory Lab

ERIC Educational Resources Information Center

Seney, Caryn S.; Yelverton, Joshua C.; Eanes, Sharon; Patel, Vikas; Riggs, Julia; Wright, Sarah; Bright, Robin M.

2007-01-01

An experiment is designed where students will be using both gold and silver nanoparticles to study the enhancement factors of organic molecules adsorbed to the surface of the nanoparticles during or after synthesis by using surface-enhanced Raman spectroscopy (SERS). The experiment has helped students learn about the theory and experimental…

Localized surface plasmon resonances in nanostructures to enhance nonlinear vibrational spectroscopies: towards an astonishing molecular sensitivity

PubMed Central

2014-01-01

Summary Vibrational transitions contain some of the richest fingerprints of molecules and materials, providing considerable physicochemical information. Vibrational transitions can be characterized by different spectroscopies, and alternatively by several imaging techniques enabling to reach sub-microscopic spatial resolution. In a quest to always push forward the detection limit and to lower the number of needed vibrational oscillators to get a reliable signal or imaging contrast, surface plasmon resonances (SPR) are extensively used to increase the local field close to the oscillators. Another approach is based on maximizing the collective response of the excited vibrational oscillators through molecular coherence. Both features are often naturally combined in vibrational nonlinear optical techniques. In this frame, this paper reviews the main achievements of the two most common vibrational nonlinear optical spectroscopies, namely surface-enhanced sum-frequency generation (SE-SFG) and surface-enhanced coherent anti-Stokes Raman scattering (SE-CARS). They can be considered as the nonlinear counterpart and/or combination of the linear surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman scattering (SERS) techniques, respectively, which are themselves a branching of the conventional IR and spontaneous Raman spectroscopies. Compared to their linear equivalent, those nonlinear vibrational spectroscopies have proved to reach higher sensitivity down to the single molecule level, opening the way to astonishing perspectives for molecular analysis. PMID:25551056

Label-free surface-enhanced Raman scattering imaging to monitor the metabolism of antitumor drug 6-mercaptopurine in living cells.

PubMed

Han, Guangmei; Liu, Renyong; Han, Ming-Yong; Jiang, Changlong; Wang, Jianping; Du, Shuhu; Liu, Bianhua; Zhang, Zhongping

2014-12-02

The molecular processes of drugs from cellular uptake to intracellular distribution as well as the intracellular interaction with the target molecule are critically important for the development of new antitumor drugs. In this work, we have successfully developed a label-free surface-enhanced Raman scattering (SERS) technique to monitor and visualize the metabolism of antitumor drug 6-mercaptopurine in living cells. It has been clearly demonstrated that Au@Ag NPs exhibit an excellent Raman enhancement effect to both 6-mercaptopurine and its metabolic product 6-mercaptopurine-ribose. Their different ways to absorb at the surface of Au@Ag NPs lead to the obvious spectral difference for distinguishing the antitumor drug and its metabolite by SERS spectra. The Au@Ag NPs can easily pass through cell membranes in a large amount and sensitively respond to the biological conversion of 6-mercaptopurine in tumor cells. The Raman imaging can visualize the real-time distribution of 6-mercaptopurine and its biotransformation with the concentrations in tumor cells. The SERS-based method reported here is simple and efficient for the assessments of drug efficacy and the understanding of the molecular therapeutic mechanism of antitumor drugs at the cellular level.

Surface-Enhanced Raman Scattering Using Silica Whispering-Gallery Mode Resonators

NASA Technical Reports Server (NTRS)

Anderson, Mark S.

2013-01-01

The motivation of this work was to have robust spectroscopic sensors for sensitive detection and chemical analysis of organic and molecular compounds. The solution is to use silica sphere optical resonators to provide surface-enhanced spectroscopic signal. Whispering-gallery mode (WGM) resonators made from silica microspheres were used for surface-enhanced Raman scattering (SERS) without coupling to a plasmonic mechanism. Large Raman signal enhancement is observed by exclusively using 5.08-micron silica spheres with 785-nm laser excitation. The advantage of this non-plasmonic approach is that the active substrate is chemically inert silica, thermally stable, and relatively simple to fabricate. The Raman signal enhancement is broadly applicable to a wide range of molecular functional groups including aliphatic hydrocarbons, siloxanes, and esters. Applications include trace organic analysis, particularly for in situ planetary instruments that require robust sensors with consistent response.

Reproducible surface-enhanced Raman quantification of biomarkers in multicomponent mixtures.

PubMed

De Luca, Anna Chiara; Reader-Harris, Peter; Mazilu, Michael; Mariggiò, Stefania; Corda, Daniela; Di Falco, Andrea

2014-03-25

Direct and quantitative detection of unlabeled glycerophosphoinositol (GroPIns), an abundant cytosolic phosphoinositide derivative, would allow rapid evaluation of several malignant cell transformations. Here we report label-free analysis of GroPIns via surface-enhanced Raman spectroscopy (SERS) with a sensitivity of 200 nM, well below its apparent concentration in cells. Crucially, our SERS substrates, based on lithographically defined gold nanofeatures, can be used to predict accurately the GroPIns concentration even in multicomponent mixtures, avoiding the preliminary separation of individual compounds. Our results represent a critical step toward the creation of SERS-based biosensor for rapid, label-free, and reproducible detection of specific molecules, overcoming limits of current experimental methods.

Rapid bacterial diagnostics via surface enhanced Raman microscopy.

PubMed

Premasiri, W R; Sauer-Budge, A F; Lee, J C; Klapperich, C M; Ziegler, L D

2012-06-01

There is a continuing need to develop new techniques for the rapid and specific identification of bacterial pathogens in human body fluids especially given the increasing prevalence of drug resistant strains. Efforts to develop a surface enhanced Raman spectroscopy (SERS) based approach, which encompasses sample preparation, SERS substrates, portable Raman microscopy instrumentation and novel identification software, are described. The progress made in each of these areas in our laboratory is summarized and illustrated by a spiked infectious sample for urinary tract infection (UTI) diagnostics. SERS bacterial spectra exhibit both enhanced sensitivity and specificity allowing the development of an easy to use, portable, optical platform for pathogen detection and identification. SERS of bacterial cells is shown to offer not only reproducible molecular spectroscopic signatures for analytical applications in clinical diagnostics, but also is a new tool for studying biochemical activity in real time at the outer layers of these organisms.

Surface-enhanced Raman sensor for trace chemical detection in water

NASA Astrophysics Data System (ADS)

Lee, Vincent Y.; Farquharson, Stuart; Rainey, Petrie M.

1999-11-01

Surface-enhanced Raman spectroscopy (SERS) promises to be one of the most sensitive methods for chemical detection and in recent years SERS has been used for chemical, biochemical, environmental, and physiological applications. A variety of methods using various media (electrodes, colloids, and substrates) have been successfully developed to enhance Raman signals by six orders of magnitude and more. However, SERS has not become a routine analytical technique because these methods are unable to provide quantitative measurements. This is largely due to the inability to fabricate a sampling medium that provides reversible chemical adsorption, analysis-to-analysis reproducibility, unrestricted solution requirements (reagent concentration and pH) or sample phase (liquid or solid). In an effort to overcome these restrictions, we have developed metal-doped sol-gels to provide surface-enhancement of Raman scattering.

Highly sensitive determination of iron (III) ion based on phenanthroline probe: Surface-enhanced Raman spectroscopy methods

NASA Astrophysics Data System (ADS)

Chen, Lei; Ma, Ning; Park, Yeonju; Jin, Sila; Hwang, Hoon; Jiang, Dayu; Jung, Young Mee

2018-05-01

In this paper, we introduced Raman spectroscopy techniques that were based on the traditional Fe3 + determination method with phenanthroline as a probe. Interestingly, surface-enhanced Raman spectroscopy (SERS)-based approach exhibited excellent sensitivities to phenanthroline. Different detection mechanisms were observed for the RR and SERS techniques, in which the RR intensity increased with increasing Fe3 + concentration due to the observation of the RR effect of the phenanthroline-Fe2 + complex, whereas the SERS intensity increased with decreasing Fe3 + concentration due to the observation of the SERS effect of the uncomplexed phenanthroline. More importantly, the determination sensitivity was substantially improved in the presence of a SERS-active substrate, giving a detection limit as low as 0.001 μg/mL, which is 20 times lower than the limit of the UV-vis and RR methods. Furthermore, the proposed SERS method was free from other ions interference and can be used quality and sensitivity for the determination of the city tap water.

Nanoshell-Enhanced Raman Spectroscopy on a Microplate for Staphylococcal Enterotoxin B Sensing.

PubMed

Wang, Wenbin; Wang, Weiwei; Liu, Liqiang; Xu, Liguang; Kuang, Hua; Zhu, Jianping; Xu, Chuanlai

2016-06-22

A sensitive surface-enhanced Raman scattering (SERS) immunosensor based on the Au nanoparticle (Au NP) shell structure was developed to detect staphylococcal enterotoxin B (SEB) on a microplate. Au NPs modified with 4-nitrothiophenol (4-NTP) and coated with Ag shell of controlled thickness at 6.6 nm exhibited excellent SERS intensity and were used as signal reporters in the detection of SEB. The engaged 4-NTP allowed the significant electromagnetic enhancement between Au NPs and the Ag shell and prevented the dissociation of the Raman reporter. More importantly, 4-NTP-differentiated SERS signals between the sample and microplate. The SERS-based immunosensor had a limit of detection of 1.3 pg/mL SEB. Analysis of SEB-spiked milk samples revealed that the developed method had high accuracy. Therefore, the SERS-encoded Au@Ag core-shell structure-based immunosensor is promising for the detection of biotoxins, pathogens, and environmental pollutants.

A nanoforest structure for practical surface-enhanced Raman scattering substrates

NASA Astrophysics Data System (ADS)

Seol, Myeong-Lok; Choi, Sung-Jin; Baek, David J.; Park, Tae Jung; Ahn, Jae-Hyuk; Lee, Sang Yup; Choi, Yang-Kyu

2012-03-01

A nanoforest structure for surface-enhanced Raman scattering (SERS) active substrates is fabricated and analyzed. The detailed morphology of the resulting structure can be easily controlled by modifying the process parameters such as initial gold layer thickness and etching time. The applicability of the nanoforest substrate as a label-free SERS immunosensor is demonstrated using influenza A virus subtype H1N1. Selective binding of the H1N1 surface antigen and the anti-H1 antibody is directly detected by the SERS signal differences. Simple fabrication and high throughput with strong in-plane hot-spots imply that the nanoforest structure can be a practical sensing component of a chip-based SERS sensing system.

Gap-mode enhancement on MoS2 probed by functionalized tip-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Alajlan, Abdulrahman M.; Voronine, Dmitri V.; Sinyukov, Alexander M.; Zhang, Zhenrong; Sokolov, Alexei V.; Scully, Marlan O.

2016-09-01

Surface enhancement of molecular spectroscopic signals has been widely used for sensing and nanoscale imaging. Because of the weak electromagnetic enhancement of Raman signals on semiconductors, it is motivating but challenging to study the electromagnetic effect separately from the chemical effects. We report tip-enhanced Raman scattering measurements on Au and bulk MoS2 substrates using a metallic tip functionalized with copper phthalocyanine molecules and demonstrate similar gap-mode enhancement on both substrates. We compare the experimental results with theoretical calculations to confirm the gap-mode enhancement on MoS2 using a well-established electrostatic model. The functionalized tip approach allows for suppressing the background and is ideal for separating electromagnetic and chemical enhancement mechanisms on various substrates. Our results may find a wide range of applications in MoS2-based devices, sensors, and metal-free nanoscale bio-imaging.

Competition Between Extinction and Enhancement in Surface Enhanced Raman Spectroscopy.

PubMed

van Dijk, Thomas; Sivapalan, Sean T; Devetter, Brent M; Yang, Timothy K; Schulmerich, Matthew V; Murphy, Catherine J; Bhargava, Rohit; Carney, P Scott

2013-04-04

Conjugated metallic nanoparticles are a promising means to achieve ultrasensitive and multiplexed sensing in intact three-dimensional samples, especially for biological applications, via surface enhanced Raman scattering (SERS). We show that enhancement and extinction are linked and compete in a collection of metallic nanoparticles. Counterintuitively, the Raman signal vanishes when nanoparticles are excited at their plasmon resonance, while increasing nanoparticle concentrations at off-resonance excitation sometimes leads to decreased signal. We develop an effective medium theory that explains both phenomena. Optimal choices of excitation wavelength, individual particle enhancement factor and concentrations are indicated. The same processes which give rise to enhancement also lead to increased extinction of both the illumination and the Raman scattered light. Nanoparticles attenuate the incident field (blue) and at the same time provide local enhancement for SERS. Likewise the radiation of the Raman-scattered field (green) is enhanced by the near-by sphere but extinguished by the rest of the spheres in the suspension on propagation.

Au-Ag-Au double shell nanoparticles-based localized surface plasmon resonance and surface-enhanced Raman scattering biosensor for sensitive detection of 2-mercapto-1-methylimidazole.

PubMed

Liao, Xue; Chen, Yanhua; Qin, Meihong; Chen, Yang; Yang, Lei; Zhang, Hanqi; Tian, Yuan

2013-12-15

In this paper, Au-Ag-Au double shell nanoparticles were prepared based on the reduction of the metal salts HAuCl4 and AgNO3 at the surface of seed particles. Due to the synergistic effect between Au and Ag, the hybrid nanoparticles are particularly stable and show excellent performances on the detection of 2-mercapto-1-methylimidazole (methimazole). The binding of target molecule at the surface of Au-Ag-Au double shell nanoparticles was demonstrated based on both localized surface plasmon resonance (LSPR) and surface-enhanced Raman scattering (SERS) spectra. The LSPR intensity is directly proportional to the methimazole concentration in the range of 0.10-3.00×10(-7) mol L(-1). The SERS spectrum can be applied in identification of methimazole molecule. The LSPR coupled with SERS based on the Au-Ag-Au double shell nanoparticles would be very attractive for the quantitative determination and qualitative analysis of the analytes in medicines. © 2013 Elsevier B.V. All rights reserved.

Surface enhanced Raman spectroscopy: A review of recent applications in forensic science.

PubMed

Fikiet, Marisia A; Khandasammy, Shelby R; Mistek, Ewelina; Ahmed, Yasmine; Halámková, Lenka; Bueno, Justin; Lednev, Igor K

2018-05-15

Surface enhanced Raman spectroscopy has many advantages over its parent technique of Raman spectroscopy. Some of these advantages such as increased sensitivity and selectivity and therefore the possibility of small sample sizes and detection of small concentrations are invaluable in the field of forensics. A variety of new SERS surfaces and novel approaches are presented here on a wide range of forensically relevant topics. Copyright © 2018 Elsevier B.V. All rights reserved.

Operando plasmon-enhanced Raman spectroscopy in silicon anodes for Li-ion battery

NASA Astrophysics Data System (ADS)

Miroshnikov, Yana; Zitoun, David

2017-11-01

Silicon, an attractive candidate for high-energy lithium-ion batteries (LIBs), displays an alloying mechanism with lithium and presents several unique characteristics which make it an interesting scientific topic and also a technological challenge. In situ local probe measurements have been recently developed to understand the lithiation process and propose an effective remedy to the failure mechanisms. One of the most specific techniques, which is able to follow the phase changes in poorly crystallized electrode materials, makes use of Raman spectroscopy within the battery, i.e., in operando mode. Such an approach has been successful but is still limited by the rather signal-to-noise ratio of the spectroscopy. Herein, the operando Raman signal from the silicon anodes is enhanced by plasmonic nanoparticles following the known surface-enhanced Raman spectroscopy (SERS). Coinage metals (Ag and Au) display a surface plasmon resonance in the visible and allow the SERS effect to take place. We have found that the as-prepared materials reach high specific capacities over 1000 mAh/g with stability over more than 1000 cycles at 1C rate and can be suitable to perform as anodes in LIB. Moreover, the incorporation of coinage metals enables SERS to take place specifically on the surface of silicon. Consequently, by using a specially designed Raman cell, it is possible to follow the processes in a silicon-coinage metal-based battery trough operando SERS measurements.

Solid-State Synthesized Nanostructured Au Dendritic Aggregates Towards Surface-Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Gentile, A.; Ruffino, F.; D'Andrea, C.; Gucciardi, P. G.; Reitano, R.; Grimaldi, M. G.

2016-06-01

Micrometric Au structures, presenting a dendritic nano-structure, have been fabricated on a Si-based substrate. The fabrication method involves the deposition of a thin Au film on the substrate and a high-temperature annealing (1100°C) using fast heating and cooling ramps. The thermal process produces the growth, from the substrate, of Si micro-pillars whose top surfaces, covered by a crystalline Au layer, present a nanodendritic morphology. In addition to the micro-pillars, the sample surface presents a complex structural and chemical composition including Si3N4 regions due to the silicon-nitrogen intermixing during the heating stage. By studying the kinetic processes at the Au-Si interface during the thermal treatment, we describe the stages involved in the micro-pillars growth, in the dendritic morphology development, and in the Au atoms entrapment at the top of the dendritic surfaces. Finally, we present the analyses of the optical and surface enhanced Raman scattering properties of the Au dendritic aggregates. We show, in particular, that: (1) the Au dendrites aggregates act as effective scattering elements for the electromagnetic radiation in the infrared spectral region; and (2) the higher surface area due to the branched dendritic structure is responsible for the improvement in the sensitivity of the surface enhanced Raman scattering activity.

Biomedical Applications of Micro-Raman and Surface-Enhanced Raman Scattering (SERS) Technology

DTIC Science & Technology

2012-10-01

to be an effective media for PSA capture. For SERS-based immunoassays, nitrocellulose offers comparable results to those obtained using gold-coated...glass substrates while offering a more cost- effective and time-saving method of detecting minute amounts of PSA; (ii) Micro-Raman imaging...technology was found to be effective in chemical mapping of arteries in the tissues of a post mortem individual whose cause of death was a cardiac event

Surface enhanced Raman spectroscopy based nanoparticle assays for rapid, point-of-care diagnostics

NASA Astrophysics Data System (ADS)

Driscoll, Ashley J.

Nucleotide and immunoassays are important tools for disease diagnostics. Many of the current laboratory-based analytical diagnostic techniques require multiple assay steps and long incubation times before results are acquired. In the development of bioassays designed for detecting the emergence and spread of diseases in point-of-care (POC) and remote settings, more rapid and portable analytical methods are necessary. Nanoparticles provide simple and reproducible synthetic methods for the preparation of substrates that can be applied in colloidal assays, providing gains in kinetics due to miniaturization and plasmonic substrates for surface enhanced spectroscopies. Specifically, surface enhanced Raman spectroscopy (SERS) is finding broad application as a signal transduction method in immunological and nucleotide assays due to the production of narrow spectral peaks from the scattering molecules and the potential for simultaneous multiple analyte detection. The application of SERS to a no-wash, magnetic capture assay for the detection of West Nile Virus Envelope and Rift Valley Fever Virus N antigens is described. The platform utilizes colloid based capture of the target antigen in solution, magnetic collection of the immunocomplexes and acquisition of SERS spectra by a handheld Raman spectrometer. The reagents for a core-shell nanoparticle, SERS based assay designed for the capture of target microRNA implicated in acute myocardial infarction are also characterized. Several new, small molecule Raman scatterers are introduced and used to analyze the enhancing properties of the synthesized gold coated-magnetic nanoparticles. Nucleotide and immunoassay platforms have shown improvements in speed and analyte capture through the miniaturization of the capture surface and particle-based capture systems can provide a route to further surface miniaturization. A reaction-diffusion model of the colloidal assay platform is presented to understand the interplay of system parameters such as particle diameter, initial analyte concentration and dissociation constants. The projected sensitivities over a broad range of assay conditions are examined and the governing regime of particle systems reported. The results provide metrics in the design of more robust analytics that are of particular interest for POC diagnostics.

Simulation of two-dimensional gratings for SERS-active substrate

NASA Astrophysics Data System (ADS)

Zou, Wenlong; Wu, Jianhong

2016-11-01

Raman spectroscopy provides intrinsic vibrational and rotational mode of molecules in materials, which is widely used in chemical, medical and environmental domains. As known, the magnitude of surface enhanced Raman scattering can be amplified several orders. Nowadays, common Raman scattering has been gradually replaced by surface enhanced Raman scattering in low concentration detection domain. Generally speaking, the signal of surface enhanced Raman scattering on periodic nanostructures is more reliable and reproducible than on irregular nanostructures. In this paper, two-dimensional gratings coated by noble metal are used as SERS-active substrate. The surface plasmon resonance can be obtained by tuning the period of two-dimensional grating when the excitation laser interacts on the grating. The local electric field distribution is simulated by finite-difference-time-domain (FDTD). The wavelength of 632.8nm and 785nm are usually assembled on commercial Raman spectrometer. The optimization procedure of two-dimensional grating period is simulated by FDTD for above two wavelengths. The relation between the grating period and surface plasmon resonance is obtained in theory. The parameters such as depth of photoresist and thickness of coated metal are systematic discussed. The simulation results will greatly guide our post manufacture, which can be served for the commercial Raman spectrometer in SERS detection.

Surface-enhanced FAST CARS: en route to quantum nano-biophotonics

NASA Astrophysics Data System (ADS)

Voronine, Dmitri V.; Zhang, Zhenrong; Sokolov, Alexei V.; Scully, Marlan O.

2018-02-01

Quantum nano-biophotonics as the science of nanoscale light-matter interactions in biological systems requires developing new spectroscopic tools for addressing the challenges of detecting and disentangling weak congested optical signals. Nanoscale bio-imaging addresses the challenge of the detection of weak resonant signals from a few target biomolecules in the presence of the nonresonant background from many undesired molecules. In addition, the imaging must be performed rapidly to capture the dynamics of biological processes in living cells and tissues. Label-free non-invasive spectroscopic techniques are required to minimize the external perturbation effects on biological systems. Various approaches were developed to satisfy these requirements by increasing the selectivity and sensitivity of biomolecular detection. Coherent anti-Stokes Raman scattering (CARS) and surface-enhanced Raman scattering (SERS) spectroscopies provide many orders of magnitude enhancement of chemically specific Raman signals. Femtosecond adaptive spectroscopic techniques for CARS (FAST CARS) were developed to suppress the nonresonant background and optimize the efficiency of the coherent optical signals. This perspective focuses on the application of these techniques to nanoscale bio-imaging, discussing their advantages and limitations as well as the promising opportunities and challenges of the combined coherence and surface enhancements in surface-enhanced coherent anti-Stokes Raman scattering (SECARS) and tip-enhanced coherent anti-Stokes Raman scattering (TECARS) and the corresponding surface-enhanced FAST CARS techniques. Laser pulse shaping of near-field excitations plays an important role in achieving these goals and increasing the signal enhancement.

Tip-enhanced near-field optical microscope with side-on and ATR-mode sample excitation for super-resolution Raman imaging of surfaces

NASA Astrophysics Data System (ADS)

Heilman, A. L.; Gordon, M. J.

2016-06-01

A tip-enhanced near-field optical microscope with side-on and attenuated total reflectance (ATR) excitation and collection is described and used to demonstrate sub-diffraction-limited (super-resolution) optical and chemical characterization of surfaces. ATR illumination is combined with an Au optical antenna tip to show that (i) the tip can quantitatively transduce the optical near-field (evanescent waves) above the surface by scattering photons into the far-field, (ii) the ATR geometry enables excitation and characterization of surface plasmon polaritons (SPPs), whose associated optical fields are shown to enhance Raman scattering from a thin layer of copper phthalocyanine (CuPc), and (iii) SPPs can be used to plasmonically excite the tip for super-resolution chemical imaging of patterned CuPc via tip-enhanced Raman spectroscopy (TERS). ATR-illumination TERS is also quantitatively compared with the more conventional side-on illumination scheme. In both cases, spatial resolution was better than 40 nm and tip on/tip off Raman enhancement factors were >6500. Furthermore, ATR illumination was shown to provide similar Raman signal levels at lower "effective" pump powers due to additional optical energy delivered by SPPs to the active region in the tip-surface gap.

Tip-enhanced near-field optical microscope with side-on and ATR-mode sample excitation for super-resolution Raman imaging of surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heilman, A. L.; Gordon, M. J.

A tip-enhanced near-field optical microscope with side-on and attenuated total reflectance (ATR) excitation and collection is described and used to demonstrate sub-diffraction-limited (super-resolution) optical and chemical characterization of surfaces. ATR illumination is combined with an Au optical antenna tip to show that (i) the tip can quantitatively transduce the optical near-field (evanescent waves) above the surface by scattering photons into the far-field, (ii) the ATR geometry enables excitation and characterization of surface plasmon polaritons (SPPs), whose associated optical fields are shown to enhance Raman scattering from a thin layer of copper phthalocyanine (CuPc), and (iii) SPPs can be used tomore » plasmonically excite the tip for super-resolution chemical imaging of patterned CuPc via tip-enhanced Raman spectroscopy (TERS). ATR-illumination TERS is also quantitatively compared with the more conventional side-on illumination scheme. In both cases, spatial resolution was better than 40 nm and tip on/tip off Raman enhancement factors were >6500. Furthermore, ATR illumination was shown to provide similar Raman signal levels at lower “effective” pump powers due to additional optical energy delivered by SPPs to the active region in the tip-surface gap.« less

Development of a drug assay using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Angel, S. M.; Roe, Jeffrey N.; Andresen, Brian D.; Myrick, Michael L.; Milanovich, Fred P.

1990-07-01

Surface-enhanced Raman spectroscopy has been used to detect low levels of several chemical compounds, including the drugs of abuse -cocaine hydrochloride and methamphetamme hydrochloride. Raman spectra of these substances have also been taken over optical fibers using red-wavelength excitation. These measurements demonstrate the feasibility of the remote determination of various target chemicals using diode laser excitation and diode array detection.

Flexible Microsphere-Embedded Film for Microsphere-Enhanced Raman Spectroscopy.

PubMed

Xing, Cheng; Yan, Yinzhou; Feng, Chao; Xu, Jiayu; Dong, Peng; Guan, Wei; Zeng, Yong; Zhao, Yan; Jiang, Yijian

2017-09-27

Dielectric microspheres with extraordinary microscale optical properties, such as photonic nanojets, optical whispering-gallery modes (WGMs), and directional antennas, have drawn interest in many research fields. Microsphere-enhanced Raman spectroscopy (MERS) is an alternative approach for enhanced Raman detection by dielectric microstructures. Unfortunately, fabrication of microsphere monolayer arrays is the major challenge of MERS for practical applications on various specimen surfaces. Here we report a microsphere-embedded film (MF) by immersing a highly refractive microsphere monolayer array in the poly(dimethylsiloxane) (PDMS) film as a flexible MERS sensing platform for one- to three-dimensional (1D to 3D) specimen surfaces. The directional antennas and wave-guided whispering-gallery modes (WG-WGMs) contribute to the majority of Raman enhancement by the MFs. Moreover, the MF can be coupled with surface-enhanced Raman spectroscopy (SERS) to provide an extra >10-fold enhancement. The limit of detection is therefore improved for sensing of crystal violet (CV) and Sudan I molecules in aqueous solutions at concentrations down to 10 -7 M. A hybrid dual-layer microsphere enhancer, constructed by depositing a MF onto a microsphere monolayer array, is also demonstrated, wherein the WG-WGMs become dominant and boost the enhancement ratio >50-fold. The present work opens up new opportunities for design of cost-effective and flexible MERS sensing platforms as individual or associated techniques toward practical applications in ultrasensitive Raman detection.

Raman spectroscopic instrumentation and plasmonic methods for material characterization

NASA Astrophysics Data System (ADS)

Tanaka, Kazuki

The advent of nanotechnology has led to incredible growth in how we consume, make and approach advanced materials. By exploiting nanoscale material properties, unique control of optical, thermal, mechanical, and electrical characteristics becomes possible. This thesis describes the development of a novel localized surface plasmon resonant (LSPR) color sensitive photosensor, based on functionalization of gold nanoparticles onto tianium dioxide nanowires and sensing by a metal-semiconducting nanowire-metal photodiode structure. This LSPR photosensor has been integrated into a system that incorporates Raman spectroscopy, microfluidics, optical trapping, and sorting flow cytometry into a unique material characterization system called the microfluidic optical fiber trapping Raman sorting flow cytometer (MOFTRSFC). Raman spectroscopy is utilized as a powerful molecular characterization technique used to analyze biological, mineralogical and nanomaterial samples. To combat the inherently weak Raman signal, plasmonic methods have been applied to exploit surface enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR), increasing Raman intensity by up to 5 orders of magnitude. The resultant MOFTRSFC system is a prototype instrument that can effectively trap, analyze, and sort micron-sized dielectric particles and biological cells. Raman spectroscopy has been presented in several modalities, including the development of a portable near-infrared Raman spectrometer and other emerging technologies.

Surface-enhanced Raman scattering on single-wall carbon nanotubes.

PubMed

Kneipp, Katrin; Kneipp, Harald; Dresselhaus, Mildred S; Lefrant, Serge

2004-11-15

Exploiting the effect of surface-enhanced Raman scattering (SERS), the Raman signal of single-wall carbon nanotubes (SWNTs) can be enhanced by up to 14 orders of magnitude when the tubes are in contact with silver or gold nanostructures and Raman scattering takes place predominantly in the enhanced local optical fields of the nanostructures. Such a level of enhancement offers exciting opportunities for ultrasensitive Raman studies on SWNTs and allows resonant and non-resonant Raman experiments to be done on single SWNTs at relatively high signal levels. Since the optical fields are highly localized within so-called "hot spots" on fractal silver colloidal clusters, lateral confinement of the Raman scattering can be as small as 5 nm, allowing spectroscopic selection of a single nanotube from a larger population. Moreover, since SWNTs are very stable "artificial molecules" with a high aspect ratio and a strong electron-phonon coupling, they are unique "test molecules" for investigating the SERS effect itself and for probing the "electromagnetic field contribution" and "charge transfer contribution" to the effect. SERS is also a powerful tool for monitoring the "chemical" interaction between the nanotube and the metal nanostructure.

One-process fabrication of metal hierarchical nanostructures with rich nanogaps for highly-sensitive surface-enhanced Raman scattering.

PubMed

Liu, Gui-qiang; Yu, Mei-dong; Liu, Zheng-qi; Liu, Xiao-shan; Huang, Shan; Pan, Ping-ping; Wang, Yan; Liu, Mu-lin; Gu, Gang

2015-05-08

One-process fabrication of highly active and reproducible surface-enhanced Raman scattering (SERS) substrates via ion beam deposition is reported. The fabricated metal-dielectric-metal (MDM) hierarchical nanostructure possesses rich nanogaps and a tunable resonant cavity. Raman scattering signals of analytes are dramatically strengthened due to the strong near-field coupling of localized surface plasmon resonances (LSPRs) and the strong interaction of LSPRs of metal NPs with surface plasmon polaritons (SPPs) on the underlying metal film by crossing over the dielectric spacer. The maximum Raman enhancement for the highest Raman peak at 1650 cm(-1) is 13.5 times greater than that of a single metal nanoparticle (NP) array. Moreover, the SERS activity can be efficiently tailored by varying the size and number of voids between adjacent metal NPs and the thickness of the dielectric spacer. These findings may broaden the scope of SERS applications of MDM hierarchical nanostructures in biomedical and analytical chemistry.

Early discrimination of nasopharyngeal carcinoma based on tissue deoxyribose nucleic acid surface-enhanced Raman spectroscopy analysis

NASA Astrophysics Data System (ADS)

Qiu, Sufang; Li, Chao; Lin, Jinyong; Xu, Yuanji; Lu, Jun; Huang, Qingting; Zou, Changyan; Chen, Chao; Xiao, Nanyang; Lin, Duo; Chen, Rong; Pan, Jianji; Feng, Shangyuan

2016-12-01

Surface-enhanced Raman spectroscopy (SERS) was employed to detect deoxyribose nucleic acid (DNA) variations associated with the development of nasopharyngeal carcinoma (NPC). Significant SERS spectral differences between the DNA extracted from early NPC, advanced NPC, and normal nasopharyngeal tissue specimens were observed at 678, 729, 788, 1337, 1421, 1506, and 1573 cm-1, which reflects the genetic variations in NPC. Principal component analysis combined with discriminant function analysis for early NPC discrimination yielded a diagnostic accuracy of 86.8%, 92.3%, and 87.9% for early NPC, advanced NPC, and normal nasopharyngeal tissue DNA, respectively. In this exploratory study, we demonstrated the potential of SERS for early detection of NPC based on the DNA molecular study of biopsy tissues.

Sensing based on surface-enhanced Raman scattering using self-forming ZnO nanoarrays coated with gold as substrates

NASA Astrophysics Data System (ADS)

Tang, Feng; Adam, Pierre-Michel; Rogers, David J.; Sandana, Vinod E.; Bove, Philippe; Teherani, Ferechteh H.

2018-03-01

Surface-Enhanced Raman spectroscopy (SERS) is a widely used technique adopted in both academia and industry for the detection of trace quantities of Raman active molecules. This is usually accomplished by functionalizing distributions of plasmonic metal nanoparticles with the analyte molecules. Recently metal-coated nanostructures have been investigated as alternatives to dispersions of metal nanoparticles in order to avoid clustering and homogeneity/reproducibility issues. In this paper, several samples of Au-coated ZnO nanoarrays are adopted as SERS substrates in order to investigate the molecular sensing capacity for methylene blue (MB) molecules. Self-forming ZnO nanoarrays were grown on both c-sapphire and silicon substrates by pulsed laser deposition. The nanoarrays were then coated with 30 nm of gold using thermal evaporation and the SERS signals of MB functionalized samples were obtained with a Raman microspectrometer. The ratio of SERS intensity to that of an MB functionalized glass substrate (ISERS/IRaman) was calculated based on the averaged SERS signals. A relatively good within-wafer homogeneity of the enhancement effect was found with ISERS/IRaman values as high as 64.2 for Au-coated nano ZnO grown on silicon substrates. The experimental results show that the Au-coated ZnO nanoarrays can be excellent SERS substrates for molecular/chemical analyte sensing.

Bioanalytical applications of SERS (surface-enhanced Raman spectroscopy).

PubMed

Hudson, Stephen D; Chumanov, George

2009-06-01

Surface-enhanced Raman scattering (SERS) is a powerful technique for analyzing biological samples as it can rapidly and nondestructively provide chemical and, in some cases, structural information about molecules in aqueous environments. In the Raman scattering process, both visible and near-infrared (NIR) wavelengths of light can be used to induce polarization of Raman-active molecules, leading to inelastic light scattering that yields specific molecular vibrational information. The development of surface enhancement has enabled Raman scattering to be an effective tool for qualitative as well as quantitative measurements with high sensitivity and specificity. Recent advances have led to many novel applications of SERS for biological analyses, resulting in new insights for biochemistry and molecular biology, the detection of biological warfare agents, and medical diagnostics for cancer, diabetes, and other diseases. This trend article highlights many of these recent investigations and provides a brief outlook in order to assess possible future directions of SERS as a bioanalytical tool.

Investigation on tip enhanced Raman spectra of graphene

NASA Astrophysics Data System (ADS)

Li, Xinjuan; Liu, Yanqi; Zeng, Zhuo; Wang, Peijie; Fang, Yan; Zhang, Lisheng

2018-02-01

Tip-enhanced Raman scattering (TERS) is a promising analytical approach for some two-dimensional materials and offers the possibility to correlate imaging and chemical data. Tip-enhanced Raman spectra of graphene are discussed in some details, including substrate, gap between tip-apex and sample surface as well as Ag-nanowire. The TERS spectra give special emphasis to the possibility of TERS tip to induce a large number of defects only while got the tip attached to sample surface. Then the dependence of the TERS spectra of graphene and gap between the probe tip and sample surface was studied, and distribution features of electromagnetic (EM) field around tip were also simulated by finite-difference time-domain (FDTD). The Raman signal enhancement of graphene was further discussed with respect to experimental data. Furthermore, the Ag-nanowire as a nano-antenna could significantly enhance the weak Raman signal of D-band of monolayer graphene is shown, and the TERS spectra of graphene with regard to different regions of Ag-nanowires (endpoints, body) were obtained toward investigating into the distribution of electromagnetic field.

Deep Raman spectroscopy for the non-invasive standoff detection of concealed chemical threat agents.

PubMed

Izake, Emad L; Cletus, Biju; Olds, William; Sundarajoo, Shankaran; Fredericks, Peter M; Jaatinen, Esa

2012-05-30

Deep Raman spectroscopy has been utilized for the standoff detection of concealed chemical threat agents from a distance of 15 m under real life background illumination conditions. By using combined time and space resolved measurements, various explosive precursors hidden in opaque plastic containers were identified non-invasively. Our results confirm that combined time and space resolved Raman spectroscopy leads to higher selectivity towards the sub-layer over the surface layer as well as enhanced rejection of fluorescence from the container surface when compared to standoff spatially offset Raman spectroscopy. Raman spectra that have minimal interference from the packaging material and good signal-to-noise ratio were acquired within 5 s of measurement time. A new combined time and space resolved Raman spectrometer has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than picosecond-based laboratory systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Whispering-gallery nanocavity plasmon-enhanced Raman spectroscopy

PubMed Central

Zhang, Jing; Li, Jinxing; Tang, Shiwei; Fang, Yangfu; Wang, Jiao; Huang, Gaoshan; Liu, Ran; Zheng, Lirong; Cui, Xugao; Mei, Yongfeng

2015-01-01

The synergy effect in nature could enable fantastic improvement of functional properties and associated effects. The detection performance of surface-enhanced Raman scattering (SERS) can be highly strengthened under the cooperation with other factors. Here, greatly-enhanced SERS detection is realized based on rolled-up tubular nano-resonators decorated with silver nanoparticles. The synergy effect between whispering-gallery-mode (WGM) and surface plasmon leads to an extra enhancement at the order of 105 compared to non-resonant flat SERS substrates, which can be well tuned by altering the diameter of micron- and nanotubes and the excitation laser wavelengths. Such synchronous and coherent coupling between plasmonics and photonics could lead to new principle and design for various sub-wavelength optical devices, e.g. plasmonic waveguides and hyperbolic metamaterials. PMID:26443526

Paper-basd surface enhanced Raman spectroscopy of pnenobarbital sodium for point-of-care therapeutic drug monitoring

NASA Astrophysics Data System (ADS)

Yokoyama, Moe; Yamada, Kenji; Nishimura, Takahiro; Kido, Michiko; Jeong, Hieyong; Ohno, Yuko

2015-03-01

Therapeutic drug monitoring (TDM) contributes to safe and effective pharmacotherapy in clinical fields. A simple, rapid, low-cost, and minimally-invasive drug measurement method attracts much interest for point-of-care TDM. Tear fluids can be collected minimally-invasively compared to blood sampling and there is a correlation between a drug concentration in tears and that in bloods. Surface enhanced Raman spectroscopy (SERS) with paper-based substrate is useful for point-of-care TDM owing to inexpensiveness and high-sensitivity. Paper is also a safe tear collection tool. Then we are studying on a paper-based SERS of tear specimen for point-of-care TDM. In this paper, to improve sensitivity in measuring drug concentration in tear fluids, we fabricated a SERS substrate by coating gold nano-rods on a paper substrate and evaluated whether the fabricated substrate can enhance Raman scattering. Sodium phenobarbital (PB), an anti-convulsant agent, was used as a target. In experiment, the fabricated substrate indicated the lower detection limit of PB in a solution than a plain paper substrate. This result showed the potential of the paper based SERS substrate to measure drug concentration in tears simply and inexpensively.

Surface- and Tip-Enhanced Raman Spectroscopy in Catalysis

PubMed Central

2016-01-01

Surface- and tip-enhanced Raman spectroscopy (SERS and TERS) techniques exhibit highly localized chemical sensitivity, making them ideal for studying chemical reactions, including processes at catalytic surfaces. Catalyst structures, adsorbates, and reaction intermediates can be observed in low quantities at hot spots where electromagnetic fields are the strongest, providing ample opportunities to elucidate reaction mechanisms. Moreover, under ideal measurement conditions, it can even be used to trigger chemical reactions. However, factors such as substrate instability and insufficient signal enhancement still limit the applicability of SERS and TERS in the field of catalysis. By the use of sophisticated colloidal synthesis methods and advanced techniques, such as shell-isolated nanoparticle-enhanced Raman spectroscopy, these challenges could be overcome. PMID:27075515

Investigation on the adsorption characteristics of anserine on the surface of colloidal silver nanoparticles.

PubMed

Thomas, S; Maiti, N; Mukherjee, T; Kapoor, S

2013-08-01

The surface-enhanced Raman scattering (SERS) studies of anserine (beta-alanyl-N-methylhistidine) was carried out on colloidal silver nanoparticles to understand its adsorption characteristics. The experimentally observed Raman bands were assigned based on the results of DFT calculations. The studies suggest that the interaction of anserine is primarily through the carboxylate group with the imidazole ring in an upright position with respect to the silver surface. Concentration dependent SERS studies suggest a change in orientation at sub-monolayer concentration. Copyright © 2013 Elsevier B.V. All rights reserved.

[Research Progress of Raman Spectroscopy on Dyestuff Identification of Ancient Relics and Artifacts].

PubMed

He, Qiu-ju; Wang, Li-qin

2016-02-01

As the birthplace of Silk Road, China has a long dyeing history. The valuable information about the production time, the source of dyeing material, dyeing process and preservation status were existed in organic dyestuff deriving from cultural relics and artifacts. However, because of the low contents, complex compositions and easily degraded of dyestuff, it is always a challenging task to identify the dyestuff in relics analyzing field. As a finger-print spectrum, Raman spectroscopy owns unique superiorities in dyestuff identification. Thus, the principle, characteristic, limitation, progress and development direction of micro-Raman spectroscopy (MRS/µ-Raman), near infrared reflection and Fourier transform Raman spectroscopy (NIR-FT-Raman), surface-enhanced Raman spectroscopy (SERS) and resonance raman spectroscopy (RRS) have been introduced in this paper. Furthermore, the features of Raman spectra of gardenia, curcumin and other natural dyestuffs were classified by MRS technology, and then the fluorescence phenomena of purpurin excitated with different wavelength laser was compared and analyzed. At last, gray green silver colloidal particles were made as the base, then the colorant of madder was identified combining with thin layer chromatography (TLC) separation technology and SERS, the result showed that the surface enhancement effect of silver colloidal particles could significantly reduce fluorescence background of the Raman spectra. It is pointed out that Raman spectroscopy is a rapid and convenient molecular structure qualitative methodology, which has broad application prospect in dyestuff analysis of cultural relics and artifacts. We propose that the combination of multi-Raman spectroscopy, separation technology and long distance transmission technology are the development trends of Raman spectroscopy.

A highly sensitive biological detection substrate based on TiO2 nanowires supporting gold nanoparticles

NASA Astrophysics Data System (ADS)

Zeng, Yuan; Tan, Hai-jun; Cheng, Xiu-Lan; Chen, Rui; Wang, Ying

2011-12-01

Surface enhanced Raman scattering (SERS) has attracted widespread concern in the field of bioassay because it can enhance normally weak Raman signal by several orders of magnitude and facilitate the highly sensitive detection of molecules. Conventional SERS substrates are prepared by placing metal nanoparticles on a planar surface. Here we show a unique SERS substrate stacked by disordered TiO2 nanowires (TiO2-NWs) supportig gold nanocrystals. The structure can be easily fabricated by chemical synthesis at low cost. The COMSOL model simulation shows the designed SERS substrate is capable of output high Local Field Enhancement (LFE) in the Near Infrared region (NIR) that is the optimal wavelength in bio-detection because of both the unique coupling enhancement effect amony nearby Au nanocrystals on TiO2-NWs and the Suface Plasmon Resonance (SPR) effect of TiO2 -NWs. The as-prepared transparent and freestanding SERS substrate is capable of detecting extremely low concentration R6G molecular, showing much higher Raman signal because of the extremely large surface area and the uniqueTiO2-NWs self-assemblied by Au nanocrystals. These results provide a new approach to ultrasensitive bioassay device.

Nanosensors based on functionalized nanoparticles and surface enhanced raman scattering

DOEpatents

Talley, Chad E.; Huser, Thomas R.; Hollars, Christopher W.; Lane, Stephen M.; Satcher, Jr., Joe H.; Hart, Bradley R.; Laurence, Ted A.

2007-11-27

Surface-Enhanced Raman Spectroscopy (SERS) is a vibrational spectroscopic technique that utilizes metal surfaces to provide enhanced signals of several orders of magnitude. When molecules of interest are attached to designed metal nanoparticles, a SERS signal is attainable with single molecule detection limits. This provides an ultrasensitive means of detecting the presence of molecules. By using selective chemistries, metal nanoparticles can be functionalized to provide a unique signal upon analyte binding. Moreover, by using measurement techniques, such as, ratiometric received SERS spectra, such metal nanoparticles can be used to monitor dynamic processes in addition to static binding events. Accordingly, such nanoparticles can be used as nanosensors for a wide range of chemicals in fluid, gaseous and solid form, environmental sensors for pH, ion concentration, temperature, etc., and biological sensors for proteins, DNA, RNA, etc.

Design of SERS nanoprobes for Raman imaging: materials, critical factors and architectures.

PubMed

Li, Mingwang; Qiu, Yuanyuan; Fan, Chenchen; Cui, Kai; Zhang, Yongming; Xiao, Zeyu

2018-05-01

Raman imaging yields high specificity and sensitivity when compared to other imaging modalities, mainly due to its fingerprint signature. However, intrinsic Raman signals are weak, thus limiting medical applications of Raman imaging. By adsorbing Raman molecules onto specific nanostructures such as noble metals, Raman signals can be significantly enhanced, termed surface-enhanced Raman scattering (SERS). Recent years have witnessed great interest in the development of SERS nanoprobes for Raman imaging. Rationally designed SERS nanoprobes have greatly enhanced Raman signals by several orders of magnitude, thus showing great potential for biomedical applications. In this review we elaborate on recent progress in design strategies with emphasis on material properties, modifying factors, and structural parameters.

Advances in UV-Plasmonics: A Detailed Analysis of Metallic Materials as Candidates for New Applications in Nanothecnology

DTIC Science & Technology

2014-08-26

Indium, Rhodium, Ruthenium, Tungsten, Titanium, Chromium, Palladium, Copper, Platinum and Magnesium . These have been chosen because all of them...performance. vii. Considering that the observed behaviors occur precisely where UV surface-enhanced Raman spectra indicated strong local field...research objective was centered on the UV plasmonic properties of Rh NPs by means of surface-enhanced Raman spectroscopy, surface-enhanced

Surface-enhanced Raman spectroscopic studies of the Au-pentacene interface: a combined experimental and theoretical investigation.

PubMed

Adil, D; Guha, S

2013-07-28

It has recently been shown [D. Adil and S. Guha, J. Phys. Chem. C 116, 12779 (2012)] that a large enhancement in the Raman intensity due to surface-enhanced Raman scattering (SERS) is observed from pentacene when probed through the Au contact in organic field-effect transistors (OFET) structures. Here, the SERS spectrum is shown to exhibit a high sensitivity to disorder introduced in the pentacene film by Au atoms. The Raman signature of the metal-semiconductor interface in pentacene OFETs is calculated with density-functional theory by explicitly considering the Au-pentacene interaction. The observed enhancement in the 1380 cm(-1) and the 1560 cm(-1) regions of the experimental Raman spectrum of pentacene is successfully modeled by Au-pentacene complexes, giving insights into the nature of disorder in the pentacene sp(2) network. Finally, we extend our previous work on high-operating voltage pentacene OFETs to low-operating voltage pentacene OFETs. No changes in the SERS spectra before and after subjecting the OFETs to a bias stress are observed, concurrent with no degradation in the threshold voltage. This shows that bias stress induced performance degradation is, in part, caused by field-induced structural changes in the pentacene molecule. Thus, we confirm that the SERS spectrum can be used as a visualization tool for correlating transport properties to structural changes, if any, in organic semiconductor based devices.

[Study of surface enhanced Raman scattering of trace trinitrotoluene based on silver colloid nanoparticles].

PubMed

Zhang, Chun-ling; Li, Zhe; Wu, Zheng-long; Han, De-jun

2012-03-01

Trinitrotoluene (TNT), a representative nitroexplosive, attracts more and more attentions because of the urgent demand for trace analysis of explosives in recent years. The present study investigated the experiment condition of the surface enhanced Raman scattering (SERS) of 10(-6) mol x L(-1) TNT solution, especially the influence of NaCl and basic hydrolysis. The results indicate that SERS spectra of TNT can not be obtained when preparing the SERS samples without NaCl, and it was also shown that the intensity of Raman peaks has a relationship with the concentration of NaCl. With the increase in the concentration of NaCl, the intensity of Raman peak at 1 392 cm(-1) has a maximum value. This report explained the reason why NaCl can affect the intensity of SERS theoretically. It was also shown that the SERS spectrum of TNT treated with basic hydrolysis is more intense than that without basic hydrolysis.

Surface-Enhanced Raman Spectroscopy.

ERIC Educational Resources Information Center

Garrell, Robin L.

1989-01-01

Reviews the basis for the technique and its experimental requirements. Describes a few examples of the analytical problems to which surface-enhanced Raman spectroscopy (SERS) has been and can be applied. Provides a perspective on the current limitations and frontiers in developing SERS as an analytical technique. (MVL)

Tip-Enhanced Raman Scattering Microscopy: A Step toward Nanoscale Control of Intrinsic Molecular Properties

NASA Astrophysics Data System (ADS)

Yano, Taka-aki; Hara, Masahiko

2018-06-01

Tip-enhanced Raman scattering microscopy, a family of scanning probe microscopy techniques, has been recognized as a powerful surface analytical technique with both single-molecule sensitivity and angstrom-scale spatial resolution. This review covers the current status of tip-enhanced Raman scattering microscopy in surface and material nanosciences, including a brief history, the basic principles, and applications for the nanoscale characterization of a variety of nanomaterials. The focus is on the recent trend of combining tip-enhanced Raman scattering microscopy with various external stimuli such as pressure, voltage, light, and temperature, which enables the local control of the molecular properties and functions and also enables chemical reactions to be induced on a nanometer scale.

Rapid and sensitive phenotypic marker detection on breast cancer cells using surface-enhanced Raman scattering (SERS) imaging.

PubMed

Lee, Sangyeop; Chon, Hyangah; Lee, Jiyoung; Ko, Juhui; Chung, Bong Hyun; Lim, Dong Woo; Choo, Jaebum

2014-01-15

We report a surface-enhanced Raman scattering (SERS)-based cellular imaging technique to detect and quantify breast cancer phenotypic markers expressed on cell surfaces. This technique involves the synthesis of SERS nano tags consisting of silica-encapsulated hollow gold nanospheres (SEHGNs) conjugated with specific antibodies. Hollow gold nanospheres (HGNs) enhance SERS signal intensity of individual particles by localizing surface electromagnetic fields through pinholes in the hollow particle structures. This capacity to enhance imaging at the level of single molecules permits the use of HGNs to detect specific biological markers expressed in living cancer cells. In addition, silica encapsulation greatly enhances the stability of nanoparticles. Here we applied a SERS-based imaging technique using SEHGNs in the multiplex imaging of three breast cancer cell phenotypes. Expression of epidermal growth factor (EGF), ErbB2, and insulin-like growth factor-1 (IGF-1) receptors were assessed in the MDA-MB-468, KPL4 and SK-BR-3 human breast cancer cell lines. SERS imaging technology described here can be used to test the phenotype of a cancer cell and quantify proteins expressed on the cell surface simultaneously. Based on results, this technique may enable an earlier diagnosis of breast cancer than is currently possible and offer guidance in treatment. © 2013 Elsevier B.V. All rights reserved.

Surface-enhanced Raman scattering from silver nanostructures with different morphologies

NASA Astrophysics Data System (ADS)

Zhang, W. C.; Wu, X. L.; Kan, C. X.; Pan, F. M.; Chen, H. T.; Zhu, J.; Chu, Paul K.

2010-07-01

Scanning electron microscopy and X-ray diffraction reveal that four different types of crystalline silver nanostructures including nanoparticles, nanowires, nanocubes, and bipyramids are synthesized by a solvothermal method by reducing silver nitrate with ethylene glycol using poly(vinylpyrrolidone) as an adsorption agent and adding different quantities of sodium chloride to the solution. These nanostructures which exhibit different surface plasma resonance properties in the ultraviolet-visible region are shown to be good surface-enhanced Raman scattering (SERS) substrates using rhodamine 6G molecules. Our results demonstrate that the silver nanocubes, bipyramids with sharp corners and edges, and aggregated silver nanoparticles possess better SERS properties than the silver nanowires, indicating that they can serve as high-sensitivity substrates in SERS-based measurements.

Nanostructure Diffraction Gratings for Integrated Spectroscopy and Sensing

NASA Technical Reports Server (NTRS)

Guo, Junpeng (Inventor)

2015-01-01

The present disclosure pertains to metal or dielectric nanostructures of the subwavelength scale within the grating lines of optical diffraction gratings. The nanostructures have surface plasmon resonances or non-plasmon optical resonances. A linear photodetector array is used to capture the resonance spectra from one of the diffraction orders. The combined nanostructure super-grating and photodetector array eliminates the use of external optical spectrometers for measuring surface plasmon or optical resonance frequency shift caused by the presence of chemical and biological agents. The nanostructure super-gratings can be used for building integrated surface enhanced Raman scattering (SERS) spectrometers. The nanostructures within the diffraction grating lines enhance Raman scattering signal light while the diffraction grating pattern of the nanostructures diffracts Raman scattering light to different directions of propagation according to their wavelengths. Therefore, the nanostructure super-gratings allows for the use of a photodetector array to capture the surface enhanced Raman scattering spectra.

Nanostructure Diffraction Gratings for Integrated Spectroscopy and Sensing

NASA Technical Reports Server (NTRS)

Guo, Junpeng (Inventor)

2016-01-01

The present disclosure pertains to metal or dielectric nanostructures of the subwavelength scale within the grating lines of optical diffraction gratings. The nanostructures have surface plasmon resonances or non-plasmon optical resonances. A linear photodetector array is used to capture the resonance spectra from one of the diffraction orders. The combined nanostructure super-grating and photodetector array eliminates the use of external optical spectrometers for measuring surface plasmon or optical resonance frequency shift caused by the presence of chemical and biological agents. The nanostructure super-gratings can be used for building integrated surface enhanced Raman scattering (SERS) spectrometers. The nanostructures within the diffraction grating lines enhance Raman scattering signal light while the diffraction grating pattern of the nanostructures diffracts Raman scattering light to different directions of propagation according to their wavelengths. Therefore, the nanostructure super-gratings allows for the use of a photodetector array to capture the surface enhanced Raman scattering spectra.

Raman Spectrograph for Ocean Worlds: Integrating Cavity Enhanced Spectroscopy

NASA Astrophysics Data System (ADS)

Retherford, Kurt D.; Moore, Thomas Z.; Davis, Michael W.; Howett, Carly; Soto, Alejandro; Raut, Ujjwal; Molyneux, Philippa M.; Nowicki, Keith; Mandt, Kathleen; E Schmidt, Britney; Mason, John; Yakovlev, Vladislav V.; Fry, Edward S.; RSO Team

2017-10-01

We present a new concept for a Raman spectrograph instrument designed to conduct high sensitivity measurements of biomarkers within Ocean Worlds environments. Our Raman Spectrograph for Ocean worlds (RSO) instrument is a UV+IR multi-laser enhanced Raman system capable of detecting complex, biologically-relevant molecular species mixed within icy surfaces in the outer Solar System. Incorporating two or more lasers with different excitation-emission pathways is crucial for thorough and definitive interpretation of the spectral fingerprints that identify unknown constituents within a sample. Our approach strives to remove fluorescence-driven ambiguities from degenerate, non-unique signatures expected for the most interesting trace constituents, i.e., those best revealed by UV excitation. Our design for deep-UV measurements is based on a novel high-reflectivity integrating cavity invented at Texas A&M University and further developed at SwRI. We report nanomole-range sensitivities of several complex organic molecules measured with our laboratory prototype cavities. Weak optical signals from Raman or fluorescence based instruments require sensitive low-noise detectors and long integration times, which by comparison are undesirable for the high radiation environment and limited battery power conditions anticipated for the Europa Lander mission. The two-to-five orders of magnitude enhanced sensitivity over standard Raman spectroscopy enabled by the integrating cavity enhanced spectroscopy technique makes it well suited for the Europa Lander payload and other future Ocean Worlds missions.

Residual pesticide detection on food with particle-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Ranjan, Bikas; Huang, LiChuan; Masui, Kyoko; Saito, Yuika; Verma, Prabhat

2014-08-01

Modern farming relies highly on pesticides to protect agricultural food items from insects for high yield and better quality. Increasing use of pesticide has raised concern about its harmful effects on human health and hence it has become very important to detect even small amount of pesticide residues. Raman spectroscopy is a suitable nondestructive method for pesticide detection, however, it is not very effective for low concentration of pesticide molecules. Here, we report an approach based on plasmonic enhancement, namely, particle enhanced Raman spectroscopy (PERS), which is rapid, nondestructive and sensitive. In this technique, Raman signals are enhanced via the resonance excitation of localized plasmons in metallic nanoparticles. Gold nanostructures are promising materials that have ability to tune surface plasmon resonance frequency in visible to near-IR, which depends on shape and size of nanostructures. We synthesized gold nanorods (GNRs) with desired shape and size by seed mediated growth method, and successfully detected very tiny amount of pesticide present on food items. We also conformed that the detection of pesticide was not possible by usual Raman spectroscopy.

Surface-Enhanced Raman Scattering Active Plasmonic Nanoparticles with Ultrasmall Interior Nanogap for Multiplex Quantitative Detection and Cancer Cell Imaging.

PubMed

Li, Jiuxing; Zhu, Zhi; Zhu, Bingqing; Ma, Yanli; Lin, Bingqian; Liu, Rudi; Song, Yanling; Lin, Hui; Tu, Song; Yang, Chaoyong

2016-08-02

Due to its large enhancement effect, nanostructure-based surface-enhanced Raman scattering (SERS) technology had been widely applied for bioanalysis and cell imaging. However, most SERS nanostructures suffer from poor signal reproducibility, which hinders the application of SERS nanostructures in quantitative detection. We report an etching-assisted approach to synthesize SERS-active plasmonic nanoparticles with 1 nm interior nanogap for multiplex quantitative detection and cancer cell imaging. Raman dyes and methoxy poly(ethylene glycol) thiol (mPEG-SH) were attached to gold nanoparticles (AuNPs) to prepare gold cores. Next, Ag atoms were deposited on gold cores in the presence of Pluronic F127 to form a Ag shell. HAuCl4 was used to etch the Ag shell and form an interior nanogap in Au@AgAuNPs, leading to increased Raman intensity of dyes. SERS intensity distribution of Au@AgAuNPs was found to be more uniform than that of aggregated AuNPs. Finally, Au@AgAuNPs were used for multiplex quantitative detection and cancer cell imaging. With the advantages of simple and rapid preparation of Au@AgAuNPs with highly uniform, stable, and reproducible Raman intensity, the method reported here will widen the applications of SERS-active nanoparticles in diagnostics and imaging.

Detection of nerve gases using surface-enhanced Raman scattering substrates with high droplet adhesion

NASA Astrophysics Data System (ADS)

Hakonen, Aron; Rindzevicius, Tomas; Schmidt, Michael Stenbæk; Andersson, Per Ola; Juhlin, Lars; Svedendahl, Mikael; Boisen, Anja; Käll, Mikael

2016-01-01

Threats from chemical warfare agents, commonly known as nerve gases, constitute a serious security issue of increasing global concern because of surging terrorist activity worldwide. However, nerve gases are difficult to detect using current analytical tools and outside dedicated laboratories. Here we demonstrate that surface-enhanced Raman scattering (SERS) can be used for sensitive detection of femtomol quantities of two nerve gases, VX and Tabun, using a handheld Raman device and SERS substrates consisting of flexible gold-covered Si nanopillars. The substrate surface exhibits high droplet adhesion and nanopillar clustering due to elasto-capillary forces, resulting in enrichment of target molecules in plasmonic hot-spots with high Raman enhancement. The results may pave the way for strategic life-saving SERS detection of chemical warfare agents in the field.Threats from chemical warfare agents, commonly known as nerve gases, constitute a serious security issue of increasing global concern because of surging terrorist activity worldwide. However, nerve gases are difficult to detect using current analytical tools and outside dedicated laboratories. Here we demonstrate that surface-enhanced Raman scattering (SERS) can be used for sensitive detection of femtomol quantities of two nerve gases, VX and Tabun, using a handheld Raman device and SERS substrates consisting of flexible gold-covered Si nanopillars. The substrate surface exhibits high droplet adhesion and nanopillar clustering due to elasto-capillary forces, resulting in enrichment of target molecules in plasmonic hot-spots with high Raman enhancement. The results may pave the way for strategic life-saving SERS detection of chemical warfare agents in the field. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06524k

Pterin detection using surface-enhanced Raman spectroscopy incorporating a straightforward silver colloid-based synthesis technique

NASA Astrophysics Data System (ADS)

Smyth, Ciarán A.; Mehigan, Sam; Rakovich, Yury P.; Bell, Steven E. J.; McCabe, Eithne M.

2011-07-01

Optical techniques toward the realization of sensitive and selective biosensing platforms have received considerable attention in recent times. Techniques based on interferometry, surface plasmon resonance, and waveguides have all proved popular, while spectroscopy in particular offers much potential. Raman spectroscopy is an information-rich technique in which the vibrational frequencies reveal much about the structure of a compound, but it is a weak process and offers poor sensitivity. In response to this problem, surface-enhanced Raman scattering (SERS) has received much attention, due to significant increases in sensitivity instigated by bringing the sample into contact with an enhancing substrate. Here we discuss a facile and rapid technique for the detection of pterins using SERS-active colloidal silver suspensions. Pterins are a family of biological compounds that are employed in nature in color pigmentation and as facilitators in metabolic pathways. In this work, small volumes of xanthopterin, isoxanthopterin, and 7,8-dihydrobiopterin have been examined while adsorbed to silver colloids. Limits of detection have been examined for both xanthopterin and isoxanthopterin using a 10-s exposure to a 12 mW 532 nm laser, which, while showing a trade-off between scan time and signal intensity, still provides the opportunity for the investigation of simultaneous detection of both pterins in solution.

Molecular structure, natural bond analysis, vibrational and electronic spectra, surface enhanced Raman scattering and Mulliken atomic charges of the normal modes of [Mn(DDTC)2] complex.

PubMed

Téllez S, Claudio A; Costa, Anilton C; Mondragón, M A; Ferreira, Glaucio B; Versiane, O; Rangel, J L; Lima, G Müller; Martin, A A

2016-12-05

Theoretical and experimental bands have been assigned for the Fourier Transform Infrared and Raman spectra of the bis(diethyldithiocarbamate)Mn(II) complex, [Mn(DDTC)2]. The calculations have been based on the DFT/B3LYP method, second derivative spectra and band deconvolution analysis. The UV-vis experimental spectra were measured in acetonitrile solution, and the calculated electronic spectrum was obtained using the TD/B3LYP method with 6-311G(d, p) basis set for all atoms. Charge transfer bands and those d-d spin forbidden were assigned in the UV-vis spectrum. The natural bond orbital analysis was carried out using the DFT/B3LYP method and the Mn(II) hybridization leading to the planar geometry of the framework was discussed. Surface enhanced Raman scattering (SERS) was also performed. Mulliken charges of the normal modes were obtained and related to the SERS enhanced bands. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, characterization, and 3D-FDTD simulation of Ag@SiO2 nanoparticles for shell-isolated nanoparticle-enhanced Raman spectroscopy.

PubMed

Uzayisenga, Viviane; Lin, Xiao-Dong; Li, Li-Mei; Anema, Jason R; Yang, Zhi-Lin; Huang, Yi-Fan; Lin, Hai-Xin; Li, Song-Bo; Li, Jian-Feng; Tian, Zhong-Qun

2012-06-19

Au-seed Ag-growth nanoparticles of controllable diameter (50-100 nm), and having an ultrathin SiO(2) shell of controllable thickness (2-3 nm), were prepared for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Their morphological, optical, and material properties were characterized; and their potential for use as a versatile Raman signal amplifier was investigated experimentally using pyridine as a probe molecule and theoretically by the three-dimensional finite-difference time-domain (3D-FDTD) method. We show that a SiO(2) shell as thin as 2 nm can be synthesized pinhole-free on the Ag surface of a nanoparticle, which then becomes the core. The dielectric SiO(2) shell serves to isolate the Raman-signal enhancing core and prevent it from interfering with the system under study. The SiO(2) shell also hinders oxidation of the Ag surface and nanoparticle aggregation. It significantly improves the stability and reproducibility of surface-enhanced Raman scattering (SERS) signal intensity, which is essential for SERS applications. Our 3D-FDTD simulations show that Ag-core SHINERS nanoparticles yield at least 2 orders of magnitude greater enhancement than Au-core ones when excited with green light on a smooth Ag surface, and thus add to the versatility of our SHINERS method.

Glucose oxidase probe as a surface-enhanced Raman scattering sensor for glucose.

PubMed

Qi, Guohua; Wang, Yi; Zhang, Biying; Sun, Dan; Fu, Cuicui; Xu, Weiqing; Xu, Shuping

2016-10-01

Glucose oxidase (GOx) possessing a Raman-active chromophore (flavin adenine dinucleotide) is used as a signal reporter for constructing a highly specific "turn off" surface-enhanced Raman scattering (SERS) sensor for glucose. This sensing chip is made by the electrostatic assembly of GOx over silver nanoparticle (Ag NP)-functionalized SERS substrate through a positively charged polyelectrolyte linker under the pH of 6.86. To trace glucose in blood serum, owing to the reduced pH value caused by the production of gluconic acid in the GOx-catalyzed oxidation reaction, the bonding force between GOx and polyelectrolyte weakens, making GOx drop off from the sensing chip. As a result, the SERS intensity of GOx on the chip decreases along with the concentration of glucose. This glucose SERS sensor exhibits excellent selectivity based on the specific GOx/glucose catalysis reaction and high sensitivity to 1.0 μM. The linear sensing range is 2.0-14.0 mM, which also meets the requirement on the working range of the human blood glucose detection. Using GOx as a probe shows superiority over other organic probes because GOx almost has no toxicity to the biological system. This sensing mechanism can be applied for intracellular in vivo SERS monitoring of glucose in the future. Graphical abstract Glucose oxidase is used as a Raman signal reporter for constructing a highly specific glucose surface-enhanced Raman scattering (SERS) sensor.

Structure-selective hot-spot Raman enhancement for direct identification and detection of trace penicilloic acid allergen in penicillin.

PubMed

Zhang, Liying; Jin, Yang; Mao, Hui; Zheng, Lei; Zhao, Jiawei; Peng, Yan; Du, Shuhu; Zhang, Zhongping

2014-08-15

Trace penicilloic acid allergen frequently leads to various fatal immune responses to many patients, but it is still a challenge to directly discriminate and detect its residue in penicillin by a chemosensing way. Here, we report that silver-coated gold nanoparticles (Au@Ag NPs) exhibit a structure-selective hot-spot Raman enhancement capability for direct identification and detection of trace penicilloic acid in penicillin. It has been demonstrated that penicilloic acid can very easily link Au@Ag NPs together by its two carboxyl groups, locating itself spontaneously at the interparticle of Au@Ag NPs to form strong Raman hot-spot. At the critical concentration inducing the nanoparticle aggregation, Raman-enhanced effect of penicilloic acid is ~60,000 folds higher than that of penicillin. In particular, the selective Raman enhancement to the two carboxyl groups makes the peak of carboxyl group at C6 of penicilloic acid appear as a new Raman signal due to the opening of β-lactam ring of penicillin. The surface-enhanced Raman scattering (SERS) nanoparticle sensor reaches a sensitive limit lower than the prescribed 1.0‰ penicilloic acid residue in penicillin. The novel strategy to examine allergen is more rapid, convenient and inexpensive than the conventional separation-based assay methods. Copyright © 2014 Elsevier B.V. All rights reserved.

M-shaped grating by nanoimprinting: a replicable, large-area, highly active plasmonic surface-enhanced Raman scattering substrate with nanogaps.

PubMed

Zhu, Zhendong; Bai, Benfeng; Duan, Huigao; Zhang, Haosu; Zhang, Mingqian; You, Oubo; Li, Qunqing; Tan, Qiaofeng; Wang, Jia; Fan, Shoushan; Jin, Guofan

2014-04-24

Plasmonic nanostructures separated by nanogaps enable strong electromagnetic-field confinement on the nanoscale for enhancing light-matter interactions, which are in great demand in many applications such as surface-enhanced Raman scattering (SERS). A simple M-shaped nanograting with narrow V-shaped grooves is proposed. Both theoretical and experimental studies reveal that the electromagnetic field on the surface of the M grating can be pronouncedly enhanced over that of a grating without such grooves, due to field localization in the nanogaps formed by the narrow V grooves. A technique based on room-temperature nanoimprinting lithography and anisotropic reactive-ion etching is developed to fabricate this device, which is cost-effective, reliable, and suitable for fabricating large-area nanostructures. As a demonstration of the potential application of this device, the M grating is used as a SERS substrate for probing Rhodamine 6G molecules. Experimentally, an average SERS enhancement factor as high as 5×10⁸ has been achieved, which verifies the greatly enhanced light-matter interaction on the surface of the M grating over that of traditional SERS surfaces. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Raman Techniques for Imaging and Sensing

NASA Astrophysics Data System (ADS)

Edwards, Perry S.

Raman scattering spectroscopy is extensively demonstrated as a label-free, chemically selective sensing and imaging technique for a multitude of chemical and biological applications. The ability to detect "fingerprint" spectral signatures of individual molecules, without the need to introduce chemical labelers, makes Raman scattering a powerful sensing technique. However, spectroscopy based on spontaneous Raman scattering traditionally suffers from inherently weak signals due to small Raman scattering cross-sections. Thus, considerable efforts have been put forth to find pathways towards enhancing Raman signals to bolster sensitivity for detecting small concentrations of molecules or particles. The development of coherent Raman techniques that can offer orders of magnitude increase in signal have garnered significant interest in recent years for their application in imaging; such techniques include coherent anti-Stokes Raman scattering and stimulated Raman scattering. Additionally, methods to enhance the local field of either the pump or generated Raman signal, such as through surface enhanced Raman scattering, have been investigated for their orders of magnitude improvement in sensitivity and single molecule sensing capability. The work presented in this dissertation describes novel techniques for performing high speed and highly sensitive Raman imaging as well as sensing applications towards bioimaging and biosensing. Coherent anti-Stokes Raman scattering (CARS) is combined with holography to enable recording of high-speed (single laser shot), wide field CARS holograms which can be used to reconstruct the both the amplitude and the phase of the anti-Stokes field therefore allowing 3D imaging. This dissertation explores CARS holography as a viable label-free bio-imaging technique. A Raman scattering particle sensing system is also developed that utilizes wave guide properties of optical fibers and ring-resonators to perform enhanced particle sensing. Resonator-enhanced particle sensing is experimentally examined as a new method for enhancing Raman scattering from particles interacting with circulating optical fields within both a fiber ring-cavity and whispering gallery mode microtoroid microresonators. The achievements described in this dissertation include: (1) Demonstration of the bio-imaging capability of CARS holography by recording of CARS holograms of subcellular components in live cancer (HeLa) cells. (2) Label-free Raman microparticle sensing using a tapered optical fibers. A tapered fiber can guide light to particles adsorbed on the surface of the taper to generate scattered Raman signal which can be collected by a microRaman detection system. (3) Demonstration of the proof of concept of resonator-enhanced Raman spectroscopy in a fiber ring resonator consisting of a section of fiber taper. (4) A method for locking the pump laser to the resonate frequencies of a resonator. This is demonstrated using a fiber ring resonator and microtoroid microresonators. (5) Raman scattered signal from particles adhered to microtoroid microresonators is acquired using 5 seconds of signal integration time and with the pump laser locked to a cavity resonance. (6) Theoretical analysis is performed that indicates resonator-enhanced Raman scattering from microparticles adhered to microresonators can be achieved with the pump laser locked to the frequency of a high-Q cavity resonant mode.

Physical chemistry of Nanogap-Enhanced Raman Scattering (NERS)

NASA Astrophysics Data System (ADS)

Suh, Yung Doug; Kim, Hyun Woo

2017-08-01

Plasmonically coupled electromagnetic field localization has generated a variety of new concepts and applications, and this has been one of the hottest topics in nanoscience, materials science, chemistry, physics and engineering and increasingly more important over the last decade. In particular, plasmonically coupled nanostructures with ultra-small gap ( 1-nm or smaller) gap have been of special interest due to their ultra-strong optical properties that can be useful for a variety of signal enhancements such surface-enhanced Raman scattering (SERS) and nanoantenna. These promising nanostructures with extraordinarily strong optical signal, however, have rendered a limited success in widespread use and commercialization largely due to the lack of designing principles, high-yield synthetic strategies with nm-level structural controllability and reproducibility and lack of systematic single-molecule and single-particle level studies. All these are extremely important challenges because even small changes ( 1 nm) of the coupled nanogap structures can significant affect plasmon mode and signal intensity and therefore structural and signal reproducibility and controllability can be in question. The plasmonic nanogap-enhanced Raman scattering (NERS) is defined as the plasmonic nanogap-based Raman signal enhancement within plasmonic nanogap particles with 1 nm gap and a Raman dye positioned inside the gap.

Surface-Enhanced Raman Spectroscopy of Carbon Nanomembranes from Aromatic Self-Assembled Monolayers.

PubMed

Zhang, Xianghui; Mainka, Marcel; Paneff, Florian; Hachmeister, Henning; Beyer, André; Gölzhäuser, Armin; Huser, Thomas

2018-02-27

Surface-enhanced Raman scattering spectroscopy (SERS) was employed to investigate the formation of self-assembled monolayers (SAMs) of biphenylthiol, 4'-nitro-1,1'-biphenyl-4-thiol, and p-terphenylthiol on Au surfaces and their structural transformations into carbon nanomembranes (CNMs) induced by electron irradiation. The high sensitivity of SERS allows us to identify two types of Raman scattering in electron-irradiated SAMs: (1) Raman-active sites exhibit similar bands as those of pristine SAMs in the fingerprint spectral region, but with indications of an amorphization process and (2) Raman-inactive sites show almost no Raman-scattering signals, except a very weak and broad D band, indicating a lack of structural order but for the presence of graphitic domains. Statistical analysis showed that the ratio of the number of Raman-active sites to the total number of measurement sites decreases exponentially with increasing the electron irradiation dose. The maximum degree of cross-linking ranged from 97 to 99% for the three SAMs. Proof-of-concept experiments were conducted to demonstrate potential applications of Raman-inactive CNMs as a supporting membrane for Raman analysis.

Surface enhanced raman spectroscopy technique in rapid detection of live and dead salmonella cells

USDA-ARS?s Scientific Manuscript database

Many research proved that Surface Enhanced Raman Spectroscopy (SERS) can detect pathogens rapidly and accurately. In this study, a silver metal substrate was used for the selected common food pathogen Salmonella typhimurium bacteria. Nano silver rods were deposited on a thin titanium coating over t...

Stable silver/biopolymer hybrid plasmonic nanostructures for high performance surface enhanced raman scattering (SERS)

USDA-ARS?s Scientific Manuscript database

Silver/biopolymer nanoparticles were prepared by adding 100 mg silver nitrate to 2% polyvinyl alcohol solution and reduced the silver nitrate into silver ion using 2 % trisodium citrate for high performance Surface Enhanced Raman Scattering (SERS) substrates. Optical properties of nanoparticle were ...

Surface-Enhanced Raman Optical Data Storage system

DOEpatents

Vo-Dinh, T.

1991-03-12

A method and apparatus for a Surface-Enhanced Raman Optical Data Storage (SERODS) System are disclosed. A medium which exhibits the Surface Enhanced Raman Scattering (SERS) phenomenon has data written onto its surface of microenvironment by means of a write-on procedure which disturbs the surface or microenvironment of the medium and results in the medium having a changed SERS emission when excited. The write-on procedure is controlled by a signal that corresponds to the data to be stored so that the disturbed regions on the storage device (e.g., disk) represent the data. After the data is written onto the storage device it is read by exciting the surface of the storage device with an appropriate radiation source and detecting changes in the SERS emission to produce a detection signal. The data is then reproduced from the detection signal. 5 figures.

Surface-enhanced raman optical data storage system

DOEpatents

Vo-Dinh, Tuan

1991-01-01

A method and apparatus for a Surface-Enhanced Raman Optical Data Storage (SERODS) System is disclosed. A medium which exhibits the Surface Enhanced Raman Scattering (SERS) phenomenon has data written onto its surface of microenvironment by means of a write-on procedure which disturbs the surface or microenvironment of the medium and results in the medium having a changed SERS emission when excited. The write-on procedure is controlled by a signal that corresponds to the data to be stored so that the disturbed regions on the storage device (e.g., disk) represent the data. After the data is written onto the storage device it is read by exciting the surface of the storage device with an appropriate radiation source and detecting changes in the SERS emission to produce a detection signal. The data is then reproduced from the detection signal.

Paper-based microfluidic approach for surface-enhanced raman spectroscopy and highly reproducible detection of proteins beyond picomolar concentration.

PubMed

Saha, Arindam; Jana, Nikhil R

2015-01-14

Although microfluidic approach is widely used in various point of care diagnostics, its implementation in surface enhanced Raman spectroscopy (SERS)-based detection is challenging. This is because SERS signal depends on plasmonic nanoparticle aggregation induced generation of stable electromagnetic hot spots and in currently available microfluidic platform this condition is difficult to adapt. Here we show that SERS can be adapted using simple paper based microfluidic system where both the plasmonic nanomaterials and analyte are used in mobile phase. This approach allows analyte induced controlled particle aggregation and electromagnetic hot spot generation inside the microfluidic channel with the resultant SERS signal, which is highly reproducible and sensitive. This approach has been used for reproducible detection of protein in the pico to femtomolar concentration. Presented approach is simple, rapid, and cost-effective, and requires low sample volume. Method can be extended for SERS-based detection of other biomolecules.

Paper-based surfaced enhanced Raman spectroscopy for drug level testing with tear fluid

NASA Astrophysics Data System (ADS)

Yamada, Kenji; Yokoyama, Moe; Jeong, Hieyong; Kido, Michiko; Ohno, Yuko

2015-07-01

The purpose of this study was to show the effectiveness of therapeutic drug level testing by Paper-based Surfaced Enhanced Raman Spectroscopy (PSERS) for artificial lacrimal fluid. We have been used substrates which consist of a common filter paper and gold nano-rods. The targets were Phenobarbital (PB) which dissolved in artificial lacrimal fluid. We measured them using PSERS which the wavelength was 785nm, the power was 30mW. It was found that there were the strong peaks of PB at 997cm-1 and 1026cm-1 which corresponded with solid PB spectral peak for 1mM artificial lacrimal fluid. The results demonstrated the usefulness of this method. It is concluded that our method for therapeutic drug level testing is very efficient.

A Colloidal Route to Detection of Organic Molecules Based on Surface-Enhanced Raman Spectroscopy Using Nanostructured Substrate Derived from Aerosols

NASA Astrophysics Data System (ADS)

Gen, Masao; Kakuta, Hideo; Kamimoto, Yoshihito; Wuled Lenggoro, I.

2011-06-01

A detection method based on the surface-enhanced Raman spectroscopy (SERS)-active substrate derived from aerosol nanoparticles and a colloidal suspension for detecting organic molecules of a model analyte (a pesticide) is proposed. This approach can detect the molecules of the derived from its solution with the concentration levels of ppb. For substrate fabrication, a gas-phase method is used to directly deposit Ag nanoparticles on to a silicon substrate having pyramidal structures. By mixing the target analyte with a suspension of Ag colloids purchased in advance, clotianidin analyte on Ag colloid can exist in junctions of co-aggregated Ag colloids. Using (i) a nanostructured substrate made from aerosol nanoparticles and (ii) colloidal suspension can increase the number of activity spots.

Surface-enhanced Raman scattering (SERS) spectra of sodium benzoate and 4-picoline in Ag colloids prepared by γ-irradiation

NASA Astrophysics Data System (ADS)

Choi, Seong-Ho; Park, Hyun Gyu

2005-04-01

PVP-protected silver colloids were prepared by γ-irradiation and chemical reduction method. Surface-enhanced Raman scattering (SERS) spectra of sodium benzoate and 4-picoline in Ag colloids prepared by γ-irradiation were recorded. The SERS spectra of sodium benzoate were successfully recorded in Ag colloids, whereas the Raman spectra did not appear without Ag colloids. The Raman spectra of 4-picoline were not detected without Ag colloids, while the SERS spectra of 4-picoline were increased by adding Ag colloids. The carboxylate group of sodium benzoate and N donor of 4-picoline were adsorbed on the surface of Ag nanoparticles.

Geometry of GLP on silver surface by surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bao, PeiDi; Bao, Lang; Huang, TianQuan; Liu, XinMing; Wu, GuoFeng

2000-05-01

Leptospirosis is one of the most harmful zoonosis, it is a serious public health issue in some area of Sichuan province. Surface-Enhance Raman Scattering (SERS) Spectroscopy is an effective approach for the study of biomolecular adsorption on metal surface and provides information about the adsorbed species. Two samples of Leptospiral Glycolipoprotein (GLP-1) and GLP-2 which have different toxic effects have been obtained and investigated.

Extracting Optical Fiber Background from Surface-Enhanced Raman Spectroscopy Spectra Based on Bi-Objective Optimization Modeling.

PubMed

Huang, Jie; Shi, Tielin; Tang, Zirong; Zhu, Wei; Liao, Guanglan; Li, Xiaoping; Gong, Bo; Zhou, Tengyuan

2017-08-01

We propose a bi-objective optimization model for extracting optical fiber background from the measured surface-enhanced Raman spectroscopy (SERS) spectrum of the target sample in the application of fiber optic SERS. The model is built using curve fitting to resolve the SERS spectrum into several individual bands, and simultaneously matching some resolved bands with the measured background spectrum. The Pearson correlation coefficient is selected as the similarity index and its maximum value is pursued during the spectral matching process. An algorithm is proposed, programmed, and demonstrated successfully in extracting optical fiber background or fluorescence background from the measured SERS spectra of rhodamine 6G (R6G) and crystal violet (CV). The proposed model not only can be applied to remove optical fiber background or fluorescence background for SERS spectra, but also can be transferred to conventional Raman spectra recorded using fiber optic instrumentation.

Transparent, flexible surface enhanced Raman scattering substrates based on Ag-coated structured PET (polyethylene terephthalate) for in-situ detection

NASA Astrophysics Data System (ADS)

Zuo, Zewen; Zhu, Kai; Gu, Chuan; Wen, Yibing; Cui, Guanglei; Qu, Jun

2016-08-01

Transparent, flexible surface-enhanced Raman scattering (SERS) substrates were fabricated by metalization of structured polyethylene terephthalate (PET) sheets. The resultant Ag-coated structured PET SERS substrates were revealed to be highly sensitive with good reproducibility and stability, an enhancement factor of 3 × 106 was acquired, which can be attributed mainly to the presence of plentiful multiple-type hot spots within the quasi-three-dimensional surface of the structured PET obtained by oxygen plasma etching. In addition, detections of model molecules on fruit skin were also carried out, demonstrating the great potential of the Ag-coated structured PET in in-situ detection of analyte on irregular objects. Importantly, the technique used for the preparation of such substrate is completely compatible with well-established silicon device technologies, and large-area fabrication with low cost can be readily realized.

Effect of film thickness on localized surface plasmon enhanced chemical sensor

NASA Astrophysics Data System (ADS)

Kassu, Aschalew; Farley, Carlton; Sharma, Anup; Kim, Wonkyu; Guo, Junpeng

2014-05-01

A highly-sensitive, reliable, simple and inexpensive chemical detection and identification platform is demonstrated. The sensing technique is based on localized surface plasmon enhanced Raman scattering measurements from gold-coated highly-ordered symmetric nanoporous ceramic membranes fabricated from anodic aluminum oxide. To investigate the effects of the thickness of the sputter-coated gold films on the sensitivity of sensor, and optimize the performance of the substrates, the geometry of the nanopores and the film thicknesses are varied in the range of 30 nm to 120 nm. To characterize the sensing technique and the detection limits, surface enhanced Raman scatterings of low concentrations of a standard chemical adsorbed on the gold coated substrates are collected and analyzed. The morphology of the proposed substrates is characterized by atomic force microscopy and the optical properties including transmittance, reflectance and absorbance of each substrate are also investigated.

Potential drug - nanosensor conjugates: Raman, infrared absorption, surface - enhanced Raman, and density functional theory investigations of indolic molecules

NASA Astrophysics Data System (ADS)

Pięta, Ewa; Paluszkiewicz, Czesława; Oćwieja, Magdalena; Kwiatek, Wojciech M.

2017-05-01

An extremely important aspect of planning cancer treatment is not only the drug efficiency but also a number of challenges associated with the side effects and control of this process. That is why it is worth paying attention to the promising potential of the gold nanoparticles combined with a compound treated as a potential drug. This work presents Raman (RS), infrared absorption (IR) and surface-enhanced Raman scattering (SERS) spectroscopic investigations of N-acetyl-5-methoxytryptamine (melatonin) and α-methyl-DL-tryptophan, regarding as anti breast cancer agents. The experimental spectroscopic analysis was supported by the quantum-chemical calculations based on the B3LYP hybrid density functional theory (DFT) at the B3LYP 6-311G(d,p) level of theory. The studied compounds were adsorbed onto two colloidal gold nanosensors synthesized by a chemical reduction method using sodium borohydride (SB) and trisodium citrate (TC), respectively. Its morphology characteristics were obtained using transmission electron microscopy (TEM). It has been suggested that the NH moiety from the aromatic ring, a well-known proton donor, causes the formation of hydrogen bonds with the negatively charged gold surface.

Development of a drug assay using surface-enhanced Raman spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Angel, S.M.; Roe, J.N.; Andresen, B.D.

1990-05-01

Surface-enhanced Raman spectroscopy has been used to detect low levels of several chemical compounds, including the drugs of abuse -- cocaine hydrochloride and methamphetamine hydrochloride. Raman spectra of these substances have also been taken over optical fibers using red-wavelength excitation. These measurements demonstrate the feasibility of the remote red-wavelength excitation. These measurements demonstrate the feasibility of the remote determination of various target chemicals using diode excitation and diode array detection. 5 refs., 5 figs.

Surface-enhanced Raman spectroscopy of half-mustard agent.

PubMed

Stuart, Douglas A; Biggs, Kevin B; Van Duyne, Richard P

2006-04-01

The detection and identification of chemical warfare agents is an important analytical goal. Herein, it is demonstrated that 2-chloroethyl ethyl sulfide (half-mustard, CEES) can be successfully analysed using surface-enhanced Raman spectroscopy (SERS). A critical component in this detection system is the fabrication of a robust, yet highly enhancing, sensor surface. Recent advances in substrate fabrication and in the fundamental understanding of the SERS phenomenon enable the development of improved substrates for practical SERS applications.

Surface enhanced Raman scattering on Tardigrada--towards monitoring and imaging molecular structures in live cryptobiotic organisms.

PubMed

Kneipp, Harald; Møbjerg, Nadja; Jørgensen, Aslak; Bohr, Henrik G; Hélix-Nielsen, Claus; Kneipp, Janina; Kneipp, Katrin

2013-10-01

Tardigrades are microscopic metazoans which are able to survive extreme physical and chemical conditions by entering a stress tolerant state called cryptobiosis. At present, the molecular mechanisms behind cryptobiosis are still poorly understood. We show that surface enhanced Raman scattering supported by plasmonic gold nanoparticles can measure molecular constituents and their local distribution in live tardigrades. Surface enhanced Raman signatures allow to differentiate between two species and indicate molecular structural differences between tardigrades in water and in a dry state. This opens new avenues for exploring cryptobiosis by studying molecular changes in live cryptobiotic organisms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size-dependent surface-enhanced Raman scattering of sodium benzoate on Silver nanoparticles

NASA Astrophysics Data System (ADS)

Badr, Y.; Mahmoud, M. A.

2005-07-01

The absorption spectrum of silver nanoparticles (Ag NPs) with different size and the transmission electron microscopy (TEM) was recorded. Surface-enhanced Raman scattering (SERS) spectra of Sodium Benzoate (SB) adsorbed on Ag NPs with different particle size were studied. The carboxylic group bands were enhanced as the particle size decreases due to the chemisorption of SB on the Ag NPs through it in which the carboxyl group was perpendicular to the surface and the benzene ring parallel to the surface; the SB bands were enhanced as the coverage density of Ag NPs increased.

Self-assembly of silver nanoparticles as high active surface-enhanced Raman scattering substrate for rapid and trace analysis of uranyl(VI) ions

NASA Astrophysics Data System (ADS)

Wang, Shaofei; Jiang, Jiaolai; Wu, Haoxi; Jia, Jianping; Shao, Lang; Tang, Hao; Ren, Yiming; Chu, Mingfu; Wang, Xiaolin

2017-06-01

A facile surface-enhanced Raman scattering (SERS) substrate based on the self-assembly of silver nanoparticles on the modified silicon wafer was obtained, and for the first time, an advanced SERS analysis method basing on this as-prepared substrate was established for high sensitive and rapid detection of uranyl ions. Due to the weakened bond strength of Odbnd Udbnd O resulting from two kinds of adsorption of uranyl species (;strong; and ;weak; adsorption) on the substrate, the ν1 symmetric stretch vibration frequency of Odbnd Udbnd O shifted from 871 cm- 1 (normal Raman) to 720 cm- 1 and 826 cm- 1 (SERS) along with significant Raman enhancement. Effects of the hydrolysis of uranyl ions on SERS were also investigated, and the SERS band at 826 cm- 1 was first used to approximately define the constitution of uranyl species at trace quantity level. Besides, the SERS intensity was proportional to the variable concentrations of uranyl nitrate ranging from 10- 7 to 10- 3 mol L- 1 with an excellent linear relation (R2 = 0.998), and the detection limit was 10- 7 mol L- 1. Furthermore, the related SERS approach involves low-cost substrate fabrication, rapid and trace analysis simultaneously, and shows great potential applications for the field assays of uranyl ions in the nuclear fuel cycle and environmental monitoring.

SERS on paper: an extremely low cost technique to measure Raman signal

NASA Astrophysics Data System (ADS)

Chamuah, Nabadweep; Hazarika, Anil; Hatiboruah, Diganta; Nath, Pabitra

2017-12-01

Finding a low cost substrate for surface-enhanced Raman spectroscopy (SERS) yielding enhanced, reproducible Raman signal from Raman active samples has been a longstanding goal for researchers for years. Herein, we demonstrate the fabrication of such a SERS substrate from paper. The proposed paper-based SERS substrate was developed by attaching polyvinylpyrrolidone (PVP) capped silver nano-particles (AgNPs) to printing grade paper. The performance of the substrate has been evaluated for paper substrates of various grades (in grams per square meter; GSM). The usability of the developed substrate for detection of two Raman active samples—namely, malachite green (MG) and rhodamine6G (R6G)—is reported. In addition to these samples, the reproducibility of the designed substrate has been evaluated for 1,2-bis(4-pyridyl)ethylene (BPE); a good degree of reproducibility was observed. Finally, applicability of the proposed substrate for reliable detection of Raman signals from two more important samples—namely, glucose and urine—has been successfully demonstrated.

Surface-enhanced Raman detection of CW agents in water using gold sol gel substrates

NASA Astrophysics Data System (ADS)

Premasiri, W. Ranjith; Clarke, Richard H.; Womble, M. Edward

2002-02-01

The development of a water analysis system capable of detecting both inanimate trace chemical contaminants and viable microbial contaminants has long been a project of interest to our group. The capability of detecting both chemical and biological agent sources in a single device configuration would clearly add to the value of such a product. In the present work, we describe results with chemical warfare agents from our efforts to produce a Raman system for the detection of both chemical and biological warfare agents in water. We utilize laser Raman light scattering and employ Surface Enhanced Raman Spectroscopy (SERS)on solid state gold sol-gel detectors combined with fiber optic collection of the enhanced light signal in the sampling system to augment the normally low intensity Raman Scattering signal from trace materials.

High-Sensitivity Surface-Enhanced Raman Scattering (SERS) Substrate Based on a Gold Colloid Solution with a pH Change for Detection of Trace-Level Polycyclic Aromatic Hydrocarbons in Aqueous Solution.

PubMed

Shi, Xiaofeng; Liu, Shu; Han, Xiaohong; Ma, Jun; Jiang, Yongchao; Yu, Guifeng

2015-05-01

In this study, a gold colloid solution whose parameters were optimized, and without any surfactants, was developed as a surface-enhanced Raman scattering (SERS) substrate for the detection of trace-level polycyclic aromatic hydrocarbons (PAHs). A gold colloid solution with 57 nm gold particles and pH 13 was prepared to be the SERS substrate. It had impressive enhancement that was two orders of magnitude higher than that of a gold colloid solution with 57 nm gold particles and without pH change (pH 6). Even with a compact field-based Raman spectrometer, naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene were detected, with limits of detection at 6.8 nM, 3.4 nM, 1.8 nM, 0.68 nM (680 pM), and 0.44 nM (440 pM), respectively. The significant enhancement was ascribed to an electromagnetic mechanism and a charge-transfer mechanism. Quantitative analyses for these five PAHs in water were also performed. The SERS intensities of PAHs were found to have good linear dependence relations with the concentrations in low concentration. This high-sensitivity, easily prepared substrate offers a promising technology for the quantitative detection of trace-level PAHs.

Quick detection of traditional Chinese medicine ‘Atractylodis Macrocephalae Rhizoma’ pieces by surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Hao; Shi, Hong; Feng, Shangyuan; Lin, Juqiang; Chen, Weiwei; Yu, Yun; Lin, Duo; Xu, Qian; Chen, Rong

2013-01-01

A surface-enhanced Raman spectroscopy (SERS) method was developed for the analysis of traditional Chinese medicine ‘Atractylodis Macrocephalae Rhizoma’ pieces (AMRP) for the first time with the aim to develop a quick method for traditional Chinese medicine detection. Both Raman spectra and SERS spectra were obtained from AMRP, and tentative assignments of the Raman bands in the measured spectra suggested that only a few weak Raman peaks could be observed in the regular Raman spectra, while primary Raman peaks at around 536, 555, 619, 648, 691, 733, 790, 958, 1004, 1031, 1112, 1244, 1324, 1395, 1469, 1574 and 1632 cm-1 could be observed in the SERS spectra, with the strongest signals at 619, 733, 958, 1324, 1395 and 1469 cm-1. This was due to a strong interaction between the silver colloids and the AMRP, which led to an extraordinary enhancement in the intensity of the Raman scattering in AMRP. This exploratory study suggests the SERS technique has great potential for providing a novel non-destructive method for effectively and accurately detecting traditional Chinese medicine without complicated separation and extraction.

Surface-enhanced Raman spectroscopy using 2D plasmons of InN nanostructures

NASA Astrophysics Data System (ADS)

Madapu, Kishore K.; Dhara, Sandip

2018-06-01

We explored the surface-enhanced Raman scattering (SERS) activity of the InN nanostructures, possessing surface electron accumulation (SEA), using the Rhodamine 6G (R6G) molecules. SERS enhancement is observed for the InN nanostructures which possess SEA. In case of high-temperature grown InN samples, a peak is observed in the low wave number (THz region) of Raman spectra of InN nanostructures originating from excitation of the two-dimensional (2D) plasmons of the SEA. The enhancement factor of four orders was calculated with the assumption of monolayer coverage of analyte molecule. SERS enhancement of InN nanostructures is attributed to the 2D plasmonic nature of InN nanostructures invoking SEA, rather than the contributions from 3D surface plasmon resonance and chemical interaction. The role of 2D plasmon excitation in SERS enhancement is corroborated by the near-field light-matter interaction studies using near-field scanning optical microscopy.

Application of surface enhanced Raman scattering and competitive adaptive reweighted sampling on detecting furfural dissolved in transformer oil

NASA Astrophysics Data System (ADS)

Chen, Weigen; Zou, Jingxin; Wan, Fu; Fan, Zhou; Yang, Dingkun

2018-03-01

Detecting the dissolving furfural in mineral oil is an essential technical method to evaluate the ageing condition of oil-paper insulation and the degradation of mechanical properties. Compared with the traditional detection method, Raman spectroscopy is obviously convenient and timesaving in operation. This study explored the method of applying surface enhanced Raman scattering (SERS) on quantitative analysis of the furfural dissolved in oil. Oil solution with different concentration of furfural were prepared and calibrated by high-performance liquid chromatography. Confocal laser Raman spectroscopy (CLRS) and SERS technology were employed to acquire Raman spectral data. Monte Carlo cross validation (MCCV) was used to eliminate the outliers in sample set, then competitive adaptive reweighted sampling (CARS) was developed to select an optimal combination of informative variables that most reflect the chemical properties of concern. Based on selected Raman spectral features, support vector machine (SVM) combined with particle swarm algorithm (PSO) was used to set up a furfural quantitative analysis model. Finally, the generalization ability and prediction precision of the established method were verified by the samples made in lab. In summary, a new spectral method is proposed to quickly detect furfural in oil, which lays a foundation for evaluating the ageing of oil-paper insulation in oil immersed electrical equipment.

Probing the adsorption mechanism in thiamazole bound to the silver surface with Surface-enhanced Raman Scattering and DFT

NASA Astrophysics Data System (ADS)

Biswas, Nandita; Thomas, Susy; Sarkar, Anjana; Mukherjee, Tulsi; Kapoor, Sudhir

2009-09-01

Surface-enhanced Raman scattering (SERS) of thiamazole have been investigated in aqueous solution. Thiamazole is an important anti-thyroid drug that is used in the treatment of hyperthyroidism (over activity of the thyroid gland). Due to its medicinal importance, the surface adsorption properties of thiamazole have been studied. The experimental Raman and SERS data are supported with DFT calculations using B3LYP functional with LANL2DZ basis set. From the SERS spectra as well as theoretical calculations, it has been inferred that thiamazole is chemisorbed to the silver surface directly through the sulphur atom and the ring N atom, with a tilted orientation.

Exceptional enhancement of Raman scattering on silver chlorobromide nanocube photonic crystals: chemical and photonic contributions

DOE PAGES

Li, Zheng; Gosztola, David J.; Sun, Cheng-Jun; ...

2015-02-02

Photonic crystals made from self-assembly of mono-dispersed AgCl xBr 1-x nanocubes, which are not plasmonically active, have been discovered to exceptionally enhance Raman scattering of molecules chemically adsorbed on their surfaces. Comprehensive control measurements and X-ray absorption near-edge structure spectroscopy indicate that the Raman enhancement on the AgCl xBr 1-x nanocube photonic crystals is primarily ascribed to the chemical enhancement mechanism associated with the chemical interactions between adsorbing molecules and the AgCl xBr 1-x surfaces. In addition, the ordering of the AgCl xBr 1-x nanocubes in the photonic crystals can selectively reflect Raman scattering back to the detector at themore » bandgap position of the photonic crystals to provide additional enhancement, i.e., photonic mode enhancement. The thiophenol molecules adsorbed on the AgCl 0.44Br 0.56 nanocube photonic crystals exhibit astonishingly strong Raman signals that are on the same order of magnitude as those recorded from the thiophenol molecules adsorbed on the assembled Ag nanocubes.« less

Practical substrate and apparatus for static and continuous monitoring by surface-enhanced raman spectroscopy

DOEpatents

Vo-Dinh, Tuan

1987-01-01

A substrate for use in surface-enhanced Raman spectroscopy (SERS) is disclosed, comprising a support, preferably flexible, coated with roughness-imparting microbodies and a metallized overcoating. Also disclosed is apparatus for using the aforesaid substrate in continuous and static SERS trace analyses, especially of organic compounds.

Investigation of surface enhanced Raman spectroscopy for hemozoin detection in malaria diagnosis

NASA Astrophysics Data System (ADS)

Chen, Keren; Xiong, Aoli; Yuen, Clement; Preiser, Peter; Liu, Quan

2016-03-01

We report two methods of surface enhanced Raman spectroscopy (SERS) for hemozoin detection in malaria infected human blood. In the first method, silver nanoparticles were synthesized separately and then mixed with lysed blood; while in the second method, silver nanoparticles were synthesized directly inside the parasites of Plasmodium falciparum.

Near-Ir surface-enhanced Raman spectrum of lignin

Treesearch

Umesh P. Agarwal; Richard S. Reiner

2009-01-01

Compacted powders of commercially available nano- and microparticles of silver were used to successfully induce the surface enhanced Raman scattering (SERS) effect in spruce milled-wood lignin (MWL). For the two silver particle sizes used in this investigation, the spectra were mostly similar. Some general characteristics of the lignin SERS spectrum are described. The...

Distinction of gastric cancer tissue based on surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ma, Jun; Zhou, Hanjing; Gong, Longjing; Liu, Shu; Zhou, Zhenghua; Mao, Weizheng; Zheng, Rong-er

2012-12-01

Gastric cancer is one of the most common malignant tumors with high recurrence rate and mortality rate in China. This study aimed to evaluate the diagnostic capability of Surface-enhanced Raman spectroscopy (SERS) based on gold colloids for distinguishing gastric tissues. Gold colloids were directly mixed with the supernatant of homogenized tissues to heighten the Raman signal of various biomolecule. A total of 56 samples were collected from normal (30) and cancer (26). Raman spectra were obtained with a 785nm excitation in the range of 600-1800 cm-1. Significant spectral differences in SERS mainly belong to nucleic acid, proteins and lipids, particularly in the range of 653, 726, 828, 963, 1004, 1032, 1088, 1130, 1243, 1369, 1474, 1596, 1723 cm-1. PCA-LDA algorithms with leave-one-patient-out cross validation yielded diagnostic sensitivities of 90% (27/30), specificities of 88.5% (23/26), and accuracy of 89.3% (50/56), for classification of normal and cancer tissues. The receiver operating characteristic (ROC) surface is 0.917, illustrating the diagnostic utility of SERS together with PCA-LDA to identify gastric cancer from normal tissue. This work demonstrated the SERS techniques can be useful for gastric cancer detection, and it is also a potential technique for accurately identifying cancerous tumor, which is of considerable clinical importance to real-time diagnosis.

Raman microspectroscopy, surface-enhanced Raman scattering microspectroscopy, and stable-isotope Raman microspectroscopy for biofilm characterization.

PubMed

Ivleva, Natalia P; Kubryk, Patrick; Niessner, Reinhard

2017-07-01

Biofilms represent the predominant form of microbial life on our planet. These aggregates of microorganisms, which are embedded in a matrix formed by extracellular polymeric substances, may colonize nearly all interfaces. Detailed knowledge of microorganisms enclosed in biofilms as well as of the chemical composition, structure, and functions of the complex biofilm matrix and their changes at different stages of the biofilm formation and under various physical and chemical conditions is relevant in different fields. Important research topics include the development and improvement of antibiotics and medical devices and the optimization of biocides, antifouling strategies, and biological wastewater treatment. Raman microspectroscopy is a capable and nondestructive tool that can provide detailed two-dimensional and three-dimensional chemical information about biofilm constituents with the spatial resolution of an optical microscope and without interference from water. However, the sensitivity of Raman microspectroscopy is rather limited, which hampers the applicability of Raman microspectroscopy especially at low biomass concentrations. Fortunately, the resonance Raman effect as well as surface-enhanced Raman scattering can help to overcome this drawback. Furthermore, the combination of Raman microspectroscopy with other microscopic techniques, mass spectrometry techniques, or particularly with stable-isotope techniques can provide comprehensive information on monospecies and multispecies biofilms. Here, an overview of different Raman microspectroscopic techniques, including resonance Raman microspectroscopy and surface-enhanced Raman scattering microspectroscopy, for in situ detection, visualization, identification, and chemical characterization of biofilms is given, and the main feasibilities and limitations of these techniques in biofilm research are presented. Future possibilities of and challenges for Raman microspectroscopy alone and in combination with other analytical techniques for characterization of complex biofilm matrices are discussed in a critical review. Graphical Abstract Applicability of Raman microspectroscopy for biofilm analysis.

Raman enhancement by graphene-Ga2O3 2D bilayer film.

PubMed

Zhu, Yun; Yu, Qing-Kai; Ding, Gu-Qiao; Xu, Xu-Guang; Wu, Tian-Ru; Gong, Qian; Yuan, Ning-Yi; Ding, Jian-Ning; Wang, Shu-Min; Xie, Xiao-Ming; Jiang, Mian-Heng

2014-01-28

2D β-Ga2O3 flakes on a continuous 2D graphene film were prepared by a one-step chemical vapor deposition on liquid gallium surface. The composite was characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy (XPS). The experimental results indicate that Ga2O3 flakes grew on the surface of graphene film during the cooling process. In particular, tenfold enhancement of graphene Raman scattering signal was detected on Ga2O3 flakes, and XPS indicates the C-O bonding between graphene and Ga2O3. The mechanism of Raman enhancement was discussed. The 2D Ga2O3-2D graphene structure may possess potential applications.

SERS and DFT study of p-hydroxybenzoic acid adsorbed on colloidal silver particles.

PubMed

Chen, Y; Chen, S J; Li, S; Wei, J J

2015-10-16

In this study, normal Raman spectra of p—hydroxybenzoic acid (PHBA) powder and its surface—enhanced Raman scattering (SERS) spectra in silver colloidal solutions were measured under near infrared excitation conditions. In theoretical calculation, two models of PHBA adsorbed on the surfaces of silver nanoparticles were established. The Raman frequencies of these two models using density functional theory (DFT) method were calculated, and compared with the experimental results. It was found that the calculated Raman frequencies were in good agreement with experimental values, which indicates that there are two enhanced mechanism physical (electromagnetic, EM) enhancement and chemical (charge—transfer, CT) enhancement, in silver colloidal solutions regarding SERS effect. Furthermore, from high—quality SERS spectrum of PHBA obtained in silver colloids, we inferred that PHBA molecules in silver colloids adsorb onto the metal surfaces through carboxyl at a perpendicular orientation. The combination of SERS spectra and DFT calculation is thus useful for studies of the adsorption—orientation of a molecule on a metal colloid.

Note: A portable Raman analyzer for microfluidic chips based on a dichroic beam splitter for integration of imaging and signal collection light paths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geng, Yijia; Xu, Shuping; Xu, Weiqing, E-mail: xuwq@jlu.edu.cn

An integrated and portable Raman analyzer featuring an inverted probe fixed on a motor-driving adjustable optical module was designed for the combination of a microfluidic system. It possesses a micro-imaging function. The inverted configuration is advantageous to locate and focus microfluidic channels. Different from commercial micro-imaging Raman spectrometers using manual switchable light path, this analyzer adopts a dichroic beam splitter for both imaging and signal collection light paths, which avoids movable parts and improves the integration and stability of optics. Combined with surface-enhanced Raman scattering technique, this portable Raman micro-analyzer is promising as a powerful tool for microfluidic analytics.

A naturally occurring diatom frustule as a SERS substrate for the detection and quantification of chemicals

NASA Astrophysics Data System (ADS)

Chamuah, Nabadweep; Chetia, Lakhi; Zahan, Nashrat; Dutta, Sibasish; Ahmed, Gazi A.; Nath, Pabitra

2017-05-01

Naturally occurring photonic crystal structures play an important role in different fields of application. Herein, we exploit the periodic pore pattern of a diatom frustule and demonstrate surface-enhanced Raman scattering (SERS) using its structure as a template for the SERS substrate. Gold nanoparticles (AuNPs) were initially allowed to self-assemble on the surface and inside the pores of the diatoms. The enhancement in the localized surface plasmon resonance (LSPR) field magnitude for the assembled AuNPs on the diatom frustule were studied using simulation software. For the proposed SERS substrate, an average field enhancement of the order of 108 magnitude was observed. We demonstrate the operation of the designed substrate for the detection and quantification of Raman signals from two Raman active samples, namely malachite green (MG) and fluoride concentrations in drinking water. Using the proposed SERS substrate, an MG concentration as low as 1 nM with a relative standard deviation (RSD) of 7.57% and a fluoride concentration of 100 nM with an RSD of 17.26% could be measured with the Raman spectrometer. We envision that the proposed technique could emerge as an inexpensive alternative fabrication method of SERS substrates which can produce an enhanced LSPR field magnitude and scatter intense Raman signals from Raman active samples.

Rapid ultrasensitive single particle surface-enhanced Raman spectroscopy using metallic nanopores.

PubMed

Cecchini, Michael P; Wiener, Aeneas; Turek, Vladimir A; Chon, Hyangh; Lee, Sangyeop; Ivanov, Aleksandar P; McComb, David W; Choo, Jaebum; Albrecht, Tim; Maier, Stefan A; Edel, Joshua B

2013-10-09

Nanopore sensors embedded within thin dielectric membranes have been gaining significant interest due to their single molecule sensitivity and compatibility of detecting a large range of analytes, from DNA and proteins, to small molecules and particles. Building on this concept we utilize a metallic Au solid-state membrane to translocate and rapidly detect single Au nanoparticles (NPs) functionalized with 589 dye molecules using surface-enhanced resonance Raman spectroscopy (SERRS). We show that, due to the plasmonic coupling between the Au metallic nanopore surface and the NP, signal intensities are enhanced when probing analyte molecules bound to the NP surface. Although not single molecule, this nanopore sensing scheme benefits from the ability of SERRS to provide rich vibrational information on the analyte, improving on current nanopore-based electrical and optical detection techniques. We show that the full vibrational spectrum of the analyte can be detected with ultrahigh spectral sensitivity and a rapid temporal resolution of 880 μs.

[Current views on surface enhanced Raman spectroscopy in microbiology].

PubMed

Jia, Xiaoxiao; Li, Jing; Qin, Tian; Deng, Aihua; Liu, Wenjun

2015-05-01

Raman spectroscopy has generated many branches during the development for more than 90 years. Surface enhanced Raman spectroscopy (SERS) improves SNR by using the interaction between tested materials and the surface of rough metal, as to quickly get higher sensitivity and precision spectroscopy without sample pretreatment. This article describes the characteristic and classification of SERS, and updates the theory and clinical application of SERS. It also summarizes the present status and progress of SERS in various disciplines and illustrates the necessity and urgency of its research, which provides rationale for the application for SERS in microbiology.

Silver vanadate nanoribbons: A label-free bioindicator in the conversion between human serum transferrin and apotransferrin via surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Zhou, Qing; Shao, Mingwang; Que, Ronghui; Cheng, Liang; Zhuo, Shujuan; Tong, Yanhua; Lee, Shuit-Tong

2011-05-01

Silver vanadate nanoribbons were synthesized via a hydrothermal process, which exhibited surface-enhanced Raman scattering effect. This surface-enhanced substrate was stable and reproducible for identifying human serum transferrin and human serum apotransferrin in the concentration of 1×10-5 M, which further exhibited significant sensitivity in monitoring the conversion of these two proteins in turn. This result showed that the silver vanadate nanoribbon might be employed as biomonitor in such systems.

Focused ultrasound delivery of Raman nanoparticles across the blood-brain barrier: potential for targeting experimental brain tumors.

PubMed

Diaz, Roberto Jose; McVeigh, Patrick Z; O'Reilly, Meaghan A; Burrell, Kelly; Bebenek, Matthew; Smith, Christian; Etame, Arnold B; Zadeh, Gelareh; Hynynen, Kullervo; Wilson, Brian C; Rutka, James T

2014-07-01

Spectral mapping of nanoparticles with surface enhanced Raman scattering (SERS) capability in the near-infrared range is an emerging molecular imaging technique. We used magnetic resonance image-guided transcranial focused ultrasound (TcMRgFUS) to reversibly disrupt the blood-brain barrier (BBB) adjacent to brain tumor margins in rats. Glioma cells were found to internalize SERS capable nanoparticles of 50nm or 120nm physical diameter. Surface coating with anti-epidermal growth factor receptor antibody or non-specific human immunoglobulin G, resulted in enhanced cell uptake of nanoparticles in-vitro compared to nanoparticles with methyl terminated 12-unit polyethylene glycol surface. BBB disruption permitted the delivery of SERS capable spherical 50 or 120nm gold nanoparticles to the tumor margins. Thus, nanoparticles with SERS imaging capability can be delivered across the BBB non-invasively using TcMRgFUS and have the potential to be used as optical tracking agents at the invasive front of malignant brain tumors. This study demonstrates the use of magnetic resonance image-guided transcranial focused ultrasound to open the BBB and enable spectral mapping of nanoparticles with surface enhanced Raman scattering (SERS)-based molecular imaging for experimental tumor tracking. Copyright © 2014 Elsevier Inc. All rights reserved.

Development of nanoparticle applications in cell imaging, bioassay and reactive oxygen species detection based on surface-enhanced raman spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Yiming

Surface-enhanced Raman scattering (SERS) has been developed over forty years with a wide variety of applications. Signals enhanced from single molecule absorbed on the surface of metallic nanoparticles can be up to 14-order-of-magnitude. This is due to the resonance between the optical field and surface plasmon of the metal substrate. Nanoshells have been chosen as substrates since they do not need to pre-aggregate due to their tunable optical property. We developed Raman imaging system by incorporating functionalized nanoshells, cells and SERS. Nanoshells have been coated with different self-assembled monolayers containing poly(ethylene glycol) (PEG) molecules. Probes have been designed by coating nanoshells with Raman active PEG molecules and delivered into macrophage cells. The imaging technique requires less preparation and provides the information of nanoshells in semi-quantitative way in vitro. We developed half-sandwich bioassay by detecting low volume of antigens on nitrocellulose membrane, detected by SERS. Antibodies were grafted to the surface of nanoshells and were conjugated to the antigens on the nitrocellulose membrane for detection. Raman active PEGs were conjugated onto the metal substrate for recognition and quantification. The benefits of this assay are that it is faster, easier to execute and requires less volume of antigen to conjugate onto the substrate. We also developed reactive oxygen species (ROS) sensors by incubating PEGs and either 4-nitrobenzenethiol (4-NBT) or 4-mercaptophenol (4-MP) on the surface of nanoshells. By analyzing the changes of SERS spectrum, the production of hydroxyl radicals produced in the Fenton reaction can be tracked in low concentrations. The sensors were designed to track ROS production within cells when they are under oxidative stress. The methods developed in this thesis are versatile, and can be broadly applied to the study of different subtracts, such as gold colloid.

Combined surface-enhanced Raman spectroscopy biotags and microfluidic platform for quantitative ratiometric discrimination between noncancerous and cancerous cells in flow

NASA Astrophysics Data System (ADS)

Pallaoro, Alessia; Hoonejani, Mehran R.; Braun, Gary B.; Meinhart, Carl; Moskovits, Martin

2013-01-01

Surface-enhanced Raman spectroscopy (SERS) biotags (SBTs) that carry peptides as cell recognition moieties were made from polymer-encapsulated silver nanoparticle dimers, infused with unique Raman reporter molecules. We previously demonstrated their potential use for identification of malignant cells, a central goal in cancer research, through a multiplexed, ratiometric method that can confidently distinguish between cancerous and noncancerous epithelial prostate cells in vitro based on receptor overexpression. Progress has been made toward the application of this quantitative methodology for the identification of cancer cells in a microfluidic flow-focusing device. Beads are used as cell mimics to evaluate the devices. Cells (and beads) are simultaneously incubated with two sets of SBTs while in suspension, then injected into the device for laser interrogation under flow. Each cell event is characterized by a composite Raman spectrum, deconvoluted into its single components to ultimately determine their relative contribution. We have found that using SBTs ratiometrically can provide cell identification in flow, insensitive to normal causes of uncertainty in optical measurements such as variations in focal plane, cell concentration, autofluorescence, and turbidity.

In situ, accurate, surface-enhanced Raman scattering detection of cancer cell nucleus with synchronous location by an alkyne-labeled biomolecular probe.

PubMed

Zhang, Jing; Liang, Lijia; Guan, Xin; Deng, Rong; Qu, Huixin; Huang, Dianshuai; Xu, Shuping; Liang, Chongyang; Xu, Weiqing

2018-01-01

A surface-enhanced Raman scattering (SERS) method for in situ detection and analysis of the intranuclear biomolecular information of a cell has been developed based on a small, biocompatible, nuclear-targeting alkyne-tagged deoxyribonucleic acid (DNA) probe (5-ethynyl-2'-deoxyuridine, EDU) that can specially accumulate in the cell nucleus during DNA replications to precisely locate the nuclear region without disturbance in cell biological activities and functions. Since the specific alkyne group shows a Raman peak in the Raman-silent region of cells, it is an interior label to visualize the nuclear location synchronously in real time when measuring the SERS spectra of a cell. Because no fluorescent-labeled dyes were used for locating cell nuclei, this method is simple, nondestructive, non- photobleaching, and valuable for the in situ exploration of vital physiological processes with DNA participation in cell organelles. Graphical abstract A universal strategy was developed to accurately locate the nuclear region and obtain precise molecular information of cell nuclei by SERS.

Ultrathin Carbon Film Protected Silver Nanostructures for Surface-Enhanced Raman Scattering.

PubMed

Peng, Yinshan; Zheng, Xianliang; Tian, Hongwei; Cui, Xiaoqiang; Chen, Hong; Zheng, Weitao

2016-06-23

In this article, ultrathin carbon film protected silver substrate (Ag/C) was prepared via a plasma-enhanced chemical vapor deposition (PECVD) method. The morphological evolution of silver nanostructures underneath, as well as the surface-enhanced Raman scattering (SERS) activity of Ag/C hybrid can be tuned by controlling the deposition time. The stability and reproducibility of the as-prepared hybrid were also studied. © The Author(s) 2016.

Rapid bacterial antibiotic susceptibility test based on simple surface-enhanced Raman spectroscopic biomarkers

NASA Astrophysics Data System (ADS)

Liu, Chia-Ying; Han, Yin-Yi; Shih, Po-Han; Lian, Wei-Nan; Wang, Huai-Hsien; Lin, Chi-Hung; Hsueh, Po-Ren; Wang, Juen-Kai; Wang, Yuh-Lin

2016-03-01

Rapid bacterial antibiotic susceptibility test (AST) and minimum inhibitory concentration (MIC) measurement are important to help reduce the widespread misuse of antibiotics and alleviate the growing drug-resistance problem. We discovered that, when a susceptible strain of Staphylococcus aureus or Escherichia coli is exposed to an antibiotic, the intensity of specific biomarkers in its surface-enhanced Raman scattering (SERS) spectra drops evidently in two hours. The discovery has been exploited for rapid AST and MIC determination of methicillin-susceptible S. aureus and wild-type E. coli as well as clinical isolates. The results obtained by this SERS-AST method were consistent with that by the standard incubation-based method, indicating its high potential to supplement or replace existing time-consuming methods and help mitigate the challenge of drug resistance in clinical microbiology.

Optical Antenna Arrays on a Fiber Facet for In Situ Surface Enhanced Raman Scattering Detection

PubMed Central

Smythe, Elizabeth J.; Dickey, Michael D.; Bao, Jiming; Whitesides, George M.

2009-01-01

This paper reports a bidirectional fiber optic probe for the detection of surface enhanced Raman scattering (SERS). One facet of the probe features an array of gold optical antennas designed to enhance Raman signal, while the other facet of the fiber is used for the input and collection of light. Simultaneous detection of benzenethiol and 2-[(E)-2-pyridin-4-ylethenyl]pyridine is demonstrated through a 35 cm long fiber. The array of nanoscale optical antennas was first defined by electron-beam lithography on a silicon wafer. The array was subsequently stripped from the wafer and then transferred to the facet of a fiber. Lithographic definition of the antennas provides a method for producing two-dimensional arrays with well-defined geometry, which allows (i) the optical response of the probe to be tuned and (ii) the density of ‘hot spots’ generating the enhanced Raman signal to be controlled. It is difficult to determine the Raman signal enhancement factor (EF) of most fiber optic Raman sensors featuring ‘hot spots’ because the geometry of the Raman enhancing nanostructures is poorly defined. The ability to control the size and spacing of the antennas enables the EF of the transferred array to be estimated. EF values estimated after focusing a laser directly onto the transferred array ranged from 2.6 × 105 to 5.1 × 105. PMID:19236032

Local Intensity Enhancements in Spherical Microcavities: Implications for Photonic Chemical and Biological Sensors

NASA Technical Reports Server (NTRS)

Fuller, Kirk A.

2005-01-01

In this report, we summarize recent findings regarding the use spherical microcavities in the amplification of light that is inelastically scattered by either fluorescent or Raman-active molecules. This discussion will focus on Raman scattering, with the understanding that analogous processes apply to fluorescence. Raman spectra can be generated through the use of a very strong light source that stimulates inelastic light scattering by molecules, with the scattering occurring at wavelengths shifted from that of the source and being most prominent at shifts associated with the molecules natural vibrational frequencies. The Raman signal can be greatly enhanced by exposing a molecule to the intense electric fields that arise near surfaces (typically of gold or silver) exhibiting nanoscale roughness. This is known as surface-enhanced Raman scattering (SERS). SERS typically produces gain factors of 103 - 106, but under special conditions, factors of 1010 - 1014 have been achieved.

Surface-enhanced Raman scattering from metal and transition metal nano-caped arrays

NASA Astrophysics Data System (ADS)

Sun, Huanhuan; Gao, Renxian; Zhu, Aonan; Hua, Zhong; Chen, Lei; Wang, Yaxin; Zhang, Yongjun

2018-03-01

The metal and transition metal cap-shaped arrays on polystyrene colloidal particle (PSCP) templates were fabricated to study the surface-enhanced Raman scattering (SERS) effect. We obtained the Ag and Fe complex film by a co-sputtering deposition method. The size of the deposited Fe particle was changed by the sputtering power. We also study the SERS enhancement mechanism by decorating the PATP probe molecule on the different films. The SERS signals increased firstly, and then decreased as the size of Fe particles grows gradually. The finite-difference time domain (FDTD) simulation and experimental Raman results manifest that SERS enhancement was mainly attributed to surface plasma resonance (SPR) between Ag and Ag nanoparticles. The SERS signals of PATP molecule were enhanced to reach a lowest detectable concentration of 10-8 mol/L. The research demonstrates that the SERS substrates with Ag-Fe cap-shaped arrays have a high sensitivity.

Development of batch producible hot embossing 3D nanostructured surface-enhanced Raman scattering chip technology

NASA Astrophysics Data System (ADS)

Huang, Chu-Yu; Tsai, Ming-Shiuan

2017-09-01

The main purpose of this study is to develop a batch producible hot embossing 3D nanostructured surface-enhanced Raman chip technology for high sensitivity label-free plasticizer detection. This study utilizing the AAO self-assembled uniform nano-hemispherical array barrier layer as a template to create a durable nanostructured nickel mold. With the hot embossing technique and the durable nanostructured nickel mold, we are able to batch produce the 3D Nanostructured Surface-enhanced Raman Scattering Chip with consistent quality. In addition, because of our SERS chip can be fabricated by batch processing, the fabrication cost is low. Therefore, the developed method is very promising to be widespread and extensively used in rapid chemical and biomolecular detection applications.

Highly sensitive immunoassay of anti-cyclic citrullinated peptide marker using surface-enhanced Raman scattering detection

NASA Astrophysics Data System (ADS)

Chon, H.; Lee, S.; Wang, R.; Bang, S.-Y.; Lee, H.-S.; Bae, S.-C.; Hong, S. H.; Yoon, Y. H.; Lim, D.; Choo, J.

2015-07-01

We report a highly sensitive anti-cyclic citrullinated peptide (anti-CCP) detection method for early diagnosis of rheumatoid arthritis (RA) using surface-enhanced Raman scattering (SERS)-based immunoassay. Herein, cyclic citrullinated peptide (CCP)-conjugated magnetic beads and anti-human IgG-conjugated hollow gold nanospheres (HGNs) were used as substrates and SERS nano-tags, respectively. First, its detection sensitivity was evaluated using anti-CCP standard solutions. Then quantitative anti-CCP levels, determined by the SERS-based assay, were compared with those obtained from three commercially available anti-CCP assay kits (Immunoscan CCPlus, ImmunnLisa™ CCP and BioPlex™ 2200) to assess its potential utility as a clinical tool. Finally, clinical samples from 20 RA patients were investigated using them. In the SERS-based assay, the anti-CCP level in human serum was successfully determined by monitoring the characteristic Raman peak intensity of SERS nano-tags. The diagnostic performance of our SERS-based immunoassay for clinical samples shows a good agreement with those measured by three commercial anti-CCP kits. In addition, our SERS-based assay results are more consistent in the low concentration range (0-25 U/mL) than those achieved by the commercial kits. Accordingly, it is estimated that the SERS-based assay is a potentially useful diagnostic tool for early diagnosis of RA.

Surface-enhanced Raman scattering on periodic metal nanotips with tunable sharpness.

PubMed

Linn, Nicholas C; Sun, Chih-Hung; Arya, Ajay; Jiang, Peng; Jiang, Bin

2009-06-03

This paper reports on a scalable bottom-up technology for producing periodic gold nanotips with tunable sharpness as surface-enhanced Raman scattering (SERS) substrates. Inverted silicon pyramidal pits, which are templated from non-close-packed colloidal crystals prepared by a spin-coating technology, are used as structural templates to replicate arrays of polymer nanopyramids with nanoscale sharp tips. The deposition of a thin layer of gold on the polymer nanopyramids leads to the formation of SERS-active substrates with a high enhancement factor (up to 10(8)). The thickness of the deposited metal determines the sharpness of the nanotips and the resulting Raman enhancement factor. Finite-element electromagnetic modeling shows that the nanotips can significantly enhance the local electromagnetic field and the sharpness of nanotips greatly affects the SERS enhancement.

Mildly reduced graphene oxide-Ag nanoparticle hybrid films for surface-enhanced Raman scattering

PubMed Central

2012-01-01

Large-area mildly reduced graphene oxide (MR-GO) monolayer films were self-assembled on SiO2/Si surfaces via an amidation reaction strategy. With the MR-GO as templates, MR-GO-Ag nanoparticle (MR-GO-Ag NP) hybrid films were synthesized by immersing the MR-GO monolayer into a silver salt solution with sodium citrate as a reducing agent under UV illumination. SEM image indicated that Ag NPs with small interparticle gap are uniformly distributed on the MR-GO monolayer. Raman spectra demonstrated that the MR-GO monolayer beneath the Ag NPs can effectively quench the fluorescence signal emitted from the Ag films and dye molecules under laser excitation, resulting in a chemical enhancement (CM). The Ag NPs with narrow gap provided numerous hot spots, which are closely related with electromagnetic mechanism (EM), and were believed to remarkably enhance the Raman signal of the molecules. Due to the co-contribution of the CM and EM effects as well as the coordination mechanism between the MR-GO and Ag NPs, the MR-GO-Ag NP hybrid films showed more excellent Raman signal enhancement performance than that of either Ag films or MR-GO monolayer alone. This will further enrich the application of surface-enhanced Raman scattering in molecule detection. PMID:22471923

Raman enhancement on ultra-clean graphene quantum dots produced by quasi-equilibrium plasma-enhanced chemical vapor deposition.

PubMed

Liu, Donghua; Chen, Xiaosong; Hu, Yibin; Sun, Tai; Song, Zhibo; Zheng, Yujie; Cao, Yongbin; Cai, Zhi; Cao, Min; Peng, Lan; Huang, Yuli; Du, Lei; Yang, Wuli; Chen, Gang; Wei, Dapeng; Wee, Andrew Thye Shen; Wei, Dacheng

2018-01-15

Graphene is regarded as a potential surface-enhanced Raman spectroscopy (SERS) substrate. However, the application of graphene quantum dots (GQDs) has had limited success due to material quality. Here, we develop a quasi-equilibrium plasma-enhanced chemical vapor deposition method to produce high-quality ultra-clean GQDs with sizes down to 2 nm directly on SiO 2 /Si, which are used as SERS substrates. The enhancement factor, which depends on the GQD size, is higher than conventional graphene sheets with sensitivity down to 1 × 10 -9  mol L -1 rhodamine. This is attributed to the high-quality GQDs with atomically clean surfaces and large number of edges, as well as the enhanced charge transfer between molecules and GQDs with appropriate diameters due to the existence of Van Hove singularities in the electronic density of states. This work demonstrates a sensitive SERS substrate, and is valuable for applications of GQDs in graphene-based photonics and optoelectronics.

Surface-Enhanced Raman Scattering Surface Selection Rules for the Proteomic Liquid Biopsy in Real Samples: Efficient Detection of the Oncoprotein c-MYC.

PubMed

Pazos, Elena; Garcia-Algar, Manuel; Penas, Cristina; Nazarenus, Moritz; Torruella, Arnau; Pazos-Perez, Nicolas; Guerrini, Luca; Vázquez, M Eugenio; Garcia-Rico, Eduardo; Mascareñas, José L; Alvarez-Puebla, Ramon A

2016-11-02

Blood-based biomarkers (liquid biopsy) offer extremely valuable tools for the noninvasive diagnosis and monitoring of tumors. The protein c-MYC, a transcription factor that has been shown to be deregulated in up to 70% of human cancers, can be used as a robust proteomic signature for cancer. Herein, we developed a rapid, highly specific, and sensitive surface-enhanced Raman scattering (SERS) assay for the quantification of c-MYC in real blood samples. The sensing scheme relies on the use of specifically designed hybrid plasmonic materials and their bioderivatization with a selective peptidic receptor modified with a SERS transducer. Peptide/c-MYC recognition events translate into measurable alterations of the SERS spectra associated with a molecular reorientation of the transducer, in agreement with the surface selection rules. The efficiency of the sensor is demonstrated in cellular lines, healthy donors and a cancer patient.

Development of thin-film tunable band-pass filters based hyper-spectral imaging system applied for both surface enhanced Raman scattering and plasmon resonance Rayleigh scattering

NASA Astrophysics Data System (ADS)

Iga, Mitsuhiro; Kakuryu, Nobuyuki; Tanaami, Takeo; Sajiki, Jiro; Isozaki, Katsumi; Itoh, Tamitake

2012-10-01

We describe the development of a hyper-spectral imaging (HSI) system composed of thin-film tunable band-pass filters (TF-TBPFs) and its application to inhomogeneous sample surfaces. Compared with existing HSI systems, the system has a simpler optical arrangement and has an optical transmittance of up to 80% owing to polarization independence. The HSI system exhibits a constant spectral resolution over a spectral window of 80 nm (530 to 610 nm) and tunable spectral resolution from 1.5 to 3.0 nm, and requires only 5.4 s per measurement. Plasmon resonance and surface enhanced Raman scattering (SERS) from inhomogeneous surfaces dispersed with Ag nanoparticles (NP) have been measured with the HSI system. The measurement of multiple Ag NPs is consistent with conventional isolated NP measurements as explained by the electromagnetic mechanism of SERS, demonstrating the validity of the HSI system.

Electromagnetic modelling of Raman enhancement from nanoscale substrates: a route to estimation of the magnitude of the chemical enhancement mechanism in SERS.

PubMed

Brown, Richard J C; Wang, Jian; Tantra, Ratna; Yardley, Rachel E; Milton, Martin J T

2006-01-01

Despite widespread use for more than two decades, the SERS phenomenon has defied accurate physical and chemical explanation. The relative contributions from electronic and chemical mechanisms are difficult to quantify and are often not reproduced under nominally similar experimental conditions. This work has used electromagnetic modelling to predict the Raman enhancement expected from three configurations: metal nanoparticles, structured metal surfaces, and sharp metal tips interacting with metal surfaces. In each case, parameters such as artefact size, artefact separation and incident radiation wavelength have been varied and the resulting electromagnetic field modelled. This has yielded an electromagnetic description of these configurations with predictions of the maximum expected Raman enhancement, and hence a prediction of the optimum substrate configuration for the SERS process. When combined with experimental observations of the dependence of Raman enhancement with changing ionic strength, the modelling results have allowed a novel estimate of the size of the chemical enhancement mechanism to be produced.

Silver Eco-Solvent Ink for Reactive Printing of Polychromatic SERS and SPR Substrates

PubMed Central

Dustov, Mavlavi; Goldt, Anastasia E.; Sukhorukova, Irina V.; Grünert, Wolfgang; Grigorieva, Anastasia V.

2018-01-01

A new reactive ink based on a silver citrate complex is proposed for a photochemical route to surface-enhanced Raman spectroscopy active substrates with controllable extinction spectra. The drop-cast test of the ink reveals homogeneous nucleation of silver and colloid particle growth originating directly from photochemical in situ reduction in droplets, while the following evaporation of the deposited ink produces small nano- and micron-size particles. The prepared nanostructures and substrates were accurately characterized by electron microscopy methods and optical extinction spectroscopy. Varying the duration of UV irradiation allows tuning the morphology of individual silver nanoparticles forming hierarchical ring structures with numerous “hot spots” for most efficient Raman enhancement. Raman measurements of probe molecules of rhodamine 6G and methylene blue reached the largest signal enhancement of 106 by the resonance effects. PMID:29425119

Silver Eco-Solvent Ink for Reactive Printing of Polychromatic SERS and SPR Substrates.

PubMed

Dustov, Mavlavi; Golovina, Diana I; Polyakov, Alexander Yu; Goldt, Anastasia E; Eliseev, Andrei A; Kolesnikov, Efim A; Sukhorukova, Irina V; Shtansky, Dmitry V; Grünert, Wolfgang; Grigorieva, Anastasia V

2018-02-09

A new reactive ink based on a silver citrate complex is proposed for a photochemical route to surface-enhanced Raman spectroscopy active substrates with controllable extinction spectra. The drop-cast test of the ink reveals homogeneous nucleation of silver and colloid particle growth originating directly from photochemical in situ reduction in droplets, while the following evaporation of the deposited ink produces small nano- and micron-size particles. The prepared nanostructures and substrates were accurately characterized by electron microscopy methods and optical extinction spectroscopy. Varying the duration of UV irradiation allows tuning the morphology of individual silver nanoparticles forming hierarchical ring structures with numerous "hot spots" for most efficient Raman enhancement. Raman measurements of probe molecules of rhodamine 6G and methylene blue reached the largest signal enhancement of 10⁶ by the resonance effects.

Unraveling the Raman Enhancement Mechanism on 1T'-Phase ReS2 Nanosheets.

PubMed

Miao, Peng; Qin, Jing-Kai; Shen, Yunfeng; Su, Huimin; Dai, Junfeng; Song, Bo; Du, Yunchen; Sun, Mengtao; Zhang, Wei; Wang, Hsing-Lin; Xu, Cheng-Yan; Xu, Ping

2018-04-01

2D transition metal dichalcogenides materials are explored as potential surface-enhanced Raman spectroscopy substrates. Herein, a systematic study of the Raman enhancement mechanism on distorted 1T (1T') rhenium disulfide (ReS 2 ) nanosheets is demonstrated. Combined Raman and photoluminescence studies with the introduction of an Al 2 O 3 dielectric layer unambiguously reveal that Raman enhancement on ReS 2 materials is from a charge transfer process rather than from an energy transfer process, and Raman enhancement is inversely proportional while the photoluminescence quenching effect is proportional to the layer number (thickness) of ReS 2 nanosheets. On monolayer ReS 2 film, a strong resonance-enhanced Raman scattering effect dependent on the laser excitation energy is detected, and a detection limit as low as 10 -9 m can be reached from the studied dye molecules such as rhodamine 6G and methylene blue. Such a high enhancement factor achieved through enhanced charge interaction between target molecule and substrate suggests that with careful consideration of the layer-number-dependent feature and excitation-energy-related resonance effect, ReS 2 is a promising Raman enhancement platform for sensing applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrospray surface-enhanced Raman spectroscopy (ES-SERS) for probing surface chemical compositions of atmospherically relevant particles

NASA Astrophysics Data System (ADS)

Gen, Masao; Chan, Chak K.

2017-11-01

We present electrospray surface-enhanced Raman spectroscopy (ES-SERS) as a new approach to measuring the surface chemical compositions of atmospherically relevant particles. The surface-sensitive SERS is realized by electrospraying Ag nanoparticle aerosols over analyte particles. Spectral features at v(SO42-), v(C-H) and v(O-H) modes were observed from the normal Raman and SERS measurements of laboratory-generated supermicron particles of ammonium sulfate (AS), AS mixed with succinic acid (AS / SA) and AS mixed with sucrose (AS / sucrose). SERS measurements showed strong interaction (or chemisorption) between Ag nanoparticles and surface aqueous sulfate [SO42-] with [SO42-]AS / sucrose > [SO42-]AS / SA > [SO42-]AS. Enhanced spectra of the solid AS and AS / SA particles revealed the formation of surface-adsorbed water on their surfaces at 60 % relative humidity. These observations of surface aqueous sulfate and adsorbed water demonstrate a possible role of surface-adsorbed water in facilitating the dissolution of sulfate from the bulk phase into its water layer(s). Submicron ambient aerosol particles collected in Hong Kong exhibited non-enhanced features of black carbon and enhanced features of sulfate and organic matter (carbonyl group), indicating an enrichment of sulfate and organic matter on the particle surface.

In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

PubMed Central

Zhang, Hua; Wang, Chen; Sun, Han-Lei; Fu, Gang; Chen, Shu; Zhang, Yue-Jiao; Chen, Bing-Hui; Anema, Jason R.; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2017-01-01

Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis. PMID:28537269

The substrate matters in the Raman spectroscopy analysis of cells

PubMed Central

Mikoliunaite, Lina; Rodriguez, Raul D.; Sheremet, Evgeniya; Kolchuzhin, Vladimir; Mehner, Jan; Ramanavicius, Arunas; Zahn, Dietrich R.T.

2015-01-01

Raman spectroscopy is a powerful analytical method that allows deposited and/or immobilized cells to be evaluated without complex sample preparation or labeling. However, a main limitation of Raman spectroscopy in cell analysis is the extremely weak Raman intensity that results in low signal to noise ratios. Therefore, it is important to seize any opportunity that increases the intensity of the Raman signal and to understand whether and how the signal enhancement changes with respect to the substrate used. Our experimental results show clear differences in the spectroscopic response from cells on different surfaces. This result is partly due to the difference in spatial distribution of electric field at the substrate/cell interface as shown by numerical simulations. We found that the substrate also changes the spatial location of maximum field enhancement around the cells. Moreover, beyond conventional flat surfaces, we introduce an efficient nanostructured silver substrate that largely enhances the Raman signal intensity from a single yeast cell. This work contributes to the field of vibrational spectroscopy analysis by providing a fresh look at the significance of the substrate for Raman investigations in cell research. PMID:26310910

The substrate matters in the Raman spectroscopy analysis of cells

NASA Astrophysics Data System (ADS)

Mikoliunaite, Lina; Rodriguez, Raul D.; Sheremet, Evgeniya; Kolchuzhin, Vladimir; Mehner, Jan; Ramanavicius, Arunas; Zahn, Dietrich R. T.

2015-08-01

Raman spectroscopy is a powerful analytical method that allows deposited and/or immobilized cells to be evaluated without complex sample preparation or labeling. However, a main limitation of Raman spectroscopy in cell analysis is the extremely weak Raman intensity that results in low signal to noise ratios. Therefore, it is important to seize any opportunity that increases the intensity of the Raman signal and to understand whether and how the signal enhancement changes with respect to the substrate used. Our experimental results show clear differences in the spectroscopic response from cells on different surfaces. This result is partly due to the difference in spatial distribution of electric field at the substrate/cell interface as shown by numerical simulations. We found that the substrate also changes the spatial location of maximum field enhancement around the cells. Moreover, beyond conventional flat surfaces, we introduce an efficient nanostructured silver substrate that largely enhances the Raman signal intensity from a single yeast cell. This work contributes to the field of vibrational spectroscopy analysis by providing a fresh look at the significance of the substrate for Raman investigations in cell research.

Capillary-driven surface-enhanced Raman scattering (SERS)-based microfluidic chip for abrin detection

NASA Astrophysics Data System (ADS)

Yang, Hao; Deng, Min; Ga, Shan; Chen, Shouhui; Kang, Lin; Wang, Junhong; Xin, Wenwen; Zhang, Tao; You, Zherong; An, Yuan; Wang, Jinglin; Cui, Daxiang

2014-03-01

Herein, we firstly demonstrate the design and the proof-of-concept use of a capillary-driven surface-enhanced Raman scattering (SERS)-based microfluidic chip for abrin detection. The micropillar array substrate was etched and coated with a gold film by microelectromechanical systems (MEMS) process to integrate into a lateral flow test strip. The detection of abrin solutions of various concentrations was performed by the as-prepared microfluidic chip. It was shown that the correlation between the abrin concentration and SERS signal was found to be linear within the range of 0.1 ng/mL to 1 μg/mL with a limit of detection of 0.1 ng/mL. Our microfluidic chip design enhanced the operability of SERS-based immunodiagnostic techniques, significantly reducing the complication and cost of preparation as compared to previous SERS-based works. Meanwhile, this design proved the superiority to conventional lateral flow test strips in respect of both sensitivity and quantitation and showed great potential in the diagnosis and treatment for abrin poisoning as well as on-site screening of abrin-spiked materials.

Horizontal silicon nanowires for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Gebavi, Hrvoje; Ristić, Davor; Baran, Nikola; Mikac, Lara; Mohaček-Grošev, Vlasta; Gotić, Marijan; Šikić, Mile; Ivanda, Mile

2018-01-01

The main purpose of this paper is to focus on details of the fabrication process of horizontally and vertically oriented silicon nanowires (SiNWs) substrates for the application of surface-enhanced Raman spectroscopy (SERS). The fabrication process is based on the vapor-liquid-solid method and electroless-assisted chemical etching, which, as the major benefit, resulting in the development of economical, easy-to-prepare SERS substrates. Furthermore, we examined the fabrication of Au coated Ag nanoparticles (NPs) on the SiNWs substrates in such a way as to diminish the influence of silver NPs corrosion, which, in turn, enhanced the SERS time stability, thus allowing for wider commercial applications. The substances on which high SERS sensitivity was proved are rhodamine (R6G) and 4-mercaptobenzoic acid (MBA), with the detection limits of 10-8 M and 10-6 M, respectively.

Reusable three-dimensional nanostructured substrates for surface-enhanced Raman scattering.

PubMed

Zhu, Zhendong; Li, Qunqing; Bai, Benfeng; Fan, Shoushan

2014-01-13

To date, fabricating three-dimensional (3D) nanostructured substrate with small nanogap was a laborious challenge by conventional fabrication techniques. In this article, we address a simple, low-cost, large-area, and spatially controllable method to fabricate 3D nanostructures, involving hemisphere, hemiellipsoid, and pyramidal pits based on nanosphere lithography (NSL). These 3D nanostructures were used as surface-enhanced Raman scattering (SERS) substrates of single Rhodamine 6G (R6G) molecule. The average SERS enhancement factor achieved up to 1011. The inevitably negative influence of the adhesion-promoting intermediate layer of Cr or Ti was resolved by using such kind of 3D nanostructures. The nanostructured quartz substrate is a free platform as a SERS substrate and is nondestructive when altering with different metal films and is recyclable, which avoids the laborious and complicated fabricating procedures.

Reusable three-dimensional nanostructured substrates for surface-enhanced Raman scattering

PubMed Central

2014-01-01

To date, fabricating three-dimensional (3D) nanostructured substrate with small nanogap was a laborious challenge by conventional fabrication techniques. In this article, we address a simple, low-cost, large-area, and spatially controllable method to fabricate 3D nanostructures, involving hemisphere, hemiellipsoid, and pyramidal pits based on nanosphere lithography (NSL). These 3D nanostructures were used as surface-enhanced Raman scattering (SERS) substrates of single Rhodamine 6G (R6G) molecule. The average SERS enhancement factor achieved up to 1011. The inevitably negative influence of the adhesion-promoting intermediate layer of Cr or Ti was resolved by using such kind of 3D nanostructures. The nanostructured quartz substrate is a free platform as a SERS substrate and is nondestructive when altering with different metal films and is recyclable, which avoids the laborious and complicated fabricating procedures. PMID:24417892

Detection of volatile organic compounds by surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Chang, Allan S. P.; Maiti, Amitesh; Ileri, Nazar; Bora, Mihail; Larson, Cindy C.; Britten, Jerald A.; Bond, Tiziana C.

2012-06-01

We present the detection of volatile organic compounds directly in their vapor phase by surface-enhanced Raman scattering (SERS) substrates based on lithographically-defined two-dimensional rectangular array of nanopillars. The type of nanopillars is known as the tapered pillars. For the tapered pillars, SERS enhancement arises from the nanofocusing effect due to the sharp tip on top. SERS experiments were carried out on these substrates using various concentrations of toluene vapor. The results show that SERS signal from a toluene vapor is strongly influenced by the substrate temperature, and the toluene vapor can be detected within minutes of exposing the SERS substrate to the vapor. A simple adsorption model is developed which gives results matching the experimental data. The results also show promising potential for the use of these substrates in environmental monitoring of gases and vapors.

Label-free SERS detection of Salmonella Typhimurium on DNA aptamer modified AgNR substrates

USDA-ARS?s Scientific Manuscript database

A straightforward label-free method based on aptamer binding and surface enhanced Raman specstroscopy (SERS) has been developed for the detection of Salmonella Typhimurium, an important foodborne pathogen that causes gastroenteritis in both humans and animals. Surface of the SERS-active silver nanor...

Surface-enhanced Raman medical probes and system for disease diagnosis and drug testing

DOEpatents

Vo-Dinh, T.

1999-01-26

A probe for a surface-enhanced Raman scattering spectrometer includes a member of optically transmissive material for receiving the excitation radiation from a laser and for carrying the radiation emitted from a specimen to a detector. An end of the member for placing against the specimen has a coating that produces surface enhancement of the specimen during Raman scattering spectroscopic analysis. Specifically the coating is formed by a first layer of microparticles on the member and a metal layer over the first layer. The first layer may form a microstructure surface over which a metal layer is applied. Alternatively the coating may be a material containing microparticles of a metal. An optional layer of a material may be applied to the metal layer to concentrate onto the probe compounds of analytical interest onto the probe. 39 figs.

Surface-enhanced raman medical probes and system for disease diagnosis and drug testing

DOEpatents

Vo-Dinh, Tuan

1999-01-01

A probe for a surface-enhanced Raman scattering spectrometer includes a member of optically transmissive material for receiving the excitation radiation from a laser and for carrying the radiation emitted from a specimen to a detector. An end of the member for placing against the specimen has a coating that produces surface enhancement of the specimen during Raman scattering spectroscopic analysis. Specifically the coating is formed by a first layer of microparticles on the member and a metal layer over the first layer. The first layer may form a microstructure surface over which a metal layer is applied. Alternatively the coating may be a material containing microparticles of a metal. An optional layer of a material may be applied to the metal layer to concentrate onto the probe compounds of analytical interest onto the probe.

A novel method for detection of phosphorylation in single cells by surface enhanced Raman scattering (SERS) using composite organic-inorganic nanoparticles (COINs).

PubMed

Shachaf, Catherine M; Elchuri, Sailaja V; Koh, Ai Leen; Zhu, Jing; Nguyen, Lienchi N; Mitchell, Dennis J; Zhang, Jingwu; Swartz, Kenneth B; Sun, Lei; Chan, Selena; Sinclair, Robert; Nolan, Garry P

2009-01-01

Detection of single cell epitopes has been a mainstay of immunophenotyping for over three decades, primarily using fluorescence techniques for quantitation. Fluorescence has broad overlapping spectra, limiting multiplexing abilities. To expand upon current detection systems, we developed a novel method for multi-color immuno-detection in single cells using "Composite Organic-Inorganic Nanoparticles" (COINs) Raman nanoparticles. COINs are Surface-Enhanced Raman Scattering (SERS) nanoparticles, with unique Raman spectra. To measure Raman spectra in single cells, we constructed an automated, compact, low noise and sensitive Raman microscopy device (Integrated Raman BioAnalyzer). Using this technology, we detected proteins expressed on the surface in single cells that distinguish T-cells among human blood cells. Finally, we measured intracellular phosphorylation of Stat1 (Y701) and Stat6 (Y641), with results comparable to flow cytometry. Thus, we have demonstrated the practicality of applying COIN nanoparticles for measuring intracellular phosphorylation, offering new possibilities to expand on the current fluorescent technology used for immunoassays in single cells.

A Novel Method for Detection of Phosphorylation in Single Cells by Surface Enhanced Raman Scattering (SERS) using Composite Organic-Inorganic Nanoparticles (COINs)

PubMed Central

Shachaf, Catherine M.; Elchuri, Sailaja V.; Koh, Ai Leen; Zhu, Jing; Nguyen, Lienchi N.; Mitchell, Dennis J.; Zhang, Jingwu; Swartz, Kenneth B.; Sun, Lei; Chan, Selena; Sinclair, Robert; Nolan, Garry P.

2009-01-01

Background Detection of single cell epitopes has been a mainstay of immunophenotyping for over three decades, primarily using fluorescence techniques for quantitation. Fluorescence has broad overlapping spectra, limiting multiplexing abilities. Methodology/Principal Findings To expand upon current detection systems, we developed a novel method for multi-color immuno-detection in single cells using “Composite Organic-Inorganic Nanoparticles” (COINs) Raman nanoparticles. COINs are Surface-Enhanced Raman Scattering (SERS) nanoparticles, with unique Raman spectra. To measure Raman spectra in single cells, we constructed an automated, compact, low noise and sensitive Raman microscopy device (Integrated Raman BioAnalyzer). Using this technology, we detected proteins expressed on the surface in single cells that distinguish T-cells among human blood cells. Finally, we measured intracellular phosphorylation of Stat1 (Y701) and Stat6 (Y641), with results comparable to flow cytometry. Conclusions/Significance Thus, we have demonstrated the practicality of applying COIN nanoparticles for measuring intracellular phosphorylation, offering new possibilities to expand on the current fluorescent technology used for immunoassays in single cells. PMID:19367337

Detection of amino acid neurotransmitters by surface enhanced Raman scattering and hollow core photonic crystal fiber

NASA Astrophysics Data System (ADS)

Tiwari, Vidhu S.; Khetani, Altaf; Monfared, Ali Momenpour T.; Smith, Brett; Anis, Hanan; Trudeau, Vance L.

2012-03-01

The present work explores the feasibility of using surface enhanced Raman scattering (SERS) for detecting the neurotransmitters such as glutamate (GLU) and gamma-amino butyric acid (GABA). These amino acid neurotransmitters that respectively mediate fast excitatory and inhibitory neurotransmission in the brain, are important for neuroendocrine control, and upsets in their synthesis are also linked to epilepsy. Our SERS-based detection scheme enabled the detection of low amounts of GLU (10-7 M) and GABA (10-4 M). It may complement existing techniques for characterizing such kinds of neurotransmitters that include high-performance liquid chromatography (HPLC) or mass spectrography (MS). This is mainly because SERS has other advantages such as ease of sample preparation, molecular specificity and sensitivity, thus making it potentially applicable to characterization of experimental brain extracts or clinical diagnostic samples of cerebrospinal fluid and saliva. Using hollow core photonic crystal fiber (HC-PCF) further enhanced the Raman signal relative to that in a standard cuvette providing sensitive detection of GLU and GABA in micro-litre volume of aqueous solutions.

Raman enhancement by graphene-Ga2O3 2D bilayer film

PubMed Central

2014-01-01

2D β-Ga2O3 flakes on a continuous 2D graphene film were prepared by a one-step chemical vapor deposition on liquid gallium surface. The composite was characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy (XPS). The experimental results indicate that Ga2O3 flakes grew on the surface of graphene film during the cooling process. In particular, tenfold enhancement of graphene Raman scattering signal was detected on Ga2O3 flakes, and XPS indicates the C-O bonding between graphene and Ga2O3. The mechanism of Raman enhancement was discussed. The 2D Ga2O3-2D graphene structure may possess potential applications. PMID:24472433

A SERS-active sensor based on heterogeneous gold nanostar core-silver nanoparticle satellite assemblies for ultrasensitive detection of aflatoxinB1

NASA Astrophysics Data System (ADS)

Li, Aike; Tang, Lijuan; Song, Dan; Song, Shanshan; Ma, Wei; Xu, Liguang; Kuang, Hua; Wu, Xiaoling; Liu, Liqiang; Chen, Xin; Xu, Chuanlai

2016-01-01

A surface-enhanced Raman scattering (SERS) sensor based on gold nanostar (Au NS) core-silver nanoparticle (Ag NP) satellites was fabricated for the first time to detect aflatoxinB1 (AFB1). We constructed the SERS sensor using AFB1 aptamer (DNA1)-modified Ag satellites and a complementary sequence (DNA2)-modified Au NS core. The Raman label (ATP) was modified on the surface of Ag satellites. The SERS signal was enhanced when the satellite NP was attached to the Au core NS. The AFB1 aptamer on the surface of Ag satellites would bind to the targets when AFB1 was present in the system, Ag satellites were then removed and the SERS signal decreased. This SERS sensor showed superior specificity for AFB1 and the linear detection range was from 1 to 1000 pg mL-1 with the limit of detection (LOD) of 0.48 pg mL-1. The excellent recovery experiment using peanut milk demonstrated that the sensor could be applied in food and environmental detection.A surface-enhanced Raman scattering (SERS) sensor based on gold nanostar (Au NS) core-silver nanoparticle (Ag NP) satellites was fabricated for the first time to detect aflatoxinB1 (AFB1). We constructed the SERS sensor using AFB1 aptamer (DNA1)-modified Ag satellites and a complementary sequence (DNA2)-modified Au NS core. The Raman label (ATP) was modified on the surface of Ag satellites. The SERS signal was enhanced when the satellite NP was attached to the Au core NS. The AFB1 aptamer on the surface of Ag satellites would bind to the targets when AFB1 was present in the system, Ag satellites were then removed and the SERS signal decreased. This SERS sensor showed superior specificity for AFB1 and the linear detection range was from 1 to 1000 pg mL-1 with the limit of detection (LOD) of 0.48 pg mL-1. The excellent recovery experiment using peanut milk demonstrated that the sensor could be applied in food and environmental detection. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08372a

Surface-enhanced Raman scattering spectroscopy characterization and identification of foodborne bacteria

NASA Astrophysics Data System (ADS)

Liu, Yongliang; Chen, Yud-Ren; Nou, Xiangwu; Chao, Kaunglin

2007-09-01

Rapid and routine identification of foodborne bacteria are considerably important, because of bio- / agro- terrorism threats, public health concerns, and economic loss. Conventional, PCR, and immunoassay methods for the detection of bacteria are generally time-consuming, chemical reagent necessary and multi-step procedures. Fast microbial detection requires minimal sample preparation, permits the routine analysis of large numbers of samples with negligible reagent costs, and is easy to operate. Therefore, we have developed silver colloidal nanoparticle based surface-enhanced Raman scattering (SERS) spectroscopy as a potential tool for the rapid and routine detection of E. coli and L. monocytogenes. This study presents the further results of our examination on S. typhimonium, one of the most commonly outbreak bacteria, for the characteristic bands and subsequent identification.

Identification of biological agents using surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Paxon, Tracy L.; Duthie, R. Scott; Renko, Casey; Burns, Andrew A.; Lesaicherre, Marie L.; Mondello, Frank J.

2011-05-01

GE Global Research Center, in collaboration with Morpho Detection, Inc. has developed an assay scheme for the identification of biological agents using Surface Enhanced Raman Scattering (SERS). Specifically, unique spectroscopic signatures are generated using SERS tags consisting of individual glass-encapsulated gold nanoparticles and surfacebound reporter molecules. These SERS tags are modified with a capture moiety specific to the antigen of interest, and serve as a spectroscopic label in a bead-based sandwich assay. Assays are being developed for a variety of pathogens and this paper will focus on aspects of assay development, optimization, stabilization and validation. Results on the development of an assay to detect Ricin toxin will be presented, and preliminary feasibility studies for the detection of additional pathogens will be discussed.

Study on nasopharyngeal cancer tissue using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ge, Xiaosong; Lin, Xueliang; Xu, Zhihong; Wei, Guoqiang; Huang, Wei; Lin, Duo

2016-10-01

Surface-enhanced Raman spectroscopy (SERS) can provide detailed molecular structure and composition information, and has demonstrated great potential in biomedical filed. This spectroscopy technology has become one of the most important optical techniques in the early diagnosis of cancer. Nasopharyngeal cancer (NPC) is a malignant neoplasm arising in the nasopharyngeal epithelial lining, which has relatively high incidence and death rate in Southeast Asia and southern China. This paper reviews the current progress of SERS in the field of cancer diagnostics, including gastric cancer, colorectal cancer, cervical cancer and nasopharyngeal cancer. In addition to above researches, we recently develop a novel NPC detection method based on tissue section using SERS, and obtain primary results. The proposed method has promising potential for the detection of nasopharyngeal carcinoma.

Large surface-enhanced Raman scattering from self-assembled gold nanosphere monolayers

NASA Astrophysics Data System (ADS)

Fontana, Jake; Livenere, John; Bezares, Francisco J.; Caldwell, Joshua D.; Rendell, Ronald; Ratna, Banahalli R.

2013-05-01

We demonstrate an average surface-enhanced Raman scattering enhancement on the order of 108 from benzenethiol molecules using self-assembled, macroscopic, and tunable gold nanosphere monolayers on non-templated substrates. The self-assembly of the nanosphere monolayers uses a simple and efficient technique that allows for the creation of a high-density, chemically functionalized gold nanosphere monolayers with enhancement factors comparable to those produced using top-down fabrication techniques. These films may provide an approach for the future development of portable chemical/biological sensors.

Analysis of 2-ethylhexyl-p-methoxycinnamate in sunscreen products by HPLC and Raman spectroscopy.

PubMed

Cheng, J; Li, Y S; L Roberts, R; Walker, G

1997-10-01

The analyses of 2-ethylhexyl-p-methoxycinnamate (EHMC) using HPLC and Raman spectroscopy have been undertaken and compared. EHMC, which is one of the most widely used sunscreen agents in suncare products in the US, exhibits a strong Raman signal. This signal clearly appears in both ethanol solutions of EHMC as well as in commercial sunscreen lotions containing this sun screen agent. A method for the direct detection and analysis of EHMC has been developed using Raman spectroscopy. This was accomplished by correlating the Raman intensities with the HPLC assays for a series of prototype suncare formulations. Based upon this information, it would be possible to employ Raman spectroscopy as an in-process control method in the commercial production of suncare products containing EHMC. The possibility of applying surface-enhanced Raman scattering for trace analysis was discussed.

Design of the sample cell in near-field surface-enhanced Raman scattering by finite difference time domain method

NASA Astrophysics Data System (ADS)

Li, Yaqin; Jian, Guoshu; Wu, Shifa

2006-11-01

The rational design of the sample cell may improve the sensitivity of surface-enhanced Raman scattering (SERS) detection in a high degree. Finite difference time domain (FDTD) simulations of the configuration of Ag film-Ag particles illuminated by plane wave and evanescent wave are performed to provide physical insight for design of the sample cell. Numerical solutions indicate that the sample cell can provide more "hot spots' and the massive field intensity enhancement occurs in these "hot spots'. More information on the nanometer character of the sample can be got because of gradient-field Raman (GFR) of evanescent wave.

Silver-nanoparticle-based surface-enhanced Raman scattering wiper for the detection of dye adulteration of medicinal herbs.

PubMed

Li, Dan; Zhu, Qingxia; Lv, Diya; Zheng, Binxing; Liu, Yanhua; Chai, Yifeng; Lu, Feng

2015-08-01

By using a silver nanoparticle wiper as a surface-enhanced Raman scattering substrate, a highly sensitive, convenient, and rapid platform for detecting dye adulteration of medicinal herbs was obtained. Commercially available filter paper was functionalized with silver nanoparticles to transform it into the flexible wiper. This device was found to collect dye molecules with unprecedented ease. Experiments were performed to optimize various factors such as the type of wiper used, the wetting reagent, and the wetting/wiping mode and time. Excellent wiper performance was observed in the detection of the simulated adulteration of samples with dyes at various concentrations. The limits of detection for nine dyes, including 10(-6) g/mL for malachite green, 10(-7) g/mL for Rhodamine 6G, and 5 × 10(-8) g/mL for methylene blue, were discerned. The results of this investigation show that this proposed method is potentially highly advantageous for field-based applications. Graphical Abstract Schematic diagram illustrating the fabrication of the paper-based SERS substrate, sample collection process on a herb and SERS examination with the portable Raman spectrometer.

Surface-enhanced Raman scattering activity of niobium surface after irradiation with femtosecond laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanov, Victor G.; Georgi Nadjakov Institute of Solid State Physics, BAS, 72 Tzarigradsko Chaussee, 1784 Sofia; Vlakhov, Emil S.

2015-11-28

The chemical modification of the niobium (Nb) surface after irradiation with femtosecond laser pulses was investigated by scanning electron microscopy coupled with energy dispersive spectroscopy, atomic force microscopy, grazing incidence X-ray diffraction, and micro-Raman spectroscopy. The physical-chemical analyses indicated that the laser treatment results in oxidation of the Nb surface, as well as in the formation of Nb hydrides. Remarkably, after the samples' washing in ethanol, a strong Surface-Enhanced Raman Scattering (SERS) signal originating from the toluene residual traces was evidenced. Further, it was observed that the laser irradiated Nb surface is able to provide a SERS enhancement of ∼1.3 × 10{supmore » 3} times for rhodamine 6G solutions. Thus, for the first time it was shown that Nb/Nb oxide surfaces could exhibit SERS functionality, and so one can expect applications in biological/biochemical screening or for sensing of dangerous environmental substances.« less

Label-free serum ribonucleic acid analysis for colorectal cancer detection by surface-enhanced Raman spectroscopy and multivariate analysis

NASA Astrophysics Data System (ADS)

Chen, Yanping; Chen, Gang; Feng, Shangyuan; Pan, Jianji; Zheng, Xiongwei; Su, Ying; Chen, Yan; Huang, Zufang; Lin, Xiaoqian; Lan, Fenghua; Chen, Rong; Zeng, Haishan

2012-06-01

Studies with circulating ribonucleic acid (RNA) not only provide new targets for cancer detection, but also open up the possibility of noninvasive gene expression profiling for cancer. In this paper, we developed a surface-enhanced Raman scattering (SERS), platform for detection and differentiation of serum RNAs of colorectal cancer. A novel three-dimensional (3-D), Ag nanofilm formed by dry MgSO4 aggregated silver nanoparticles, Ag NP, as the SERS-active substrate was presented to effectively enhance the RNA Raman signals. SERS measurements were performed on two groups of serum RNA samples. One group from patients, n=55 with pathologically diagnosed colorectal cancer and the other group from healthy controls, n=45. Tentative assignments of the Raman bands in the normalized SERS spectra demonstrated that there are differential expressions of cancer-related RNAs between the two groups. Linear discriminate analysis, based on principal component analysis, generated features can differentiate the colorectal cancer SERS spectra from normal SERS spectra with sensitivity of 89.1 percent and specificity of 95.6 percent. This exploratory study demonstrated great potential for developing serum RNA SERS analysis into a useful clinical tool for label-free, noninvasive screening and detection of colorectal cancers.

3D ZnO/Ag Surface-Enhanced Raman Scattering on Disposable and Flexible Cardboard Platforms

PubMed Central

Pimentel, Ana; Araújo, Andreia; Águas, Hugo; Martins, Rodrigo; Fortunato, Elvira

2017-01-01

In the present study, zinc oxide (ZnO) nanorods (NRs) with a hexagonal structure have been synthesized via a hydrothermal method assisted by microwave radiation, using specialized cardboard materials as substrates. Cardboard-type substrates are cost-efficient and robust paper-based platforms that can be integrated into several opto-electronic applications for medical diagnostics, analysis and/or quality control devices. This class of substrates also enables highly-sensitive Raman molecular detection, amiable to several different operational environments and target surfaces. The structural characterization of the ZnO NR arrays has been carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical measurements. The effects of the synthesis time (5–30 min) and temperature (70–130 °C) of the ZnO NR arrays decorated with silver nanoparticles (AgNPs) have been investigated in view of their application for surface-enhanced Raman scattering (SERS) molecular detection. The size and density of the ZnO NRs, as well as those of the AgNPs, are shown to play a central role in the final SERS response. A Raman enhancement factor of 7 × 105 was obtained using rhodamine 6 G (R6G) as the test analyte; a ZnO NR array was produced for only 5 min at 70 °C. This condition presents higher ZnO NR and AgNP densities, thereby increasing the total number of plasmonic “hot-spots”, their volume coverage and the number of analyte molecules that are subject to enhanced sensing.

Visible wavelength surface-enhanced Raman spectroscopy from In-InP nanopillars for biomolecule detection

NASA Astrophysics Data System (ADS)

Murdoch, B. J.; Portoles, J. F.; Tardio, S.; Barlow, A. J.; Fletcher, I. W.; Cumpson, P. J.

2016-12-01

Visible wavelength surface-enhanced Raman spectroscopy (SERS) has been observed from bovine serum albumin (BSA) using In-InP nanopillars synthesised by Ar gas cluster ion beam sputtering of InP wafers. InP provides a high local refractive index for plasmonic In structures, which increases the wavelength of the In surface plasmon resonance. The Raman scattering signal was determined to be up to 285 times higher for BSA deposited onto In-InP nanopillars when compared with Si wafer substrates. These substrates demonstrate the label-free detection of biomolecules by visible wavelength SERS, without the use of noble metal particles.

Tip-enhanced Raman scattering of bacillus subtilis spores

NASA Astrophysics Data System (ADS)

Rusciano, G.; Zito, G.; Pesce, G.; Sasso, A.; Isticato, R.; Ricca, E.

2015-07-01

Understanding of the complex interactions of molecules at biological interfaces is a fundamental issue in biochemistry, biotechnology as well as biomedicine. A plethora of biological processes are ruled by the molecular texture of cellular membrane: cellular communications, drug transportations and cellular recognition are just a few examples of such chemically-mediated processes. Tip-Enhanced Raman Scattering (TERS) is a novel, Raman-based technique which is ideally suited for this purpose. TERS relies on the combination of scanning probe microscopy and Raman spectroscopy. The basic idea is the use of a metalled tip as a sort of optical nano-antenna, which gives place to SERS effect close to the tip end. Herein, we present the application of TERS to analyze the surface of Bacillus subtilis spores. The choice of this biological systems is related to the fact that a number of reasons support the use of spores as a mucosal delivery system. The remarkable and well-documented resistance of spores to various environmental and toxic effects make them clear potentials as a novel, surface-display system. Our experimental outcomes demonstrate that TERS is able to provide a nano-scale chemical imaging of spore surface. Moreover, we demonstrate that TERS allows differentiation between wilde-type spore and genetically modified strains. These results hold promise for the characterization and optimization of spore surface for drug-delivery applications.

SERS-active ZnO/Ag hybrid WGM microcavity for ultrasensitive dopamine detection

NASA Astrophysics Data System (ADS)

Lu, Junfeng; Xu, Chunxiang; Nan, Haiyan; Zhu, Qiuxiang; Qin, Feifei; Manohari, A. Gowri; Wei, Ming; Zhu, Zhu; Shi, Zengliang; Ni, Zhenhua

2016-08-01

Dopamine (DA) is a potential neuro modulator in the brain which influences a variety of motivated behaviors and plays a key role in life science. A hybrid ZnO/Ag microcavity based on Whispering Gallery Mode (WGM) effect has been developed for ultrasensitive detection of dopamine. Utilizing this effect of structural cavity mode, a Raman signal of R6G (5 × 10-3 M) detected by this designed surface-enhanced Raman spectroscopy (SERS)-active substrate was enhanced more than 10-fold compared with that of ZnO film/Ag substrate. Also, this hybrid microcavity substrate manifests high SERS sensitivity to rhodamine 6 G and detection limit as low as 10-12 M to DA. The Localized Surface Plasmons of Ag nanoparticles and WGM-enhanced light-matter interaction mainly contribute to the high SERS sensitivity and help to achieve a lower detection limit. This designed SERS-active substrate based on the WGM effect has the potential for detecting neurotransmitters in life science.

Achieving Very Low Levels of Detection: An Improved Surface-Enhanced Raman Scattering Experiment for the Physical Chemistry Teaching Laboratory

ERIC Educational Resources Information Center

McMillan, Brian G.

2016-01-01

This experiment was designed and successfully introduced to complement the nanochemistry taught to undergraduate students in a useful and interesting way. Colloidal Ag nanoparticles were synthesized by a simple, room-temperature method, and the resulting suspension was then used to study the surface-enhanced Raman scattering (SERS) of methylene…

Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

ERIC Educational Resources Information Center

Schnitzer, Cheryl S.; Reim, Candace Lawson; Sirois, John J.; House, Paul G.

2010-01-01

Advanced chemistry students are introduced to surface-enhanced resonance Raman scattering (SERRS) by studying how sodium copper chlorophyllin (CuChl) adsorbs onto silver colloids (CuChl/Ag) as a function of pH. Using both SERRS and visible extinction spectroscopy, the extent of CuChl adsorption and colloidal aggregation are monitored. Initially at…

Application of silver films with different roughness parameter for septic human serum albumin detection by Surface Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Zyubin, A. Y.; Konstantinova, E. I.; Matveeva, K. I.; Slezhkin, V. A.; Samusev, I. G.; Demin, M. V.; Bryukhanov, V. V.

2018-01-01

In this paper, the rough silver films parameters investigation, used as media for surface enhancement Raman spectroscopy for health and septic human serum albumin (HSA) study results have been presented. The detection of small concentrations of HSA isolated from blood serum and it main vibrational groups identification has been done.

Surface enhanced Raman scattering of biospecies on anodized aluminum oxide films

NASA Astrophysics Data System (ADS)

Zhang, C.; Smirnov, A. I.; Hahn, D.; Grebel, H.

2007-06-01

Traditionally, aluminum and anodized aluminum oxide films (AAO) are not the platforms of choice for surface-enhanced raman scattering (SERS) experiments despite of the aluminum's large negative permittivity value. Here we examine the usefulness of aluminum and nanoporous alumina platforms for detecting soft biospecies ranging from bacterial spores to protein markers. We used these flat platforms to examine SERS of a model protein (cytochrome c from bovine heart tissue) and bacterial cells (spores of Bacillus subtilis ATCC13933 used as Anthrax simulant) and demonstrated clear Raman amplification.

Nanogap embedded silver gratings for surface plasmon enhanced fluorescence

NASA Astrophysics Data System (ADS)

Bhatnagar, Kunal

Plasmonic nanostructures have been extensively used in the past few decades for applications in sub-wavelength optics, data storage, optoelectronic circuits, microscopy and bio-photonics. The enhanced electromagnetic field produced at the metal and dielectric interface by the excitation of surface plasmons via incident radiation can be used for signal enhancement in fluorescence and surface enhanced Raman scattering studies. Novel plasmonic structures have shown to provide very efficient and extreme light concentration at the nano-scale in recent years. The enhanced electric field produced within a few hundred nanometers of these surfaces can be used to excite fluorophores in the surrounding environment. Fluorescence based bio-detection and bio-imaging are two of the most important tools in the life sciences and improving the qualities and capabilities of fluorescence based detectors and imaging equipment remains a big challenge for industry manufacturers. We report a novel fabrication technique for producing nano-gap embedded periodic grating substrates on the nanoscale using a store bought HD-DVD and conventional soft lithography procedures. Polymethylsilsesquioxane (PMSSQ) polymer is used as the ink for the micro-contact printing process with PDMS stamps obtained from the inexpensive HD-DVDs as master molds. Fluorescence enhancement factors of up to 118 times were observed with these silver nanostructures in conjugation with Rhodamine-590 fluorescent dye. These substrates are ideal candidates for a robust and inexpensive optical system with applications such as low-level fluorescence based analyte detection, single molecule imaging, and surface enhanced Raman studies. Preliminary results in single molecule experiments have also been obtained by imaging individual 3 nm and 20 nm dye-doped nanoparticles attached to the silver plasmonic gratings using epi-fluorescence microscopy.

Chemo-spectroscopic sensor for carboxyl terminus overexpressed in carcinoma cell membrane.

PubMed

Stanca, Sarmiza E; Matthäus, Christian; Neugebauer, Ute; Nietzsche, Sandor; Fritzsche, Wolfgang; Dellith, Jan; Heintzmann, Rainer; Weber, Karina; Deckert, Volker; Krafft, Christoph; Popp, Jürgen

2015-10-01

Certain carboxyl groups of the plasma membrane are involved in tumorgenesis processes. A gold core-hydroxyapatite shell (AuHA) nanocomposite is introduced as chemo-spectroscopic sensor to monitor these carboxyl groups of the cell membrane. Hydroxyapatite (HA) plays the role both of a chemical detector and of a biocompatible Raman marker. The principle of detection is based on chemical interaction between the hydroxyl groups of the HA and the carboxyl terminus of the proteins. The AuHA exhibits a surface enhanced Raman scattering (SERS) signal at 954 cm(-1) which can be used for its localization. The bio-sensing capacity of AuHA towards human skin epidermoid carcinoma (A431) and Chinese hamster ovary (CHO) cell lines is investigated using Raman microspectroscopic imaging. The localization of AuHA on cells is correlated with scanning electron microscopy, transmission electron microscopy and structured illumination fluorescence microscopy. This qualitative approach is a step towards a quantitative study of the proteins terminus. This method would enable further studies on the molecular profiling of the plasma membrane, in an attempt to provide accurate cell identification. Using a gold core-hydroxyapatite shell (AuHA) nanocomposite, the authors in this paper showed the feasibility of detecting and differentiating cell surface molecules by surface enhanced Raman scattering. Copyright © 2015 Elsevier Inc. All rights reserved.

Tapered Optical Fiber Probe Assembled with Plasmonic Nanostructures for Surface-Enhanced Raman Scattering Application.

PubMed

Huang, Zhulin; Lei, Xing; Liu, Ye; Wang, Zhiwei; Wang, Xiujuan; Wang, Zhaoming; Mao, Qinghe; Meng, Guowen

2015-08-12

Optical fiber-Raman devices integrated with plasmonic nanostructures have promising potentials for in situ probing remote liquid samples and biological samples. In this system, the fiber probe is required to simultaneously demonstrate stable surface enhanced Raman scattering (SERS) signals and high sensitivity toward the target species. Here we demonstrate a generic approach to integrate presynthesized plasmonic nanostructures with tapered fiber probes that are prepared by a dipping-etching method, through reversed electrostatic attraction between the silane couple agent modified silica fiber probe and the nanostructures. Using this approach, both negatively and positively charged plasmonic nanostructures with various morphologies (such as Au nanosphere, Ag nanocube, Au nanorod, Au@Ag core-shell nanorod) can be stably assembled on the tapered silica fiber probes. Attributed to the electrostatic force between the plasmonic units and the fiber surface, the nanostructures do not disperse in liquid samples easily, making the relative standard deviation of SERS signals as low as 2% in analyte solution. Importantly, the detection sensitivity of the system can be optimized by adjusting the cone angle (from 3.6° to 22°) and the morphology of nanostructures assembled on the fiber. Thus, the nanostructures-sensitized optical fiber-Raman probes show great potentials in the applications of SERS-based environmental detection of liquid samples.

Correlative SEM SERS for quantitative analysis of dimer nanoparticles.

PubMed

Timmermans, F J; Lenferink, A T M; van Wolferen, H A G M; Otto, C

2016-11-14

A Raman microscope integrated with a scanning electron microscope was used to investigate plasmonic structures by correlative SEM-SERS analysis. The integrated Raman-SEM microscope combines high-resolution electron microscopy information with SERS signal enhancement from selected nanostructures with adsorbed Raman reporter molecules. Correlative analysis is performed for dimers of two gold nanospheres. Dimers were selected on the basis of SEM images from multi aggregate samples. The effect of the orientation of the dimer with respect to the polarization state of the laser light and the effect of the particle gap size on the Raman signal intensity is observed. Additionally, calculations are performed to simulate the electric near field enhancement. These simulations are based on the morphologies observed by electron microscopy. In this way the experiments are compared with the enhancement factor calculated with near field simulations and are subsequently used to quantify the SERS enhancement factor. Large differences between experimentally observed and calculated enhancement factors are regularly detected, a phenomenon caused by nanoscale differences between the real and 'simplified' simulated structures. Quantitative SERS experiments reveal the structure induced enhancement factor, ranging from ∼200 to ∼20 000, averaged over the full nanostructure surface. The results demonstrate correlative Raman-SEM microscopy for the quantitative analysis of plasmonic particles and structures, thus enabling a new analytical method in the field of SERS and plasmonics.

Vibrational fingerprinting of bacterial pathogens by surface enhanced Raman scattering (SERS)

NASA Astrophysics Data System (ADS)

Premasiri, W. Ranjith; Moir, D. T.; Ziegler, Lawrence D.

2005-05-01

The surface enhanced Raman scattering (SERS) spectra of vegetative whole-cell bacteria were obtained using in-situ grown gold nanoparticle cluster-covered silicon dioxide substrates excited at 785 nm. SERS spectra of Gram-negative bacteria; E. coli and S. typhimurium, and Gram-positive bacteria; B. subtilis, B. cereus, B. thuringeinsis and B. anthracis Sterne, have been observed. Raman enhancement factors of ~104-105 per cell are found for both Gram positive and Gram negative bacteria on this novel SERS substrate. The bacterial SERS spectra are species specific and exhibit greater species differentiation and reduced spectral congestion than their corresponding non-SERS (bulk) Raman spectra. Fluorescence observed in the 785 nm excited bulk Raman emission of Bacillus species is not apparent in the corresponding SERS spectra. The surface enhancement effect allows the observation of Raman spectra at the single cell level excited by low incident laser powers (< 3 mW) and short data acquisition times (~20 sec.). Comparison with previous SERS studies suggests that these SERS vibrational signatures are sensitively dependent on the specific morphology and nature of the SERS active substrate. Exposure to biological environments, such as human blood serum, has an observable effect on the bacterial SERS spectra. However, reproducible, species specific SERS vibrational fingerprints are still obtained. The potential of SERS for detection and identification of bacteria with species specificity on these gold nanoparticle coated substrates is demonstrated by these results.

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials.

PubMed

Dick, Susan; Konrad, Magdalena P; Lee, Wendy W Y; McCabe, Hannah; McCracken, John N; Rahman, Taifur M D; Stewart, Alan; Xu, Yikai; Bell, Steven E J

2016-07-01

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of substrate on electric field enhancement of Tip-enhanced Raman spectroscopy (TERS)

NASA Astrophysics Data System (ADS)

Bahreini, Maryam

2018-01-01

The characterization of materials down to a few-molecule level is a key challenge in nanotechnology. Raman spectroscopy is a powerful method that provides chemical information via nondestructive vibrational fingerprinting. Unfortunately, this method suffers from signal weakness which prevents the study of small quantities. Tip-enhanced Raman spectroscopy (TERS) which combines the chemical sensitivity of Raman spectroscopy (RS) with high spatial resolution of scanning probe microscopy (SPM), provides chemical images of surfaces at the nanometer scale. In this method, irradiation of an SPM tip by a focused laser beam results in enhancement of local electric field via two reasons of localized surface plasmon resonance and lightning rod effect. This enhancement leads to the enhancement in Raman intensity from the sample surface in the vicinity of tip. In all TERS measurements, samples should be located on a substrate. In this paper, the dependence of the electric field enhancement to the substrate has been investigated. In simulations, three-dimensional finite-difference time-domain (3D-FDTD) method is used for numerical solution of Maxwell's equations. Our results show that the electric field enhancement is weak for the tip alone case. Introducing a substrate provides further electric field enhancement via near field electromagnetic dipole-dipole coupling between the tip and substrate. Since the side-illumination geometry is used for laser irradiation, the vertical component of the incident field plays a dominant role in the electric field enhancement. Therefore, the coupling effect between the tip and the substrate is the key contribution to the enhancement. For the case of silicon tip and the gold substrate, the electric field enhancement is improved considerably. There is an optimal tip size for TERS because of the competing effects of the radiation damping and the surface scattering of the tip. The results show the substrate as an effective tool for the improvement of the TERS detection sensitivity.

Periodic array-based substrates for surface-enhanced infrared spectroscopy

NASA Astrophysics Data System (ADS)

Mayerhöfer, Thomas G.; Popp, Jürgen

2018-01-01

At the beginning of the 1980s, the first reports of surface-enhanced infrared spectroscopy (SEIRS) surfaced. Probably due to signal-enhancement factors of only 101 to 103, which are modest compared to those of surface-enhanced Raman spectroscopy (SERS), SEIRS did not reach the same significance up to date. However, taking the compared to Raman scattering much larger cross-sections of infrared absorptions and the enhancement factors together, SEIRS reaches about the same sensitivity for molecular species on a surface in terms of the cross-sections as SERS and, due to the complementary nature of both techniques, can valuably augment information gained by SERS. For the first 20 years since its discovery, SEIRS relied completely on metal island films, fabricated by either vapor or electrochemical deposition. The resulting films showed a strong variance concerning their structure, which was essentially random. Therefore, the increase in the corresponding signal-enhancement factors of these structures stagnated in the last years. In the very same years, however, the development of periodic array-based substrates helped SEIRS to gather momentum. This development was supported by technological progress concerning electromagnetic field solvers, which help to understand plasmonic properties and allow targeted design. In addition, the strong progress concerning modern fabrication methods allowed to implement these designs into practice. The aim of this contribution is to critically review the development of these engineered surfaces for SEIRS, to compare the different approaches with regard to their performance where possible, and report further gain of knowledge around and in relation to these structures.

High-speed Raman-encoded molecular imaging of freshly excised tissue surfaces with topically applied SERRS nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Yu "Winston"; Yang, Qian; Kang, Soyoung; Wall, Matthew A.; Liu, Jonathan T. C.

2018-04-01

Surface-enhanced Raman scattering (SERS) nanoparticles (NPs) are increasingly being engineered for a variety of disease-detection and treatment applications. For example, we have previously developed a fiber-optic Raman-encoded molecular imaging (REMI) system for spectral imaging of biomarker-targeted SERS NPs topically applied on tissue surfaces to identify residual tumors at surgical margins. Although accurate tumor detection was achieved, the commercial SERS NPs used in our previous studies lacked the signal strength to enable high-speed imaging with high pixel counts (large fields of view and/or high spatial resolution), which limits their use for certain time-constrained clinical applications. As a solution, we explored the use of surface-enhanced resonant Raman scattering (SERRS) NPs to enhance imaging speeds. The SERRS NPs were synthesized de novo, and then conjugated to HER2 antibodies to achieve high binding affinity, as validated by flow cytometry. Under identical tissue-staining and imaging conditions, the targeted SERRS NPs enabled reliable identification of HER2-overexpressed tumor xenografts with 50-fold-enhanced imaging speed compared with our standard targeted SERS NPs. This enables our REMI system to image tissue surfaces at a rate of 150 cm2 per minute at a spatial resolution of 0.5 mm.

Design of label-free, homogeneous biosensing platform based on plasmonic coupling and surface-enhanced Raman scattering using unmodified gold nanoparticles.

PubMed

Yi, Zi; Li, Xiao-Yan; Liu, Feng-Juan; Jin, Pei-Yan; Chu, Xia; Yu, Ru-Qin

2013-05-15

Surface-enhanced Raman scattering (SERS) has emerged as a promising spectroscopic technique for biosensing. However, to design a SERS-based biosensor, almost all currently used methods involve the time-consuming and complicated modification of the metallic nanoparticles with the Raman active dye and biorecognition element, which restricts their widespread applications. Herein, we report a label-free, homogeneous and easy-to-operate biosensing platform for the rapid, simple and sensitive SERS detection by using the unmodified gold nanoparticles (Au NPs). This strategy utilizes the difference in adsorption property of single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) on citrate-coated Au NPs. In the presence of dsDNA, the aggregation of Au NPs takes place after adding salt solution because the dsDNA cannot adsorb on the Au NPs to protect them from salt-induced aggregation. Such aggregation gives rise to the plasmonic coupling of adjacent metallic NPs and turns on the enhancement of the Raman scattering, displaying a strong SERS signal. In contrast, the ssDNA can adsorb on the Au NPs surface through strong electrostatic attraction and protect them from salt-induced aggregation, showing a weak SERS signal. This approach is not only straightforward and simple in design but also rapid and convenient in operation. The feasibility and universality of the design have been demonstrated successfully by the detection of DNA and Hg(2+), and the assay possesses the superior signal-to-background ratio as high as ∼30 and excellent selectivity. The method can be extended to detect various analytes, such as other metal ions, proteins and small molecules by using the oligonucleotides that can selectively bind the analytes. Copyright © 2012 Elsevier B.V. All rights reserved.

Quantitative surface-enhanced resonance Raman scattering of phthalocyanine-labelled oligonucleotides

PubMed Central

Macaskill, A.; Chernonosov, A. A.; Koval, V. V.; Lukyanets, E. A.; Fedorova, O. S.; Smith, W. E.; Faulds, K.; Graham, D.

2007-01-01

The evaluation of phthalocyanine labels for the surface-enhanced resonance Raman scattering (SERRS) detection of oligonucleotides is reported. Three phthalocyanine-labelled oligonucleotides were assessed, each containing a different metal centre. Detection limits for each labelled oligonucleotide were determined using two excitation frequencies where possible. Limits of detection as low as 2.8 × 10−11 mol. dm−3 were obtained which are comparable to standard fluorescently labelled probes used in previous SERRS studies. The identification of two phthalocyanine-labelled oligonucleotides without separation was also demonstrated indicating their suitability for multiplexing. This study extends the range of labels suitable for quantitative surface-enhanced resonance Raman scattering with silver nanoparticles and offers more flexibility and choice when considering SERRS for quantitative DNA detection. PMID:17289751

Near field plasmonic gradient effects on high vacuum tip-enhanced Raman spectroscopy.

PubMed

Fang, Yurui; Zhang, Zhenglong; Chen, Li; Sun, Mengtao

2015-01-14

Near field gradient effects in high vacuum tip-enhanced Raman spectroscopy (HV-TERS) are a recent developing ultra-sensitive optical and spectral analysis technology on the nanoscale, based on the plasmons and plasmonic gradient enhancement in the near field and under high vacuum. HV-TERS can not only be used to detect ultra-sensitive Raman spectra enhanced by surface plasmon, but also to detect clear molecular IR-active modes enhanced by strongly plasmonic gradient. Furthermore, the molecular overtone modes and combinational modes can also be experimentally measured, where the Fermi resonance and Darling-Dennison resonance were successfully observed in HV-TERS. Theoretical calculations using electromagnetic field theory firmly supported experimental observation. The intensity ratio of the plasmon gradient term over the linear plasmon term can reach values greater than 1. Theoretical calculations also revealed that with the increase in gap distance between tip and substrate, the decrease in the plasmon gradient was more significant than the decrease in plasmon intensity, which is the reason that the gradient Raman can be only observed in the near field. Recent experimental results of near field gradient effects on HV-TERS were summarized, following the section of the theoretical analysis.

Surface-enhanced Raman scattering of amorphous silica gel adsorbed on gold substrates for optical fiber sensors

NASA Astrophysics Data System (ADS)

Degioanni, S.; Jurdyc, A. M.; Cheap, A.; Champagnon, B.; Bessueille, F.; Coulm, J.; Bois, L.; Vouagner, D.

2015-10-01

Two kinds of gold substrates are used to produce surface-enhanced Raman scattering (SERS) of amorphous silica obtained via the sol-gel route using tetraethoxysilane Si(OC2H5)4 (TEOS) solution. The first substrate consists of a gold nanometric film elaborated on a glass slide by sputter deposition, controlling the desired gold thickness and sputtering current intensity. The second substrate consists of an array of micrometer-sized gold inverted pyramidal pits able to confine surface plasmon (SP) enhancing electric field, which results in a distribution of electromagnetic energy inside the cavities. These substrates are optically characterized to observe SPR with, respectively, extinction and reflectance spectrometries. Once coated with thin layers of amorphous silica (SiO2) gel, these samples show Raman amplification of amorphous SiO2 bands. This enhancement can occur in SERS sensors using amorphous SiO2 gel as shells, spacers, protective coatings, or waveguides, and represents particularly a potential interest in the field of Raman distributed sensors, which use the amorphous SiO2 core of optical fibers as a transducer to make temperature measurements.

Method of Stamping Surface-Enhance Raman Spectroscopy for Label-Free, Multiplexed, Molecular Sensing and Imaging

NASA Technical Reports Server (NTRS)

Shih, Wei-Chuan (Inventor)

2017-01-01

The present disclosure relates the use of a stamping surface enhanced Raman scattering (S-SERS) technique with nanoporous gold disk (NPGD) plasmonic substrates to produce a label-free, multiplexed molecular sensing and imaging technique. A NPGD SERS substrate is stamped onto a surface containing one or more target molecules, followed by SERS measurement of the target molecules located between the surface and SERS substrate. The target molecules may be deposited on the surface, which may be a carrier substrate such as polydimethylsiloxane (PDMS).

Analysis of low active-pharmaceutical-ingredient signal drugs based on thin layer chromatography and surface-enhanced Raman spectroscopy.

PubMed

Li, Xiao; Chen, Hui; Zhu, Qingxia; Liu, Yan; Lu, Feng

2016-11-30

Active pharmaceutical ingredients (API) embedded in the excipients of the formula can usually be unravelled by normal Raman spectroscopy (NRS). However, more and more drugs with low API content and/or low Raman scattering coefficient were insensitive to NRS analysis, which was for the first time defined as Low API-Signal Drugs (LASIDs) in this paper. The NRS spectra of these LASIDs were similar to their dominant excipients' profiles, such as lactose, starch, microcrystalline cellulose (MCC), etc., and were classified into three types as such. 21 out of 100 kinds of drugs were screened as LASIDs and characterized further by Raman microscopic mapping. Accordingly, we proposed a tailored solution to the qualitation and quantitation problem of these LASIDs, using surface-enhanced Raman spectroscopic (SERS) detection on the thin layer chromatographic (TLC) plate both in situ and after-separation. Experimental conditions and parameters including TLC support matrix, SERS substrate, detection mode, similarity threshold, internal standard, etc., were optimized. All LASIDs were satisfactorily identified and the quantitation results agreed well with those of high performance liquid chromatography (HPLC). For some structural analogues of LASIDs, although they presented highly similar SERS spectra and were tough to distinguish even with Raman microscopic mapping, they could be successfully discriminated from each other by coupling SERS (with portable Raman spectrometer) with TLC. These results demonstrated that the proposed solution could be employed to detect the LASIDs with high accuracy and cost-effectiveness. Copyright © 2016 Elsevier B.V. All rights reserved.

Towards advanced biological detection using surface enhanced raman scattering (SERS)-based sensors

NASA Astrophysics Data System (ADS)

Hankus, Mikella E.; Stratis-Cullum, Dimitra N.; Pellegrino, Paul M.

2010-08-01

The Army has a need for an accurate, fast, reliable and robust means to identify and quantify defense related materials. Raman spectroscopy is a form of vibrational spectroscopy that is rapidly becoming a valuable tool for homeland defense applications, as it is well suited for the molecular identification of a variety of compounds, including explosives and chemical and biological hazards. To measure trace levels of these types of materials, surface enhanced Raman scattering (SERS), a specialized form of Raman scattering, can be employed. The SERS enhancements are produced on, or in close proximity to, a nanoscale roughened metal surface and are typically associated with increased local electromagnetic field strengths. However, before application of SERS in the field and in particular to biological and other hazard sensing applications, significant improvements in substrate performance are needed. In this work, we will report the use of several SERS substrate architectures (colloids, film-over-nanospheres (FONs) and commercially available substrates) for detecting and differentiating numerous endospore samples. The variance in spectra as obtained using different sensing architectures will also be discussed. Additionally, the feasibility of using a modified substrate architecture that is tailored with molecular recognition probe system for detecting biological samples will be explored. We will discuss the progress towards an advanced, hybrid molecular recognition with a SERS/Fluorescence nanoprobe system including the optimization, fabrication, and spectroscopic analysis of samples on a commercially available substrate. Additionally, the feasibility of using this single-step switching architecture for hazard material detection will also be explored.

Dealloyed Intra-Nanogap Particles with Highly Robust, Quantifiable Surface-Enhanced Raman Scattering Signals for Biosensing and Bioimaging Applications

PubMed Central

2018-01-01

Uniformly controlling a large number of metal nanostructures with a plasmonically enhanced signal to generate quantitative optical signals and the widespread use of these structures for surface-enhanced Raman scattering (SERS)-based biosensing and bioimaging applications are of paramount importance but are extremely challenging. Here, we report a highly controllable, facile selective-interdiffusive dealloying chemistry for synthesizing the dealloyed intra-nanogap particles (DIPs) with a ∼2 nm intragap in a high yield (∼95%) without the need for an interlayer. The SERS signals from DIPs are highly quantitative and polarization-independent with polarized laser sources. Remarkably, all the analyzed particles displayed the SERS enhancement factors (EFs) of ≥1.1 × 108 with a very narrow distribution of EFs. Finally, we show that DIPs can be used as ultrasensitive SERS-based DNA detection probes for detecting 10 aM to 1 pM target concentrations and highly robust, quantitative real-time cell imaging probes for long-term imaging with low laser power and short exposure time. PMID:29532028

Cellular imaging by targeted assembly of hot-spot SERS and photoacoustic nanoprobes using split-fluorescent protein scaffolds.

PubMed

Köker, Tuğba; Tang, Nathalie; Tian, Chao; Zhang, Wei; Wang, Xueding; Martel, Richard; Pinaud, Fabien

2018-02-09

The in cellulo assembly of plasmonic nanomaterials into photo-responsive probes is of great interest for many bioimaging and nanophotonic applications but remains challenging with traditional nucleic acid scaffolds-based bottom-up methods. Here, we address this quandary using split-fluorescent protein (FP) fragments as molecular glue and switchable Raman reporters to assemble gold or silver plasmonic nanoparticles (NPs) into photonic clusters directly in live cells. When targeted to diffusing surface biomarkers in cancer cells, the NPs self-assemble into surface-enhanced Raman-scattering (SERS) nanoclusters having hot spots homogenously seeded by the reconstruction of full-length FPs. Within plasmonic hot spots, autocatalytic activation of the FP chromophore and near-field amplification of its Raman fingerprints enable selective and sensitive SERS imaging of targeted cells. This FP-driven assembly of metal colloids also yields enhanced photoacoustic signals, allowing the hybrid FP/NP nanoclusters to serve as contrast agents for multimodal SERS and photoacoustic microscopy with single-cell sensitivity.

Achieving optimal SERS through enhanced experimental design.

PubMed

Fisk, Heidi; Westley, Chloe; Turner, Nicholas J; Goodacre, Royston

2016-01-01

One of the current limitations surrounding surface-enhanced Raman scattering (SERS) is the perceived lack of reproducibility. SERS is indeed challenging, and for analyte detection, it is vital that the analyte interacts with the metal surface. However, as this is analyte dependent, there is not a single set of SERS conditions that are universal. This means that experimental optimisation for optimum SERS response is vital. Most researchers optimise one factor at a time, where a single parameter is altered first before going onto optimise the next. This is a very inefficient way of searching the experimental landscape. In this review, we explore the use of more powerful multivariate approaches to SERS experimental optimisation based on design of experiments and evolutionary computational methods. We particularly focus on colloidal-based SERS rather than thin film preparations as a result of their popularity. © 2015 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons, Ltd.

Detection of Multiple Pathogens in Serum Using Silica-Encapsulated Nanotags in a Surface-Enhanced Raman Scattering-Based Immunoassay.

PubMed

Neng, Jing; Li, Yina; Driscoll, Ashley J; Wilson, William C; Johnson, Patrick A

2018-06-06

A robust immunoassay based on surface-enhanced Raman scattering (SERS) has been developed to simultaneously detect trace quantities of multiple pathogenic antigens from West Nile virus, Rift Valley fever virus, and Yersinia pestis in fetal bovine serum. Antigens were detected by capture with silica-encapsulated nanotags and magnetic nanoparticles conjugated with polyclonal antibodies. The magnetic pull-down resulted in aggregation of the immune complexes, and the silica-encapsulated nanotags provided distinct spectra corresponding to each antigen captured. The limit of detection was ∼10 pg/mL in 20% fetal bovine serum, a significant improvement over previous studies in terms of sensitivity, level of multiplexing, and medium complexity. This highly sensitive multiplex immunoassay platform provides a promising method to detect various antigens directly in crude serum samples without the tedious process of sample preparation, which is desirable for on-site diagnostic testing and real-time disease monitoring.

Fluorescence-Raman Dual Modal Endoscopic System for Multiplexed Molecular Diagnostics

NASA Astrophysics Data System (ADS)

Jeong, Sinyoung; Kim, Yong-Il; Kang, Homan; Kim, Gunsung; Cha, Myeong Geun; Chang, Hyejin; Jung, Kyung Oh; Kim, Young-Hwa; Jun, Bong-Hyun; Hwang, Do Won; Lee, Yun-Sang; Youn, Hyewon; Lee, Yoon-Sik; Kang, Keon Wook; Lee, Dong Soo; Jeong, Dae Hong

2015-03-01

Optical endoscopic imaging, which was recently equipped with bioluminescence, fluorescence, and Raman scattering, allows minimally invasive real-time detection of pathologies on the surface of hollow organs. To characterize pathologic lesions in a multiplexed way, we developed a dual modal fluorescence-Raman endomicroscopic system (FRES), which used fluorescence and surface-enhanced Raman scattering nanoprobes (F-SERS dots). Real-time, in vivo, and multiple target detection of a specific cancer was successful, based on the fast imaging capability of fluorescence signals and the multiplex capability of simultaneously detected SERS signals using an optical fiber bundle for intraoperative endoscopic system. Human epidermal growth factor receptor 2 (HER2) and epidermal growth factor receptor (EGFR) on the breast cancer xenografts in a mouse orthotopic model were successfully detected in a multiplexed way, illustrating the potential of FRES as a molecular diagnostic instrument that enables real-time tumor characterization of receptors during routine endoscopic procedures.

Optical properties of nucleobase thin films as studied by attenuated total reflection and surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Kim, MinSuk; Ham, Won Kyu; Kim, Wonyoung; Hwangbo, Chang Kwon; Choi, Eun Ha; Lee, Geon Joon

2018-04-01

Optical properties of nucleobase thin films were studied by attenuated total reflection (ATR) and surface-enhanced Raman spectroscopy (SERS). Adenine and guanine films were deposited on fused silica and silver at room temperature by thermal evaporation, and the normal dispersion of refractive indices of transparent adenine and guanine films in the visible and near-infrared regions were analyzed. The measured ATR spectra of adenine (guanine) films and numerical simulations by optical transfer matrix formalism demonstrate that the shift of surface plasmon resonance (SPR) wavelength is approximately linearly proportional to the adenine (guanine) film thickness, indicating that SPR can be used for quantitative measurements of biomaterials. The Raman spectra indicated that the adenine (guanine) films can be deposited by thermal evaporation. The adenine (guanine) films on silver exhibited Raman intensity enhancement as compared to those on glass, which was attributed to the SPR effect of silver platform and might play a role as a hot plate for SERS detection of biomaterials.

Facile synthesis of gold coated copper(II) hydroxide pine-needle-like micro/nanostructures for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Long, Kailin; Du, Deyang; Luo, Xiaoguang; Zhao, Weiwei; Wu, Zhangting; Si, Lifang; Qiu, Teng

2014-08-01

This work reports a facile method to fabricate gold coated copper(II) hydroxide pine-needle-like micro/nanostructures for surface-enhanced Raman scattering (SERS) application. The effects of reaction parameters on the shape, size and surface morphology of the products are systematically investigated. The as-prepared 3D hierarchical structures have the advantage of a large surface area available for the formation of hot spots and the adsorption of target analytes, thus dramatically improving the Raman signals. The finite difference time domain calculations indicate that the pine-needle-like model pattern may demonstrate a high quality SERS property owing to the high density and abundant hot spot characteristic in closely spaced needle-like arms.

Bifunctional nanoparticles for surface-enhanced Raman spectroscopy-based leukemia biomarker detection

NASA Astrophysics Data System (ADS)

Mehn, Dora; Morasso, Carlo; Vanna, Renzo; Schiumarini, Domitilla; Bedoni, Marzia; Ciceri, Fabio; Gramatica, Furio

2014-03-01

The Wilms tumor gene (WT1) is a biomarker overexpressed in more than 90% of acute myeloid leukemia patients. Fast and sensitive detection of the WT1 in blood samples would allow monitoring of the minimal residual disease during clinical remission and would permit early detection of a potential relapse in acute myeloid leukemia. In this work, Surface Enhanced Raman Spectroscopy (SERS) based detection of the WT1 sequence using bifunctional, magnetic core - gold shell nanoparticles is presented. The classical co-precipitation method was applied to generate magnetic nanoparticles which were coated with a gold shell after modification with aminopropyltriethoxy silane and subsequent deposition of gold nanoparticle seeds. Simple hydroquinone based reduction procedure was applied for the shell growing in water based reaction mixture at room temperature. Thiolated ssDNA probes of the WT1 sequence were immobilized as capture oligonucleotides on the gold surface. Malachite green was applied both for testing the amplification performance of the core-shell colloidal SERS substrate and also as label dye of the target DNA sequence. The SERS enhancer efficacy of the core-shell nanomaterial was compared with the efficacy of classical spherical gold particles produced using the conventional citrate reduction method. The core-shell particles were found not only to provide an opportunity for facile separation in a heterogeneous reaction system but also to be superior regarding robustness as SERS enhancers.

Trace detection of perchlorate in industrial-grade emulsion explosive with portable surface-enhanced Raman spectroscopy.

PubMed

Nuntawong, N; Eiamchai, P; Limwichean, S; Wong-ek, B; Horprathum, M; Patthanasettakul, V; Leelapojanaporn, A; Nakngoenthong, S; Chindaudom, P

2013-12-10

Recent analyses by ion-exchange chromatography (IC) showed that, beside nitrate, the majority of the industrial-grade emulsion explosives, extensively used by most separatists in the southern Thailand insurgency, contained small traces of perchlorate anions. In demand for the faster, reliable, and simple detection methods, the portable detection of nitrate and perchlorate became the great interest for the forensic and field-investigators. This work proposed a unique method to detect the trace amount of perchlorate in seven industrial-grade emulsion explosives under the field tests. We utilized the combination of the portable Raman spectroscope, the developed surfaced-enhanced Raman substrates, and the sample preparation procedures. The portable Raman spectroscope with a laser diode of 785 nm for excitation and a thermoelectric-cooled CCD spectrometer for detection was commercially available. The SERS substrates, with uniformly distributed nanostructured silver nanorods, were fabricated by the DC magnetron sputtering system, based on the oblique-angle deposition technique. The sample preparation procedures were proposed based on (1) pentane extraction technique and (2) combustion technique, prior to being dissolved in the purified water. In comparison to the ion chromatography and the conventional Raman measurements, our proposed methods successfully demonstrated the highly sensitive detectability of the minimal trace amount of perchlorate from five of the explosives with minimal operating time. This work was therefore highly practical to the development for the forensic analyses of the post-blast explosive residues under the field-investigations. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Using a silver-enhanced microarray sandwich structure to improve SERS sensitivity for protein detection.

PubMed

Gu, Xuefang; Yan, Yuerong; Jiang, Guoqing; Adkins, Jason; Shi, Jian; Jiang, Guomin; Tian, Shu

2014-03-01

A simple and sensitive method, based on surface-enhanced Raman scattering (SERS), for immunoassay and label-free protein detection is reported. A series of bowl-shaped silver cavity arrays were fabricated by electrodeposition using a self-assembled polystyrene spheres template. The reflection spectra of these cavity arrays were recorded as a function of film thickness, and then correlated with SERS enhancement using sodium thiophenolate as the probe molecule. The results reveal that SERS enhancement can be maximized when the frequency of both the incident laser and the Raman scattering approach the frequency of the localized surface plasmon resonance. The optimized array was then used as the bottom layer of a silver nanoparticle-protein-bowl-shaped silver cavity array sandwich. The second layer of silver was introduced by the interactions between the proteins in the middle layer of the sandwich architecture and silver nanoparticles. Human IgG bound to the surface of this microcavity array can retain its recognition function. With the Raman reporter molecules labeled on the antibody, a detection limit down to 0.1 ng mL(-1) for human IgG is easily achieved. Furthermore, the SERS spectra of label-free proteins (catalase, cytochrome C, avidin and lysozyme) from the assembled sandwich have excellent reproducibility and high quality. The results reveal that the proposed approach has potential for use in qualitative and quantitative detection of biomolecules.

A practical method to fabricate gold substrates for surface-enhanced Raman spectroscopy.

PubMed

Tantra, Ratna; Brown, Richard J C; Milton, Martin J T; Gohil, Dipak

2008-09-01

We describe a practical method of fabricating surface-enhanced Raman spectroscopy (SERS) substrates based on dip-coating poly-L-lysine derivatized microscope slides in a gold colloidal suspension. The use of only commercially available starting materials in this preparation is particularly advantageous, aimed at both reducing time and the inconsistency associated with surface modification of substrates. The success of colloid deposition has been demonstrated by scanning electron microscopy (SEM) and the corresponding SERS response (giving performance comparable to the corresponding traditional colloidal SERS substrates). Reproducibility was evaluated by conducting replicate measurements across six different locations on the substrate and assessing the extent of the variability (standard deviation values of spectral parameters: peak width and height), in response to either Rhodamine 6G or Isoniazid. Of particular interest is the observation of how some peaks in a given spectrum are more susceptible to data variability than others. For example, in a Rhodamine 6G SERS spectrum, spectral parameters of the peak at 775 cm(-1) were shown to have a relative standard deviation (RSD) % of <10%, while the peak at 1573 cm(-1) has a RSD of >or=10%. This observation is best explained by taking into account spectral variations that arise from the effect of a chemisorption process and the local nature of chemical enhancement mechanisms, which affects the enhancement of some spectral peaks but not others (analogous to resonant Raman phenomenon).

Fabrication of multi-functional silicon surface by direct laser writing

NASA Astrophysics Data System (ADS)

Verma, Ashwani Kumar; Soni, R. K.

2018-05-01

We present a simple, quick and one-step methodology based on nano-second laser direct writing for the fabrication of micro-nanostructures on silicon surface. The fabricated surfaces suppress the optical reflection by multiple reflection due to light trapping effect to a much lower value than polished silicon surface. These textured surfaces offer high enhancement ability after gold nanoparticle deposition and then explored for Surface Enhanced Raman Scattering (SERS) for specific molecular detection. The effect of laser scanning line interval on optical reflection and SERS signal enhancement ability was also investigated. Our results indicate that low optical reflection substrates exhibit uniform SERS enhancement with enhancement factor of the order of 106. Furthermore, this methodology provide an alternative approach for cost-effective large area fabrication with good control over feature size.

Rapid label-free identification of Klebsiella pneumoniae antibiotic resistant strains by the drop-coating deposition surface-enhanced Raman scattering method

NASA Astrophysics Data System (ADS)

Cheong, Youjin; Kim, Young Jin; Kang, Heeyoon; Choi, Samjin; Lee, Hee Joo

2017-08-01

Although many methodologies have been developed to identify unknown bacteria, bacterial identification in clinical microbiology remains a complex and time-consuming procedure. To address this problem, we developed a label-free method for rapidly identifying clinically relevant multilocus sequencing typing-verified quinolone-resistant Klebsiella pneumoniae strains. We also applied the method to identify three strains from colony samples, ATCC70063 (control), ST11 and ST15; these are the prevalent quinolone-resistant K. pneumoniae strains in East Asia. The colonies were identified using a drop-coating deposition surface-enhanced Raman scattering (DCD-SERS) procedure coupled with a multivariate statistical method. Our workflow exhibited an enhancement factor of 11.3 × 106 to Raman intensities, high reproducibility (relative standard deviation of 7.4%), and a sensitive limit of detection (100 pM rhodamine 6G), with a correlation coefficient of 0.98. All quinolone-resistant K. pneumoniae strains showed similar spectral Raman shifts (high correlations) regardless of bacterial type, as well as different Raman vibrational modes compared to Escherichia coli strains. Our proposed DCD-SERS procedure coupled with the multivariate statistics-based identification method achieved excellent performance in discriminating similar microbes from one another and also in subtyping of K. pneumoniae strains. Therefore, our label-free DCD-SERS procedure coupled with the computational decision supporting method is a potentially useful method for the rapid identification of clinically relevant K. pneumoniae strains.

Diagnostic potential for gold nanoparticle-based surface-enhanced Raman spectroscopy to provide colorectal cancer screening using blood serum sample

NASA Astrophysics Data System (ADS)

Lin, Duo; Feng, Shangyuan; Pan, Jianji; Chen, Yanping; Lin, Juqiang; Sun, Liqing; Chen, Rong

2011-11-01

Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopic technique that is capable of probing the biomolecular changes associated with diseased transformation. The objective of our study was to explore gold nanoparticle based SERS to obtain blood serum biochemical information for non-invasive colorectal cancer detection. SERS measurements were performed on two groups of blood serum samples: one group from patients (n = 38) with pathologically confirmed colorectal cancer and the other group from healthy volunteers (control subjects, n = 45). Tentative assignments of the Raman bands in the measured SERS spectra suggested interesting cancer specific biomolecular changes, including an increase in the relative amounts of nucleic acid, a decrease in the percentage of saccharide and proteins contents in the blood serum of colorectal cancer patients as compared to that of healthy subjects. Principal component analysis (PCA) of the measured SERS spectra separated the spectral features of the two groups into two distinct clusters with little overlaps. Linear discriminate analysis (LDA) based on the PCA generated features differentiated the nasopharyngeal cancer SERS spectra from normal SERS spectra with high sensitivity (97.4%) and specificity (100%). The results from this exploratory study demonstrated that gold nanoparticle based SERS serum analysis combined with PCA-LDA has tremendous potential for the non-invasive detection of colorectal cancers.

Diagnostic potential for gold nanoparticle-based surface-enhanced Raman spectroscopy to provide colorectal cancer screening using blood serum sample

NASA Astrophysics Data System (ADS)

Lin, Duo; Feng, Shangyuan; Pan, Jianji; Chen, Yanping; Lin, Juqiang; Sun, Liqing; Chen, Rong

2012-03-01

Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopic technique that is capable of probing the biomolecular changes associated with diseased transformation. The objective of our study was to explore gold nanoparticle based SERS to obtain blood serum biochemical information for non-invasive colorectal cancer detection. SERS measurements were performed on two groups of blood serum samples: one group from patients (n = 38) with pathologically confirmed colorectal cancer and the other group from healthy volunteers (control subjects, n = 45). Tentative assignments of the Raman bands in the measured SERS spectra suggested interesting cancer specific biomolecular changes, including an increase in the relative amounts of nucleic acid, a decrease in the percentage of saccharide and proteins contents in the blood serum of colorectal cancer patients as compared to that of healthy subjects. Principal component analysis (PCA) of the measured SERS spectra separated the spectral features of the two groups into two distinct clusters with little overlaps. Linear discriminate analysis (LDA) based on the PCA generated features differentiated the nasopharyngeal cancer SERS spectra from normal SERS spectra with high sensitivity (97.4%) and specificity (100%). The results from this exploratory study demonstrated that gold nanoparticle based SERS serum analysis combined with PCA-LDA has tremendous potential for the non-invasive detection of colorectal cancers.

Remote excitation and detection of surface-enhanced Raman scattering from graphene.

PubMed

Coca-López, Nicolás; Hartmann, Nicolai F; Mancabelli, Tobia; Kraus, Jürgen; Günther, Sebastian; Comin, Alberto; Hartschuh, Achim

2018-06-07

We demonstrate the remote excitation and detection of surface-enhanced Raman scattering (SERS) from graphene using a silver nanowire as a plasmonic waveguide. By investigating a nanowire touching a graphene sheet at only one terminal, we first show the remote excitation of SERS from graphene by propagating surface plasmon polaritons (SPPs) launched by a focused laser over distances on the order of 10 μm. Remote detection of SERS is then demonstrated for the same nanowire by detecting light emission at the distal end of the nanowire that was launched by graphene Raman scattering and carried to the end of the nanowire by SPPs. We then show that the transfer of the excitation and Raman scattered light along the nanowire can also be visualized through spectrally selective back focal plane imaging. Back focal plane images detected upon focused laser excitation at one of the nanowire's tips reveal propagating surface plasmon polaritons at the laser energy and at the energies of the most prominent Raman bands of graphene. With this approach the identification of remote excitation and detection of SERS for nanowires completely covering the Raman scatterer is achieved, which is typically not possible by direct imaging.

Development of a miRNA surface-enhanced Raman scattering assay using benchtop and handheld Raman systems

NASA Astrophysics Data System (ADS)

Schechinger, Monika; Marks, Haley; Locke, Andrea; Choudhury, Mahua; Cote, Gerard

2018-01-01

DNA-functionalized nanoparticles, when paired with surface-enhanced Raman spectroscopy (SERS), can rapidly detect microRNA. However, widespread use of this approach is hindered by drawbacks associated with large and expensive benchtop Raman microscopes. MicroRNA-17 (miRNA-17) has emerged as a potential epigenetic indicator of preeclampsia, a condition that occurs during pregnancy. Biomarker detection using an SERS point-of-care device could enable prompt diagnosis and prevention as early as the first trimester. Recently, strides have been made in developing portable Raman systems for field applications. An SERS assay for miRNA-17 was assessed and translated from traditional benchtop Raman microscopes to a handheld system. Three different photoactive molecules were compared as potential Raman reporter molecules: a chromophore, malachite green isothiocyanate (MGITC), a fluorophore, tetramethylrhodamine isothiocyanate, and a polarizable small molecule 5,5-dithio-bis-(2-nitrobenzoic acid) (DTNB). For the benchtop Raman microscope, the DTNB-labeled assay yielded the greatest sensitivity under 532-nm laser excitation, but the MGITC-labeled assay prevailed at 785 nm. Conversely, DTNB was preferable for the miniaturized 785-nm Raman system. This comparison showed significant SERS enhancement variation in response to 1-nM miRNA-17, implying that the sensitivity of the assay may be more heavily dependent on the excitation wavelength, instrumentation, and Raman reporter chosen than on the plasmonic coupling from DNA/miRNA-mediated nanoparticle assemblies.

Highly active surface-enhanced Raman scattering (SERS) substrates based on gold nanoparticles infiltrated into SiO2 inverse opals

NASA Astrophysics Data System (ADS)

Ankudze, Bright; Philip, Anish; Pakkanen, Tuula T.; Matikainen, Antti; Vahimaa, Pasi

2016-11-01

SiO2 inverse opal (IO) films with embedded gold nanoparticles (AuNPs) for surface-enhanced Raman scattering (SERS) application are reported. SiO2 IO films were loaded with AuNPs by a simple infiltration in a single cycle to form Au-SiO2 IOs. The optical property and the morphology of the Au-SiO2 IO substrates were characterized; it was observed that they retained the Bragg diffraction of SiO2 IO and the localized surface plasmon resonance (LSPR) of AuNPs. The SERS property of the Au-SiO2 IO substrates were studied with methylene blue (MB) and 4-aminothiophenol (4-ATP). The SERS enhancement factors were 107 and 106 for 4-ATP and MB, respectively. A low detection limit of 10-10 M for 4-ATP was also obtained with the Au-SiO2 IO substrate. A relative standard deviation of 18.5% for the Raman signals intensity at 1077 cm-1 for 4-ATP shows that the Au-SiO2 IO substrates have good signal reproducibility. The results of this study indicate that the Au-SiO2 IO substrates can be used in sensing and SERS applications.

Detection of tobacco-related biomarkers in urine samples by surface-enhanced Raman spectroscopy coupled with thin-layer chromatography.

PubMed

Huang, Rongfu; Han, Sungyub; Li, Xiao Sheryl

2013-08-01

The nicotine metabolites, cotinine and trans-3'-hydroxycotinine (3HC) are considered as superior biomarkers for identifying tobacco exposure. More importantly, the ratio of 3HC to cotinine is a good indicator to phenotype individuals for cytochrome P450 2A6 activity and to individualize pharmacotherapy for tobacco addiction. In this paper, a simple, robust and novel method based on surface-enhanced Raman spectroscopy coupled with thin-layer chromatography (TLC) was developed to directly quantify the biomarkers in human urine samples. This is the first time surface-enhanced Raman spectroscopy (SERS) was used to detect cotinine and 3HC in urine samples. The linear dynamic range for the detection of cotinine is from 40 nM to 8 μM while that of 3HC is from 1 μM to 15 μM. The detection limits are 10 nM and 0.2 μM for cotinine and 3HC, respectively. The proposed method was further validated by quantifying the concentration of both cotinine and 3HC in smokers' urine samples. This TLC-SERS method allows the direct detection of cotinine in the urine samples of both active and passive smokers and the detection of 3HC in smokers.

Novel Surface-Enhanced Raman Scattering-based Assays for Ultra-sensitive Detection of Human Pluripotent Stem Cells

PubMed Central

Han, Jingjia; Qian, Ximei; Wu, Qingling; Jha, Rajneesh; Duan, Jinshuai; Yang, Zhou; Maher, Kevin O.; Nie, Shuming; Xu, Chunhui

2017-01-01

Human pluripotent stem cells (hPSCs) are a promising cell source for regenerative medicine, but their derivatives need to be rigorously evaluated for residual stem cells to prevent teratoma formation. Here, we report the development of novel surface-enhanced Raman scattering (SERS)-based assays that can detect trace numbers of undifferentiated hPSCs in mixed cell populations in a highly specific, ultra-sensitive, and time-efficient manner. By targeting stem cell surface markers SSEA-5 and TRA-1-60 individually or simultaneously, these SERS assays were able to identify as few as 1 stem cell in 106 cells, a sensitivity (0.0001%) which was ~2,000 to 15,000-fold higher than that of flow cytometry assays. Using the SERS assay, we demonstrate that the aggregation of hPSC-based cardiomyocyte differentiation cultures into 3D spheres significantly reduced SSEA-5+ and TRA-1-60+ cells compared with parallel 2D cultures. Thus, SERS may provide a powerful new technology for quality control of hPSC-derived products for preclinical and clinical applications. PMID:27509304

Characterization and Discrimination of Gram-Positive Bacteria Using Raman Spectroscopy with the Aid of Principal Component Analysis.

PubMed

Colniță, Alia; Dina, Nicoleta Elena; Leopold, Nicolae; Vodnar, Dan Cristian; Bogdan, Diana; Porav, Sebastian Alin; David, Leontin

2017-09-01

Raman scattering and its particular effect, surface-enhanced Raman scattering (SERS), are whole-organism fingerprinting spectroscopic techniques that gain more and more popularity in bacterial detection. In this work, two relevant Gram-positive bacteria species, Lactobacillus casei ( L. casei ) and Listeria monocytogenes ( L. monocytogenes ) were characterized based on their Raman and SERS spectral fingerprints. The SERS spectra were used to identify the biochemical structures of the bacterial cell wall. Two synthesis methods of the SERS-active nanomaterials were used and the recorded spectra were analyzed. L. casei and L. monocytogenes were successfully discriminated by applying Principal Component Analysis (PCA) to their specific spectral data.

Characterization and Discrimination of Gram-Positive Bacteria Using Raman Spectroscopy with the Aid of Principal Component Analysis

PubMed Central

Leopold, Nicolae; Vodnar, Dan Cristian; Bogdan, Diana; Porav, Sebastian Alin; David, Leontin

2017-01-01

Raman scattering and its particular effect, surface-enhanced Raman scattering (SERS), are whole-organism fingerprinting spectroscopic techniques that gain more and more popularity in bacterial detection. In this work, two relevant Gram-positive bacteria species, Lactobacillus casei (L. casei) and Listeria monocytogenes (L. monocytogenes) were characterized based on their Raman and SERS spectral fingerprints. The SERS spectra were used to identify the biochemical structures of the bacterial cell wall. Two synthesis methods of the SERS-active nanomaterials were used and the recorded spectra were analyzed. L. casei and L. monocytogenes were successfully discriminated by applying Principal Component Analysis (PCA) to their specific spectral data. PMID:28862655

Design and measurement technique of surface-enhanced Raman scattering for detection of bisphenol A

NASA Astrophysics Data System (ADS)

Abu Bakar, Norhayati; Mat Salleh, Muhamad; Umar, Akrajas Ali; Shapter, Joseph George

2017-06-01

Surface-enhanced Raman scattering (SERS) is a highly sensitive measurement technique that provides Raman peaks at different Raman shift for different molecule structures. The SERS sensor is potentially used to detect food contamination and monitor environmental pollutants. A self-developed SERS system for specific analysis with low development cost is a challenging issue. This study attempts to develop a simple SERS sensor system for detection of bisphenol A (BPA) molecule using SERS substrate of silver nanoplate film. A SERS sensor system was developed, consisting of a light source to excite analyte molecules, Inphotonic Raman probe, sensor chamber and spectrophotometer as an analyser system. A duplex fibre optic is used to transmit light from the source to the probe and from the probe to the spectrophotometer. For SERS measurement, BPA detection was done by comparing the Raman signal spectra of the BPA on the quartz substrate and BPA on the silver nanoplate film. This SERS sensor successfully sensed BPA with SERS enhancement factor (EF) 5.55  ×  103 and a detection limit of BPA concentration at 1 mM.

Cytochrome c at charged interfaces studied by resonance Raman and surface-enhanced resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Hildebrandt, Peter

1991-05-01

The effect of electrostatic fields on the structure of cytochrome c bound to charged interfaces was studied by resonance Raman and surface enhanced resonance Raman spectroscopy. Binding of this heme protein to the Ag electrode or heteropolytungstates which may be regarded as simple model systems for biological interfaces establishes an equilibrium between two conformational states (I II). In state I the structure and the redox potential are the same as for the uncomplexed cytochrome c. In state II however the heme pocket assumes an open structure and the axial iron Met80 bond is weakened leading to thennal coordination equilibrium between the fivecoordinated high spin and the sixcoordinated low spin configuration. These structural changes are accompanied by a decrease of the redox potential by 420 mV. The structural rearrangement of the heme pocket in state II is presumably initiated by the dissociation of the internal salt bridge of Lys13 due to electrostatic interactions with the negatively charged surfaces of the model systems. From detailed Raman spectroscopic studies characteristic spectral properties of the states I and II were identified. Based on these findings the interactions of cytochrome c with phospholipid vesicles as well as with its physiological reaction partner cytocbrome c oxidase were analysed. A systematic study of the cytochmme c/phospholipid system by varying the lipid composition and the temperature revealed mutual structural changes in both the lipid and the protein structure.

Spectroscopy on the wing: naturally inspired SERS substrates for biochemical analysis.

PubMed

Garrett, Natalie L; Vukusic, Peter; Ogrin, Feodor; Sirotkin, Evgeny; Winlove, C Peter; Moger, Julian

2009-03-01

We show that naturally occurring chitinous nanostructures found on the wings of the Graphium butterfly can be used as substrates for surface-enhanced Raman scattering when coated with a thin film of gold or silver. The substrates were found to exhibit excellent biocompatibility and sensitivity, making them ideal for protein assaying. An assay using avidin/biotin binding showed that the substrates could be used to quantify protein binding directly from changes in the surface-enhanced Raman scattering (SERS) spectra and were sensitive over a concentration range comparable with a typical enzyme-linked immunosorbent assays (ELISA) assay. A biomimetic version of the wing nanostructures produced using a highly reproducible, large-scale fabrication process, yielded comparable enhancement factors and biocompatibility. The excellent biocompatibility of the wings and biomimetic substrates is unparalleled by other lithographically produced substrates, and this could pave the way for widespread application of ultrasensitive SERS-based bioassays.

Highly sensitive surface enhanced Raman scattering substrates based on Ag decorated Si nanocone arrays and their application in trace dimethyl phthalate detection

NASA Astrophysics Data System (ADS)

Zuo, Zewen; Zhu, Kai; Ning, Lixin; Cui, Guanglei; Qu, Jun; Cheng, Ying; Wang, Junzhuan; Shi, Yi; Xu, Dongsheng; Xin, Yu

2015-01-01

Wafer-scale three-dimensional (3D) surface enhancement Raman scattering (SERS) substrates were prepared using the plasma etching and ion sputtering methods that are completely compatible with well-established silicon device technologies. The substrates are highly sensitive with excellent uniformity and reproducibility, exhibiting an enhancement factor up to 1012 with a very low relative standard deviation (RSD) around 5%. These are attributed mainly to the uniform-distributed, multiple-type high-density hot spots originating from the structural characteristics of Ag nanoparticles (NPs) decorated Si nanocone (NC) arrays. We demonstrate that the trace dimethyl phthalate (DMP) at a concentration of 10-7 M can be well detected using this SERS substrate, showing that the AgNPs-decorated SiNC arrays can serve as efficient SERS substrates for phthalate acid esters (PAEs) detection with high sensitivity.

Particle-Film Plasmons on Periodic Silver Film over Nanosphere (AgFON): A Hybrid Plasmonic Nanoarchitecture for Surface-Enhanced Raman Spectroscopy.

PubMed

Lee, Jiwon; Zhang, Qianpeng; Park, Seungyoung; Choe, Ayoung; Fan, Zhiyong; Ko, Hyunhyub

2016-01-13

Plasmonic systems based on particle-film plasmonic couplings have recently attracted great attention because of the significantly enhanced electric field at the particle-film gaps. Here, we introduce a hybrid plasmonic architecture utilizing combined plasmonic effects of particle-film gap plasmons and silver film over nanosphere (AgFON) substrates. When gold nanoparticles (AuNPs) are assembled on AgFON substrates with controllable particle-film gap distances, the AuNP-AgFON system supports multiple plasmonic couplings from interparticle, particle-film, and crevice gaps, resulting in a huge surface-enhanced Raman spectroscopy (SERS) effect. We show that the periodicity of AgFON substrates and the particle-film gaps greatly affects the surface plasmon resonances, and thus, the SERS effects due to the interplay between multiple plasmonic couplings. The optimally designed AuNP-AgFON substrate shows a SERS enhancement of 233 times compared to the bare AgFON substrate. The ultrasensitive SERS sensing capability is also demonstrated by detecting glutathione, a neurochemical molecule that is an important antioxidant, down to the 10 pM level.

Raman and surface enhanced Raman spectroscopy of amino acids and peptide

NASA Astrophysics Data System (ADS)

Yuan, Xiaojuan; Gu, Huaimin; Wu, Jiwei; Kang, Jian; Dong, Xiao

2009-08-01

Surface enhanced Raman scattering (SERS) is potentially tool in the characterization of biomolecules such as amino acids, complicated peptides and proteins, and even tissues or living cells. Amino acids and short peptides contain different functional groups. Therefore, they are suitable for the investigations of the competitive-interactions of these functional groups with colloidal silver surfaces. In this paper, Normal Raman and SERS of amino acids Leucine and Isoleucine and short peptide Leu-Leu were measured on the silver colloidal substrate. Raman shifts that stem from different vibrational mode in the molecular inner structure, and the variations of SERS of the samples were analyzed in this study. The results show that different connection of one methyl to the main chains of the isomer amino acids resulted in different vibration modes in the Normal Raman spectra of Leucine and Isoleucine. In the SERS spectra of the isomer amino acids, all frequency shifts are expressed more differently than those in Normal Raman spectra of solid state. Orientation of this isomer amino acids, as well as specific-competitive interactions of their functional groups with the colloidal silver surface, were speculated by detailed spectral analysis of the obtained SERS spectra. In addition, the dipeptide Leu-Leu, as the corresponding homodipeptide of Leucine, was also measured adsorbed on the colloidal silver surface. The SERS spectrum of Leu-Leu is different from its corresponding amino acid Leucine but both of them are adsorbed on the silver surface through the carboxylate moiety.

Raman imaging of lipid bilayer membrane by surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Mori, Motoaki; Abe, Shunsuke; Kondo, Takahiro; Saito, Yuika

2018-04-01

We investigated two-dimensional lipid bilayers by spectroscopic imaging with surface enhanced Raman spectroscopy (SERS). A DSPC lipid bilayer incubated on a glass substrate was coated with a thin layer of silver. Due to the strong electromagnetic enhancement of the silver film and the affinity to lipid molecules, the Raman spectrum of a single bilayer was obtained in a 1 s exposure time with 0.1 mW of incident laser power. In the C-H vibrational region of the spectra, which is sensitive to bilayer configurations, a randomly stacked area was dominated by the CH3 asymmetric-stretch mode, whereas flat areas including double bilayers showed typical SERS spectra. The spectral features of the randomly stacked area are explained by the existence of many free lipid molecules, which is supported by DFT calculations of paired DSPC molecules. Our method can be applied to reveal the local crystallinity of single lipid bilayers, which is difficult to assess by conventional Raman imaging.

Interaction of proflavine with DNA studied by colloid surface enhanced resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Koglin, E.; Séquaris, J.-M.

1986-03-01

The interaction of the mutagenic highly fluourescing proflavine (3,6-diaminoacridine: PF) dye with calf thymus DNA has been studied by Surface Enhanced Resonance Raman Scattering (SERRS). Since the Ag-colloids almost completely quenche the strong fluorescence it is possible to obtain excellent vibrational spectra in a wide frequency range providing valuable information about the intercalation. The intercalation does not affect the vibrational frequencies of the proflavine dye. On the other hand, intensity changes are observed in some of the ring- and NH 2-modes of proflavine upon intercalation. This Raman hypochromism is characteristic for ring stacking interactions and in the SERRS spetroscopy for an additional effects of the dye orientation to the surface.

Enhancing SERS by Means of Supramolecular Charge Transfer

NASA Technical Reports Server (NTRS)

Wong, Eric; Flood, Amar; Morales, Alfredo

2009-01-01

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

The use of surface-enhanced Raman scattering for detecting molecular evidence of life in rocks, sediments, and sedimentary deposits.

PubMed

Bowden, Stephen A; Wilson, Rab; Cooper, Jonathan M; Parnell, John

2010-01-01

Raman spectroscopy is a versatile analytical technique capable of characterizing the composition of both inorganic and organic materials. Consequently, it is frequently suggested as a payload on many planetary landers. Only approximately 1 in every 10(6) photons are Raman scattered; therefore, the detection of trace quantities of an analyte dispersed in a sample matrix can be much harder to achieve. To overcome this, surface-enhanced Raman scattering (SERS) and surface-enhanced resonance Raman scattering (SERRS) both provide greatly enhanced signals (enhancements between 10(5) and 10(9)) through the analyte's interaction with the locally generated surface plasmons, which occur at a "roughened" or nanostructured metallic surface (e.g., Cu, Au, and Ag). Both SERS and SERRS may therefore provide a viable technique for trace analysis of samples. In this paper, we describe the development of SERS assays for analyzing trace amounts of compounds present in the solvent extracts of sedimentary deposits. These assays were used to detect biological pigments present in an Arctic microoasis (a small locale of elevated biological productivity) and its detrital regolith, characterize the pigmentation of microbial mats around hydrothermal springs, and detect fossil organic matter in hydrothermal deposits. These field study examples demonstrate that SERS technology is sufficiently mature to be applied to many astrobiological analog studies on Earth. Many current and proposed imaging systems intended for remote deployment already posses the instrumental components needed for SERS. The addition of wet chemistry sample processing facilities to these instruments could yield field-deployable analytical instruments with a broadened analytical window for detecting organic compounds with a biological or geological origin.

Measurement of the surface-enhanced coherent anti-Stokes Raman scattering (SECARS) due to the 1574 cm(-1) surface-enhanced Raman scattering (SERS) mode of benzenethiol using low-power (<20 mW) CW diode lasers.

PubMed

Aggarwal, Roshan L; Farrar, Lewis W; Greeneltch, Nathan G; Van Duyne, Richard P; Polla, Dennis L

2013-02-01

The surface-enhanced coherent anti-Stokes Raman scattering (SECARS) from a self-assembled monolayer (SAM) of benzenethiol on a silver-coated surface-enhanced Raman scattering (SERS) substrate has been measured for the 1574 cm(-1) SERS mode. A value of 9.6 ± 1.7×10(-14) W was determined for the resonant component of the SECARS signal using 17.8 mW of 784.9 nm pump laser power and 7.1 mW of 895.5 nm Stokes laser power; the pump and Stokes lasers were polarized parallel to each other but perpendicular to the grooves of the diffraction grating in the spectrometer. The measured value of resonant component of the SECARS signal is in agreement with the calculated value of 9.3×10(-14) W using the measured value of 8.7 ± 0.5 cm(-1) for the SERS linewidth Γ (full width at half-maximum) and the value of 5.7 ± 1.4×10(-7) for the product of the Raman cross section σSERS and the surface concentration Ns of the benzenethiol SAM. The xxxx component of the resonant part of the third-order nonlinear optical susceptibility |3 χxxxx((3)R)| for the 1574 cm(-1) SERS mode has been determined to be 4.3 ± 1.1×10(-5) cm·g(-1)·s(2). The SERS enhancement factor for the 1574 cm(-1) mode was determined to be 3.6 ± 0.9×10(7) using the value of 1.8×10(15) molecules/cm(2) for Ns.

Ultrafast Dynamics of Energetic Materials

DTIC Science & Technology

2014-01-23

redistributed in condensed-phase materials. In this subproject we developed a technique termed three-dimensional IR- Raman spectroscopy that allowed us to...Fang, 2011, “The distribution of local enhancement factors in surface enhanced Raman -active substrates and the vibrational dynamics in the liquid phase...3. (invited) “Vibrational energy and molecular thermometers in liquids: Ultrafast IR- Raman spectroscopy”, Brandt C. Pein and Dana D. Dlott, To

Surface enhanced Raman gene probe and methods thereof

DOEpatents

Vo-Dinh, T.

1998-09-29

The subject invention disclosed herein is a new gene probe biosensor and methods based on surface enhanced Raman scattering (SERS) label detection. The SER gene probe biosensor comprises a support means, a SER gene probe having at least one oligonucleotide strand labeled with at least one SERS label, and a SERS active substrate disposed on the support means and having at least one of the SER gene probes adsorbed thereon. Biotargets such as bacterial and viral DNA, RNA and PNA are detected using a SER gene probe via hybridization to oligonucleotide strands complementary to the SER gene probe. The support means supporting the SERS active substrate includes a fiberoptic probe, an array of fiberoptic probes for performance of multiple assays and a waveguide microsensor array with charge-coupled devices or photodiode arrays. 18 figs.

Surface enhanced Raman gene probe and methods thereof

DOEpatents

Vo-Dinh, Tuan

1998-01-01

The subject invention disclosed herein is a new gene probe biosensor and methods thereof based on surface enhanced Raman scattering (SERS) label detection. The SER gene probe biosensor comprises a support means, a SER gene probe having at least one oligonucleotide strand labeled with at least one SERS label, and a SERS active substrate disposed on the support means and having at least one of the SER gene probes adsorbed thereon. Biotargets such as bacterial and viral DNA, RNA and PNA are detected using a SER gene probe via hybridization to oligonucleotide strands complementary to the SER gene probe. The support means supporting the SERS active substrate includes a fiberoptic probe, an array of fiberoptic probes for performance of multiple assays and a waveguide microsensor array with charge-coupled devices or photodiode arrays.

Surface enhanced Raman gene probe and methods thereof

DOEpatents

Vo-Dinh, T.

1998-02-24

The subject invention disclosed is a new gene probe biosensor and methods based on surface enhanced Raman scattering (SERS) label detection. The SER gene probe biosensor comprises a support means, a SER gene probe having at least one oligonucleotide strand labeled with at least one SERS label, and a SERS active substrate disposed on the support means and having at least one of the SER gene probes adsorbed thereon. Biotargets such as bacterial and viral DNA, RNA and PNA are detected using a SER gene probe via hybridization to oligonucleotide strands complementary to the SER gene probe. The support means includes a fiberoptic probe, an array of fiberoptic probes for performance of multiple assays and a waveguide microsensor array with charge-coupled devices or photodiode arrays. 18 figs.

Surface enhanced Raman gene probe and methods thereof

DOEpatents

Vo-Dinh, T.

1998-07-21

The subject invention disclosed is a new gene probe biosensor and methods based on surface enhanced Raman scattering (SERS) label detection. The SER gene probe biosensor comprises a support means, a SER gene probe having at least one oligonucleotide strand labeled with at least one SERS label, and a SERS active substrate disposed on the support means and having at least one of the SER gene probes adsorbed. Biotargets such as bacterial and viral DNA, RNA and PNA are detected using a SER gene probe via hybridization to oligonucleotide strands complementary to the SER gene probe. The support means supporting the SERS active substrate includes a fiberoptic probe, an array of fiberoptic probes for performance of multiple assays and a waveguide microsensor array with charge-coupled devices or photodiode arrays. 18 figs.

Characterization and noninvasive diagnosis of bladder cancer with serum surface enhanced Raman spectroscopy and genetic algorithms

NASA Astrophysics Data System (ADS)

Li, Shaoxin; Li, Linfang; Zeng, Qiuyao; Zhang, Yanjiao; Guo, Zhouyi; Liu, Zhiming; Jin, Mei; Su, Chengkang; Lin, Lin; Xu, Junfa; Liu, Songhao

2015-05-01

This study aims to characterize and classify serum surface-enhanced Raman spectroscopy (SERS) spectra between bladder cancer patients and normal volunteers by genetic algorithms (GAs) combined with linear discriminate analysis (LDA). Two group serum SERS spectra excited with nanoparticles are collected from healthy volunteers (n = 36) and bladder cancer patients (n = 55). Six diagnostic Raman bands in the regions of 481-486, 682-687, 1018-1034, 1313-1323, 1450-1459 and 1582-1587 cm-1 related to proteins, nucleic acids and lipids are picked out with the GAs and LDA. By the diagnostic models built with the identified six Raman bands, the improved diagnostic sensitivity of 90.9% and specificity of 100% were acquired for classifying bladder cancer patients from normal serum SERS spectra. The results are superior to the sensitivity of 74.6% and specificity of 97.2% obtained with principal component analysis by the same serum SERS spectra dataset. Receiver operating characteristic (ROC) curves further confirmed the efficiency of diagnostic algorithm based on GA-LDA technique. This exploratory work demonstrates that the serum SERS associated with GA-LDA technique has enormous potential to characterize and non-invasively detect bladder cancer through peripheral blood.

Cavitands Endow All-Dielectric Beads With Selectivity for Plasmon-Free Enhanced Raman Detection of Nε-Methylated Lysine.

PubMed

Alessandri, Ivano; Biavardi, Elisa; Gianoncelli, Alessandra; Bergese, Paolo; Dalcanale, Enrico

2016-06-22

SiO2/TiO2 microbeads (T-rex) are promising materials for plasmon-free surface-enhanced Raman scattering (SERS), offering several key advantages in biodiagnostics. In this paper we report the combination of T-rex beads with tetraphosphonate cavitands (Tiiii), which imparts selectivity toward Nε-methylated lysine. SERS experiments demonstrated the efficiency and selectivity of the T-rex-Tiiii assays in detecting methylated lysine hydrochloride (Nε-Me-Lys-Fmoc) from aqueous solutions, even in the presence of the parent Lys-Fmoc hydrochloride as interferent. The negative results obtained in control experiments using TSiiii ruled out any other form of surface recognition or preferential physisorption. MALDI-TOF analyses on the beads exposed to Nε-Me-Lys-Fmoc revealed the presence of the Tiiii•Nε-Me-Lys-Fmoc complex. Raman analyses based on the intensity ratio of Nε-Me-Lys-Fmoc and cavitand-specific modes resulted in a dose-response plot, which allowed for estimating the concentration of Nε-methylated lysine from initial solutions in the 1 × 10(-3) to 1 × 10(-5) M range. These results can set the basis for the development of new Raman assays for epigenetic diagnostics.

Polarization Dependence of Surface Enhanced Raman Scattering on a Single Dielectric Nanowire

DTIC Science & Technology

2012-01-01

original work is properly cited. Our measurements of surface enhanced Raman scattering (SERS) on Ga2O3 dielectric nanowires (NWs) core/silver composites...process has been widely discussed [15–21]. In this work, a highly effective SERS composite of dielectric Ga2O3 NWs core/silver was employed to investigate...self-assembled monolayer of active SERS molecules on the NWs may affect the SERS enhancement as well. 2. Experimental Details Random Ga2O3 NWs were

Surface-enhanced Raman scattering (SERS) of riboflavin on nanostructured Ag surfaces: The role of excitation wavelength, plasmon resonance and molecular resonance

NASA Astrophysics Data System (ADS)

Šubr, Martin; Kuzminova, Anna; Kylián, Ondřej; Procházka, Marek

2018-05-01

Optimization of surface-enhanced Raman scattering (SERS)-based sensors for (bio)analytical applications has received much attention in recent years. For optimum sensitivity, both the nanostructure fabrication process and the choice of the excitation wavelength used with respect to the specific analyte studied are of crucial importance. In this contribution, detailed SERS intensity profiles were measured using gradient nanostructures with the localized surface-plasmon resonance (LSPR) condition varying across the sample length and using riboflavin as the model biomolecule. Three different excitation wavelengths (633 nm, 515 nm and 488 nm) corresponding to non-resonance, pre-resonance and resonance excitation with respect to the studied molecule, respectively, were tested. Results were interpreted in terms of a superposition of the enhancement provided by the electromagnetic mechanism and intrinsic properties of the SERS probe molecule. The first effect was dictated mainly by the degree of spectral overlap between the LSPR band, the excitation wavelength along with the scattering cross-section of the nanostructures, while the latter was influenced by the position of the molecular resonance with respect to the excitation wavelength. Our experimental findings contribute to a better understanding of the SERS enhancement mechanism.

Optimization of surface enhanced Raman scattering (SERS) assay for the transition from benchtop to handheld Raman systems

NASA Astrophysics Data System (ADS)

Schechinger, Monika; Marks, Haley; Locke, Andrea; Choudhury, Mahua; Coté, Gerard

2017-02-01

Human biomarkers are indicative of the body's relative state prior to the onset of disease, and sometimes before symptoms present. While blood biomarker detection has achieved considerable success in laboratory settings, its clinical application is lagging and commercial point-of-care devices are rare. A physician's ability to detect biomarkers such as microRNA-17, a potential epigenetic indicator of preeclampsia in pregnant woman, could enable early diagnosis and preventive intervention as early as the 1st trimester. One detection approach employing DNA-functionalized nanoparticles to detect microRNA-17, in conjunction with surface-enhanced Raman spectroscopy (SERS), has shown promise but is hindered, in part, by the use of large and expensive benchtop Raman microscopes. However, recent strides have been made in developing portable Raman systems for field applications. Characteristics of the SERS assay responsible for strengthening the assay's plasmonic response were explored, whilst comparing the results from both benchtop and portable Raman systems. The Raman spectra and intensity of three different types of photoactive molecules were compared as potential Raman reporter molecules: chromophores, fluorophores, and highly polarizable small molecules. Furthermore, the plasmonic characteristics governing the formation of SERS colloidal nanoparticle assemblies in response to DNA/miRNA hybridization were investigated. There were significant variations in the SERS enhancement in response to microRNA-17 using our assay depending on the excitation lasers at wavelengths of 532 nm and 785 nm, depending on which of the three different Raman systems were used (benchtop, portable, and handheld), and depending on which of the three different Raman reporters (chromophore, fluorophore, or Raman active molecule) were used. Analysis of data obtained did indicate that signal enhancement was better for the chromophore (MGITC) and Raman active molecule (DTNB) than it was for the fluorophore (TRITC) and that, although it is possible to obtain enhancements when using excitation lasers that do not directly coincide with the optical properties of the Raman reporter molecule, clearly the enhancements are more significant when it reaches to the characteristic wavelengths of those molecules.

Tip-enhanced Raman spectroscopy and near-field polarization

NASA Astrophysics Data System (ADS)

Saito, Yuika; Mino, Toshihiro; Verma, Prabhat

2015-12-01

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for High-resolution Raman spectroscopy. In this method, a metal coated nano-tip acts as a plasmonic antenna to enhance the originally weak Raman scattering from a nanometric volume of a sample. The technique enables to detect Raman scattering light from nano-scale area and also enhance the light intensity with combination of near-filed light and localized surface plasmon generated at a metallized tip apex. Nowadays TERS is used to investigate various nano-scale samples, for examples, carbon nanotubes, graphenes DNA and biomaterials. As the TERS developed, there is high demand to investigate the properties of near-field light e.g. polarization properties. We have analyzed the polarization properties of near-field light in TERS and successfully realized the quantitative nano-imaging by visible light.

Surface-enhanced Raman spectroscopy using silver-coated porous glass-ceramic substrates.

PubMed

Pan, Z; Zavalin, A; Ueda, A; Guo, M; Groza, M; Burger, A; Mu, R; Morgan, S H

2005-06-01

Surface-enhanced Raman scattering (SERS) has been studied using a silver-coated porous glass-ceramic material as a new type of substrate. The porous glass-ceramic is in the CaO-TiO2-P2O5 system prepared by controlled crystallization and subsequent chemical leaching of the dense glass-ceramic, leaving a solid skeleton with pores ranging in size from 50 nm to submicrometer. Silver was coated on the surface of the porous glass-ceramic by radio frequency (RF) sputtering or e-beam evaporation in vacuum. SERS spectra of excellent quality were obtained from several dyes and carboxylic acid molecules, including rhodamine 6G, crystal violet, isonicotinic acid, and benzoic acid, using this new substrate. This new substrate showed a good compatibility with these molecules. The porous glass ceramic with a nanometer-structured surface accommodated both test molecules and silver film. The absorbed molecules were therefore better interfaced with silver for surface-enhanced Raman scattering.

Principal component analysis of bacteria using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Guicheteau, Jason; Christesen, Steven D.

2006-05-01

Surface-enhanced Raman scattering (SERS) provides rapid fingerprinting of biomaterial in a non-destructive manner. The problem of tissue fluorescence, which can overwhelm a normal Raman signal from biological samples, is largely overcome by treatment of biomaterials with colloidal silver. This work presents a study into the applicability of qualitative SER spectroscopy with principal component analysis (PCA) for the discrimination of four biological threat simulants; Bacillus globigii, Pantoea agglomerans, Brucella noetomae, and Yersinia rohdei. We also demonstrate differentiation of gram-negative and gram-positive species and as well as spores and vegetative cells of Bacillus globigii.

Surface-enhanced Raman scattering on molecular self-assembly in nanoparticle-hydrogel composite.

PubMed

Miljanić, Snezana; Frkanec, Leo; Biljan, Tomislav; Meić, Zlatko; Zinić, Mladen

2006-10-24

Surface-enhanced Raman scattering has been applied to study weak intermolecular interactions between small organic gelling molecules involved in the silver nanoparticle-hydrogel composite formation. Assembly and disassembly of the gelator molecules in close vicinity to embedded silver nanoparticles were followed by changes in Raman intensity of the amide II and carboxyl vibrational bands, whereas the strength of the bands related to benzene modes remained constant. This implied that the gelator molecules were strongly attached to the silver particles through the benzene units, while participating in gel structure organization by intermolecular hydrogen bonding between oxalyl amide and carboxyl groups.

Strong surface enhanced Raman scattering from gold nanoarrays obtained by direct laser writing

NASA Astrophysics Data System (ADS)

Ivanov, V. G.; Todorov, N. D.; Petrov, L. S.; Ritacco, T.; Giocondo, M.; Vlakhov, E. S.

2016-10-01

We report for surface enhanced Raman scattering (SERS) from arrays of gold nanoparticles produced by 2-photons photo-reduction of the metallic precursor (HAuCl4) hosted in a Poly-Vinyl Alcohol (PVA) matrix, on glass substrates. Samples with the same pattern but featuring different nanoparticles size and density were obtained by varying the writing laser power and scanning speed. The Raman spectra were recorded from samples immersed in a solution of rhodamine-6G (R6G), as well as, after exposure of the samples in xylene. SERS enhancement factors of up to ∼104 were obtained for both analytes. The measurements show that the SERS enhancement is maximized on golden strips produced at higher writing laser power and lower scanning speed, where closer nanoparticles packing is obtained..

Surface-enhanced Raman spectroscopy applied to food safety.

PubMed

Craig, Ana Paula; Franca, Adriana S; Irudayaraj, Joseph

2013-01-01

Surface-enhanced Raman spectroscopy (SERS) is an advanced Raman technique that enhances the vibrational spectrum of molecules adsorbed on or in the vicinity of metal particles and/or surfaces. Because of its readiness, sensitivity, and minimum sample preparation requirements, SERS is being considered as a powerful technique for food inspection. Key aspects of food-safety assurance, spectroscopy methods, and SERS are briefly discussed in an extended introduction of this review. The recent and potential advances in SERS are highlighted in sections that deal with the (a) detection of food-borne pathogenic microorganisms and (b) the detection of food contaminants and adulteration, concentrated specifically on antibiotics, drugs, hormones, melamine, and pesticides. This review provides an outlook of the work done and a perspective on the future directions of SERS as a reliable tool for food-safety assessment.

Application of Raman spectroscopy and surface-enhanced Raman scattering to the analysis of synthetic dyes found in ballpoint pen inks.

PubMed

Geiman, Irina; Leona, Marco; Lombardi, John R

2009-07-01

The applicability of Raman spectroscopy and surface-enhanced Raman scattering (SERS) to the analysis of synthetic dyes commonly found in ballpoint inks was investigated in a comparative study. Spectra of 10 dyes were obtained using a dispersive system (633 nm, 785 nm lasers) and a Fourier transform system (1064 nm laser) under different analytical conditions (e.g., powdered pigments, solutions, thin layer chromatography [TLC] spots). While high fluorescence background and poor spectral quality often characterized the normal Raman spectra of the dyes studied, SERS was found to be generally helpful. Additionally, dye standards and a single ballpoint ink were developed on a TLC plate following a typical ink analysis procedure. SERS spectra were successfully collected directly from the TLC plate, thus demonstrating a possible forensic application for the technique.

Ultrasensitive detection of phenolic antioxidants by surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ornelas-Soto, N.; Aguilar-Hernández, I. A.; Afseth, N.; López-Luke, T.; Contreras-Torres, F. F.; Wold, J. P.

2017-08-01

Surface-Enhanced Raman Spectroscopy (SERS) is a powerful surface-sensitive technique to study the vibrational properties of analytes at very low concentrations. In this study, ferulic acid, p-coumaric acid, caffeic acid and sinapic acid were analyzed by SERS using Ag colloids. Analytes were detected up to 2.5x10-9M. For caffeic acid and coumaric acid, this detection limit has been reached for the first time, as well as the SERS analysis of sinapic acid using silver colloids.

Label and label-free based surface-enhanced Raman scattering for pathogen bacteria detection: A review.

PubMed

Liu, Yu; Zhou, Haibo; Hu, Ziwei; Yu, Guangxia; Yang, Danting; Zhao, Jinshun

2017-08-15

Rapid, accurate detection of pathogen bacteria is a highly topical research area for the sake of food safety and public health. Surface-enhanced Raman scattering (SERS) is being considered as a powerful and attractive technique for pathogen bacteria detection, due to its sensitivity, high speed, comparatively low cost, multiplexing ability and portability. This contribution aims to give a comprehensive overview of SERS as a technique for rapid detection of pathogen bacteria based on label and label-free strategies. A brief tutorial on SERS is given first of all. Then we summarize the recent trends and developments of label and label-free based SERS applied to detection of pathogen bacteria, including the relatively complete interpretation of SERS spectra. In addition, multifunctional SERS platforms for pathogen bacteria in matrix are discussed as well. Furthermore, an outlook of the work done and a perspective on the future directions of SERS as a reliable tool for real-time pathogen bacteria detection are given. Copyright © 2017 Elsevier B.V. All rights reserved.

Monitoring the chemical production of citrus-derived bioactive 5-demethylnobiletin using surface enhanced Raman spectroscopy

PubMed Central

Zheng, Jinkai; Fang, Xiang; Cao, Yong; Xiao, Hang; He, Lili

2013-01-01

To develop an accurate and convenient method for monitoring the production of citrus-derived bioactive 5-demethylnobiletin from demethylation reaction of nobiletin, we compared surface enhanced Raman spectroscopy (SERS) methods with a conventional HPLC method. Our results show that both the substrate-based and solution-based SERS methods correlated with HPLC method very well. The solution method produced lower root mean square error of calibration and higher correlation coefficient than the substrate method. The solution method utilized an ‘affinity chromatography’-like procedure to separate the reactant nobiletin from the product 5-demthylnobiletin based on their different binding affinity to the silver dendrites. The substrate method was found simpler and faster to collect the SERS ‘fingerprint’ spectra of the samples as no incubation between samples and silver was needed and only trace amount of samples were required. Our results demonstrated that the SERS methods were superior to HPLC method in conveniently and rapidly characterizing and quantifying 5-demethylnobiletin production. PMID:23885986

Potential of non-invasive esophagus cancer detection based on urine surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Shaohua; Wang, Lan; Chen, Weisheng; Feng, Shangyuan; Lin, Juqiang; Huang, Zufang; Chen, Guannan; Li, Buhong; Chen, Rong

2014-11-01

Non-invasive esophagus cancer detection based on urine surface-enhanced Raman spectroscopy (SERS) analysis was presented. Urine SERS spectra were measured on esophagus cancer patients (n = 56) and healthy volunteers (n = 36) for control analysis. Tentative assignments of the urine SERS spectra indicated some interesting esophagus cancer-specific biomolecular changes, including a decrease in the relative content of urea and an increase in the percentage of uric acid in the urine of esophagus cancer patients compared to that of healthy subjects. Principal component analysis (PCA) combined with linear discriminant analysis (LDA) was employed to analyze and differentiate the SERS spectra between normal and esophagus cancer urine. The diagnostic algorithms utilizing a multivariate analysis method achieved a diagnostic sensitivity of 89.3% and specificity of 83.3% for separating esophagus cancer samples from normal urine samples. These results from the explorative work suggested that silver nano particle-based urine SERS analysis coupled with PCA-LDA multivariate analysis has potential for non-invasive detection of esophagus cancer.

Noninvasive detection of nasopharyngeal carcinoma based on saliva proteins using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Lin, Xueliang; Lin, Duo; Ge, Xiaosong; Qiu, Sufang; Feng, Shangyuan; Chen, Rong

2017-10-01

The present study evaluated the capability of saliva analysis combining membrane protein purification with surface-enhanced Raman spectroscopy (SERS) for noninvasive detection of nasopharyngeal carcinoma (NPC). A rapid and convenient protein purification method based on cellulose acetate membrane was developed. A total of 659 high-quality SERS spectra were acquired from purified proteins extracted from the saliva samples of 170 patients with pathologically confirmed NPC and 71 healthy volunteers. Spectral analysis of those saliva protein SERS spectra revealed specific changes in some biochemical compositions, which were possibly associated with NPC transformation. Furthermore, principal component analysis combined with linear discriminant analysis (PCA-LDA) was utilized to analyze and classify the saliva protein SERS spectra from NPC and healthy subjects. Diagnostic sensitivity of 70.7%, specificity of 70.3%, and diagnostic accuracy of 70.5% could be achieved by PCA-LDA for NPC identification. These results show that this assay based on saliva protein SERS analysis holds promising potential for developing a rapid, noninvasive, and convenient clinical tool for NPC screening.

Research on identification and determination of mixed pesticides in apples using surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zhai, Chen; Li, Yongyu; Peng, Yankun; Xu, Tianfeng; Dhakal, Sagar; Chao, Kuanglin; Qin, Jianwei

2015-05-01

Residual pesticides in fruits and vegetables have become one of the major food safety concerns around the world. At present, routine analytical methods used for the determination of pesticide residue on the surface of fruits and vegetables are destructive, complex, time-consuming, high cost and not environmentally friendly. In this study, a novel Surface Enhanced Raman Spectroscopy (SERS) method with silver colloid was developed for fast and sensitive nondestructive detection of residual pesticides in fruits and vegetables by using a self-developed Raman system. SERS technology is a combination of Raman spectroscopy and nanotechnology. SERS can greatly enhance the Raman signal intensity, achieve single-molecule detection, and has a simple sample pre-treatment characteristic of high sensitivity and no damage; in recent years it has begun to be used in food safety testing research. In this study a rapid and sensitive method was developed to identify and analyze mixed pesticides of chlorpyrifos, deltamethrin and acetamiprid in apple samples by SERS. Silver colloid was used for SERS measurement by hydroxylamine hydrochloride reduced. The advantages of this method are seen in its fast preparation at room temperature, good reproducibility and immediate applicability. Raman spectrum is highly interfered by noise signals and fluorescence background, which make it too complex to get good result. In this study the noise signals and fluorescence background were removed by Savitzky-Golay filter and min-max signal adaptive zooming method. Under optimal conditions, pesticide residues in apple samples can be detected by SERS at 0.005 μg/cm2 and 0.002 μg/cm2 for individual acetamiprid and thiram, respectively. When mixing the two pesticides at low concentrations, their characteristic peaks can still be identified from the SERS spectrum of the mixture. Based on the synthesized material and its application in SERS operation, the method represents an ultrasensitive SERS performance in apple samples detection without sample pre-treatment, which indicates that it could be served as a useful means in monitoring pesticide residues.

A monolayer of hierarchical silver hemi-mesoparticles with tunable surface topographies for highly sensitive surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zhu, Shuangmei; Fan, Chunzhen; Mao, Yanchao; Wang, Junqiao; He, Jinna; Liang, Erjun; Chao, Mingju

2016-02-01

We proposed a facile green synthesis system to synthesize large-scale Ag hemi-mesoparticles monolayer on Cu foil. Ag hemi-mesoparticles have different surface morphologies on their surfaces, including ridge-like, meatball-like, and fluffy-like shapes. In the reaction, silver nitrate was reduced by copper at room temperature in dimethyl sulfoxide via the galvanic displacement reaction. The different surface morphologies of the Ag hemi-mesoparticles were adjusted by changing the reaction time, and the hemi-mesoparticle surface formed fluffy-spherical nanoprotrusions at longer reaction time. At the same time, we explored the growth mechanism of silver hemi-mesoparticles with different surface morphologies. With 4-mercaptobenzoic acid as Raman probe molecules, the fluffy-like silver hemi-mesoparticles monolayer with the best activity of surface enhanced Raman scattering (SERS), the enhancement factor is up to 7.33 × 107 and the detection limit can reach 10-10M. SERS measurements demonstrate that these Ag hemi-mesoparticles can serve as sensitive SERS substrates. At the same time, using finite element method, the distribution of the localized electromagnetic field near the particle surface was simulated to verify the enhanced mechanism. This study helps us to understand the relationship between morphology Ag hemi-mesoparicles and the properties of SERS.

A monolayer of hierarchical silver hemi-mesoparticles with tunable surface topographies for highly sensitive surface-enhanced Raman spectroscopy.

PubMed

Zhu, Shuangmei; Fan, Chunzhen; Mao, Yanchao; Wang, Junqiao; He, Jinna; Liang, Erjun; Chao, Mingju

2016-02-21

We proposed a facile green synthesis system to synthesize large-scale Ag hemi-mesoparticles monolayer on Cu foil. Ag hemi-mesoparticles have different surface morphologies on their surfaces, including ridge-like, meatball-like, and fluffy-like shapes. In the reaction, silver nitrate was reduced by copper at room temperature in dimethyl sulfoxide via the galvanic displacement reaction. The different surface morphologies of the Ag hemi-mesoparticles were adjusted by changing the reaction time, and the hemi-mesoparticle surface formed fluffy-spherical nanoprotrusions at longer reaction time. At the same time, we explored the growth mechanism of silver hemi-mesoparticles with different surface morphologies. With 4-mercaptobenzoic acid as Raman probe molecules, the fluffy-like silver hemi-mesoparticles monolayer with the best activity of surface enhanced Raman scattering (SERS), the enhancement factor is up to 7.33 × 10(7) and the detection limit can reach 10(-10)M. SERS measurements demonstrate that these Ag hemi-mesoparticles can serve as sensitive SERS substrates. At the same time, using finite element method, the distribution of the localized electromagnetic field near the particle surface was simulated to verify the enhanced mechanism. This study helps us to understand the relationship between morphology Ag hemi-mesoparicles and the properties of SERS.

Ambiance-dependent agglomeration and surface-enhanced Raman spectroscopy response of self-assembled silver nanoparticles for plasmonic photovoltaic devices

NASA Astrophysics Data System (ADS)

Gwamuri, Jephias; Venkatesan, Ragavendran; Sadatgol, Mehdi; Mayandi, Jeyanthinath; Guney, Durdu O.; Pearce, Joshua M.

2017-07-01

The agglomeration/dewetting process of thin silver films provides a scalable method of obtaining self-assembled nanoparticles (SANPs) for plasmonics-based thin-film solar photovoltaic (PV) devices. We show the effect of annealing ambiance on silver SANP average size, particle/cluster finite shape, substrate area coverage/particle distribution, and how these physical parameters influence optical properties and surface-enhanced Raman scattering (SERS) responses of SANPs. Statistical analysis performed indicates that generally Ag SANPs processed in the presence of a gas (argon and nitrogen) ambiance tend to have smaller average size particles compared to those processed under vacuum. Optical properties are observed to be highly dependent on particle size, separation distance, and finite shape. The greatest SERS enhancement was observed for the argon-processed samples. There is a correlation between simulation and experimental data that indicate argon-processed AgNPs have a great potential to enhance light coupling when integrated to thin-film PV.

Note: A novel technique for analysis of aqueous solutions by laser-induced breakdown spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rusak, D. A.; Bell, Z. T.; Anthony, T. P.

2015-11-15

Surface-enhanced Raman spectroscopy (SERS) substrates typically consist of gold or silver nanoparticles deposited on a non-conductive substrate. In Raman spectroscopy, the nanoparticles produce an enhancement of the electromagnetic field which, in turn, leads to greater electronic excitation of molecules in the local environment. Here, we show that these same surfaces can be used to enhance the signal-to-noise ratio obtained in laser-induced breakdown spectroscopy of aqueous solutions. In this case, the SERS substrates not only lower breakdown thresholds and lead to more efficient plasma initiation but also provide an appropriately wettable surface for the deposition of the liquid. We refer tomore » this technique as surface-enhanced laser-induced breakdown spectroscopy.« less

Aggregation of nanoparticles in endosomes and lysosomes produces surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Lucas, Leanne J.; Chen, Xiaoke K.; Smith, Aaron J.; Korbelik, Mladen; Zeng, Haishan; Lee, Patrick W. K.; Hewitt, Kevin Cecil

2015-01-01

The purpose of this study was to explore the use of surface-enhanced Raman spectroscopy (SERS) to image the distribution of epidermal growth factor receptor (EGFR) in cells. To accomplish this task, 30-nm gold nanoparticles (AuNPs) tagged with antibodies to EGFR (1012 per mL) were incubated with cells (106 per mL) of the A431 human epidermoid carcinoma and normal human bronchial epithelial cell lines. Using the 632.8-nm excitation line of a He-Ne laser, Raman spectroscopy measurements were performed using a point mapping scheme. Normal cells show little to no enhancement. SERS signals were observed inside the cytoplasm of A431 cells with an overall enhancement of 4 to 7 orders of magnitude. Raman intensity maps of the 1450 and 1583 cm-1 peaks correlate well with the expected distribution of EGFR and AuNPs, aggregated following uptake by endosomes and lysosomes. Spectral features from tyrosine and tryptophan residues dominate the SERS signals.

Single-Molecule Chemistry with Surface- and Tip-Enhanced Raman Spectroscopy.

PubMed

Zrimsek, Alyssa B; Chiang, Naihao; Mattei, Michael; Zaleski, Stephanie; McAnally, Michael O; Chapman, Craig T; Henry, Anne-Isabelle; Schatz, George C; Van Duyne, Richard P

2017-06-14

Single-molecule (SM) surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) have emerged as analytical techniques for characterizing molecular systems in nanoscale environments. SERS and TERS use plasmonically enhanced Raman scattering to characterize the chemical information on single molecules. Additionally, TERS can image single molecules with subnanometer spatial resolution. In this review, we cover the development and history of SERS and TERS, including the concept of SERS hot spots and the plasmonic nanostructures necessary for SM detection, the past and current methodologies for verifying SMSERS, and investigations into understanding the signal heterogeneities observed with SMSERS. Moving on to TERS, we cover tip fabrication and the physical origins of the subnanometer spatial resolution. Then, we highlight recent advances of SMSERS and TERS in fields such as electrochemistry, catalysis, and SM electronics, which all benefit from the vibrational characterization of single molecules. SMSERS and TERS provide new insights on molecular behavior that would otherwise be obscured in an ensemble-averaged measurement.

Cancer imaging using Surface-Enhanced Resonance Raman Scattering (SERRS) nanoparticles

PubMed Central

Harmsen, Stefan; Wall, Matthew A.; Huang, Ruimin

2017-01-01

The unique spectral signatures and biologically inert compositions of surface-enhanced (resonance) Raman scattering (SE(R)RS) nanoparticles make them promising contrast agents for in vivo cancer imaging. Subtle aspects of their preparation can shift their limit of detection by orders of magnitude. In this protocol, we present the optimized, step-by-step procedure for generating reproducible SERRS nanoparticles with femtomolar (10−15 M) limits of detection. We introduce several applications of these nanoprobes for biomedical research, with a focus on intraoperative cancer imaging via Raman imaging. A detailed account is provided for successful intravenous administration of SERRS nanoparticles such that delineation of cancerous lesions may be achieved without the need for specific biomarker targeting. The time estimate for this straightforward, yet comprehensive protocol from initial de novo gold nanoparticle synthesis to SE(R)RS nanoparticle contrast-enhanced preclinical Raman imaging in animal models is ~96 h. PMID:28686581

Fabrication of large area plasmonic nanoparticle grating structure on silver halide based transmission electron microscope film and its application as a surface enhanced Raman spectroscopy substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sudheer,, E-mail: sudheer@rrcat.gov.in; Tiwari, P.; Singh, M. N.

The plasmonic responses of silver nanoparticle grating structures of different periods made on silver halide based electron microscope film are investigated. Raster scan of the conventional scanning electron microscope (SEM) is used to carry out electron beam lithography for fabricating the plasmonic nanoparticle grating (PNG) structures. Morphological characterization of the PNG structures, carried out by the SEM and the atomic force microscope, indicates that the depth of the groove decreases with a decrease in the grating period. Elemental characterization performed by the energy dispersive spectroscopy and the x-ray diffraction shows the presence of nanoparticles of silver in the PNG grating.more » The optical characterization of the gratings shows that the localized surface plasmon resonance peak shifts from 366 to 378 nm and broadens with a decrease in grating period from 10 to 2.5 μm. The surface enhanced Raman spectroscopy of the Rhodamine-6G dye coated PNG structure shows the maximum enhancement by two orders of magnitude in comparison to the randomly distributed silver nanoparticles having similar size and shape as the PNG structure.« less

Utilization of a lateral flow colloidal gold immunoassay strip based on surface-enhanced Raman spectroscopy for ultrasensitive detection of antibiotics in milk

NASA Astrophysics Data System (ADS)

Shi, Qiaoqiao; Huang, Jie; Sun, Yaning; Yin, Mengqi; Hu, Mei; Hu, Xiaofei; Zhang, Zhijun; Zhang, Gaiping

2018-05-01

An ultrasensitive method for the detection of antibiotics in milk is developed based on inexpensive, simple, rapid and portable lateral flow immunoassay (LFI) strip, in combination with high sensitivity surface-enhanced Raman spectroscopy (SERS). In our strategy, an immunoprobe was prepared from colloidal gold (AuNPs) conjugated with both a monoclonal antibody against neomycin (NEO-mAb) and a Raman probe molecule 4-aminothiophenol (PATP). The competitive interaction with immunoprobe between free NEO and the coated antigen (NEO-OVA) resulted in the change of the amount of the immobilized immunoprobe on the paper substrate. The LFI procedure was completed within 15 min. The Raman intensity of PATP on the test line of the LFI strip was measured for the quantitative determination of NEO. The IC50 and the limit of detection (LOD) of this assay are 0.04 ng/mL and 0.216 pg/mL of NEO, respectively. There is no cross-reactivity (CR) of the assay with other compounds, showing high specificity of the assay. The recoveries for milk samples with added NEO are in the range of 89.7%-105.6% with the relative standard deviations (RSD) of 2.4%-5.3% (n = 3). The result reveals that this method possesses high specificity, sensitivity, reproducibility and stability, and can be used to detect a variety of antibiotic residues in milk samples.

Sensitive and simple determination of zwitterionic morphine in human urine based on liquid-liquid micro-extraction coupled with surface-enhanced Raman spectroscopy.

PubMed

Yu, Borong; Cao, Chentai; Li, Pan; Mao, Mei; Xie, Qiwen; Yang, Liangbao

2018-08-15

Morphine, a kind of illicit drugs, is also one of the main heroin metabolites. In consideration of a noninvasive way to monitor and identify drug abuse during forensic cases, the urine samples are usually detected. Here, colloidal gold nanorods (Au NRs) were introduced to act as active substrate, because of the strong optical extinction and spectral tunability of the longitudinal surface plasmon resonance (SPR). Thus, well surface-enhanced Raman spectra of morphine even at low concentrations could be obtained by portable Raman spectrometer. For the complex matrix environment of urine, liquid-liquid micro-extraction (LLME), a simple and inexpensive pretreatment, was employed to avoid the interferences. And then, the coupled surface-enhanced Raman spectroscopy (SERS) can give full play to the advantages of high sensitivity and unique spectroscopic fingerprint. According to the zwitterionic structure and physicochemical parameters of morphine molecules, the pH value of urine sample was adjusted to about 9 by buffer solution (KOH/NaB 4 O 7 ) and the mixture of chloroform and isopropyl alcohol (V/V=9:1) was chosen as extractant. Moreover, such pretreatment was proved to be appropriate for separation and concentration of morphine from urine. The developed LLME-SERS method could provide a detection limit less than 1 ppm in the human urine environment and the whole process of detection just needed take 5-6 min. What's more, the results of urine samples from heroin users exhibited application value of the proposed technique. The excellent performance makes it promising to become a rapid, reliable, and on-spot analyzer, especially for public safety and healthcare. Copyright © 2018 Elsevier B.V. All rights reserved.

Portable and Reliable Surface-Enhanced Raman Scattering Silicon Chip for Signal-On Detection of Trace Trinitrotoluene Explosive in Real Systems.

PubMed

Chen, Na; Ding, Pan; Shi, Yu; Jin, Tengyu; Su, Yuanyuan; Wang, Houyu; He, Yao

2017-05-02

There is an increasing interest in the development of surface-enhanced Raman scattering (SERS) sensors for rapid and accurate on-site detection of hidden explosives. However, portable SERS methods for trace explosive detection in real systems remain scarce, mainly due to their relatively poor reliability and portability. Herein, we present the first demonstration of a portable silicon-based SERS analytical platform for signal-on detection of trace trinitrotoluene (TNT) explosives, which is made of silver nanoparticle (AgNP)-decorated silicon wafer chip (0.5 cm × 0.5 cm). In principle, under 514 nm excitation, the Raman signals of p-aminobenzenethiol (PABT) modified on the AgNP surface could be largely lit up due to the formation of electronic resonance-active TNT-PABT complex. In addition, the surface of AgNPs and silicon substrate-induced plasmon resonances also contribute the total SERS enhancement. For quantitative evaluation, the as-prepared chip features ultrahigh sensitivity [limit of detection is down to ∼1 pM (∼45.4 fg/cm 2 )] and adaptable reproducibility (relative standard deviation is less than 15%) in the detection of TNT standard solutions. More importantly, the developed chip can couple well with a hand-held Raman spectroscopic device using 785 nm excitation, suitable for qualitative analysis of trace TNT even at ∼10 -8 M level from environmental samples including lake water, soil, envelope, and liquor with a short data acquisition time (∼1 min). Furthermore, TNT vapors diffusing from TNT residues (∼10 -6 M) can be detected by using such a portable device, indicating its feasibility in determination of hidden samples.

Mechanism of Surface-Enhanced Raman Scattering Based on 3D Graphene-TiO2 Nanocomposites and Application to Real-Time Monitoring of Telomerase Activity in Differentiation of Stem Cells.

PubMed

Zheng, Tingting; Feng, Enduo; Wang, Zhiqiang; Gong, Xueqing; Tian, Yang

2017-10-25

With a burst development of new nanomaterials for plasmon-free surface-enhanced Raman scattering (SERS), the understanding of chemical mechanism (CM) and further applications have become more and more attractive. Herein, a novel SERS platform was specially designed through electrochemical deposition of graphene onto TiO 2 nanoarrays (EG-TiO 2 ). The developed EG-TiO 2 nanocomposite SERS platform possessed remarkable Raman activity using copper phthalocyanine (CuPc) as a probe molecule. X-ray photoelectron spectroscopy measurement revealed that the chemical bond Ti-O-C was formed at the interface between graphene and TiO 2 in EG-TiO 2 nanocomposites. Both experimental and theoretical results demonstrated that the obvious Raman enhancement was attributed to TiO 2 -induced Fermi level shift of graphene, resulting in effective charge transfer between EG-TiO 2 nanocomposites and molecules. Taking advantage of a marked Raman response of the CuPc molecule on the EG-TiO 2 nanocomposite surface as well as specific recognition of CuPc toward multiple telomeric G-quadruplex, EG-TiO 2 nanocomposites were tactfully employed as the SERS substrate for selective and ultrasensitive determination of telomerase activity, with a low detection limit down to 2.07 × 10 -16 IU. Interestingly, the self-cleaning characteristic of EG-TiO 2 nanocomposites under visible light irradiation successfully provided a recycling ability for this plasmon-free EG-TiO 2 substrate. The present SERS biosensor with high analytical performance, such as high selectivity and sensitivity, has been further explored to determine telomerase activity in stem cells as well as to count the cell numbers. More importantly, using this useful tool, it was discovered that telomerase activity plays an important role in the proliferation and differentiation from human mesenchymal stem cells to neural stem cells. This work has not only established an approach for gaining fundamental insights into the chemical mechanism (CM) of Raman enhancement but also has opened a new way in the investigation of long-term dynamics of stem cell differentiation and clinical drug screening.

Trace detection of analytes using portable raman systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alam, M. Kathleen; Hotchkiss, Peter J.; Martin, Laura E.

Apparatuses and methods for in situ detection of a trace amount of an analyte are disclosed herein. In a general embodiment, the present disclosure provides a surface-enhanced Raman spectroscopy (SERS) insert including a passageway therethrough, where the passageway has a SERS surface positioned therein. The SERS surface is configured to adsorb molecules of an analyte of interest. A concentrated sample is caused to flow over the SERS surface. The SERS insert is then provided to a portable Raman spectroscopy system, where it is analyzed for the analyte of interest.

Rapid prototyping of all-solution-processed multi-lengthscale electrodes using polymer-induced thin film wrinkling

PubMed Central

Gabardo, Christine M.; Adams-McGavin, Robert C.; Fung, Barnabas C.; Mahoney, Eric J.; Fang, Qiyin; Soleymani, Leyla

2017-01-01

Three-dimensional electrodes that are controllable over multiple lengthscales are very important for use in bioanalytical systems that integrate solid-phase devices with solution-phase samples. Here we present a fabrication method based on all-solution-processing and thin film wrinkling using smart polymers that is ideal for rapid prototyping of tunable three-dimensional electrodes and is extendable to large volume manufacturing. Although all-solution-processing is an attractive alternative to vapor-based techniques for low-cost manufacturing of electrodes, it often results in films suffering from low conductivity and poor substrate adhesion. These limitations are addressed here by using a smart polymer to create a conformal layer of overlapping wrinkles on the substrate to shorten the current path and embed the conductor onto the polymer layer. The structural evolution of these wrinkled electrodes, deposited by electroless deposition onto a nanoparticle seed layer, is studied at varying deposition times to understand its effects on structural parameters such as porosity, wrinkle wavelength and height. Furthermore, the effect of structural parameters on functional properties such as electro-active surface area and surface-enhanced Raman scattering is investigated. It is found that wrinkling of electroless-deposited thin films can be used to reduce sheet resistance, increase surface area, and enhance the surface-enhanced Raman scattering signal. PMID:28211898

Rapid prototyping of all-solution-processed multi-lengthscale electrodes using polymer-induced thin film wrinkling

NASA Astrophysics Data System (ADS)

Gabardo, Christine M.; Adams-McGavin, Robert C.; Fung, Barnabas C.; Mahoney, Eric J.; Fang, Qiyin; Soleymani, Leyla

2017-02-01

Three-dimensional electrodes that are controllable over multiple lengthscales are very important for use in bioanalytical systems that integrate solid-phase devices with solution-phase samples. Here we present a fabrication method based on all-solution-processing and thin film wrinkling using smart polymers that is ideal for rapid prototyping of tunable three-dimensional electrodes and is extendable to large volume manufacturing. Although all-solution-processing is an attractive alternative to vapor-based techniques for low-cost manufacturing of electrodes, it often results in films suffering from low conductivity and poor substrate adhesion. These limitations are addressed here by using a smart polymer to create a conformal layer of overlapping wrinkles on the substrate to shorten the current path and embed the conductor onto the polymer layer. The structural evolution of these wrinkled electrodes, deposited by electroless deposition onto a nanoparticle seed layer, is studied at varying deposition times to understand its effects on structural parameters such as porosity, wrinkle wavelength and height. Furthermore, the effect of structural parameters on functional properties such as electro-active surface area and surface-enhanced Raman scattering is investigated. It is found that wrinkling of electroless-deposited thin films can be used to reduce sheet resistance, increase surface area, and enhance the surface-enhanced Raman scattering signal.

Multifunctional silver nanoparticle-doped silica for solid-phase extraction and surface-enhanced Raman scattering detection

NASA Astrophysics Data System (ADS)

Markina, Natalia E.; Markin, Alexey V.; Zakharevich, Andrey M.; Gorin, Dmitry A.; Rusanova, Tatiana Yu.; Goryacheva, Irina Yu.

2016-12-01

Multifunctional silica gel with embedded silver nanoparticles (SiO2-AgNP) is proposed for application as sorbent for solid-phase extraction (SPE) and simultaneously as substrate for surface-enhanced Raman spectroscopy (SERS) due to their high sorption properties and ability to enhance Raman signal (SERS-active sorbents). SiO2-AgNP was synthesized via alkaline hydrolysis of tetraethyl orthosilicate with simultaneous reduction of silver ions to silver nanoparticles (AgNP) within the SiO2 bulk. Synthesis of AgNP directly to the SiO2 matrix enables to exclude any additional stabilizers for the nanoparticles that educes signal-to-noise ratio during SERS measurement. Apart from Raman spectroscopy, obtained sorbents were also characterized by scanning electron microscopy and UV-visible diffuse reflectance spectroscopy. The influence of AgNO3 concentration used during the SiO2-AgNP synthesis on its gelling time, color, diffuse reflectance spectra, and enhancement of Raman signal was investigated. A Raman enhancement factor of SiO2-AgNP with optimal composition was around 105. Finally, the sorbents were applied for SPE and subsequent SERS detection of model compounds (rhodamine 6G and folic acid). It was found that SPE enables to decrease detectable concentrations by two orders. Therefore, SPE combined with SERS has high potential for further analytical investigations.

Surface-enhanced Raman spectroscopy substrate based on Ag-coated self-assembled polystyrene spheres

NASA Astrophysics Data System (ADS)

Mikac, Lara; Ivanda, Mile; Gotić, Marijan; Janicki, Vesna; Zorc, Hrvoje; Janči, Tibor; Vidaček, Sanja

2017-10-01

The silver (Ag) films were deposited on the monodispersed polystyrene spheres that were drop-coated on hydrophilic glass substrates in order to form a self-assembled 2D monolayer. Thus prepared Ag films over polystyrene nanospheres (AgFONs) were used to record the surface-enhanced Raman scattering (SERS) spectra of rhodamine 6G (R6G) and pyridine (λex = 514.5 nm). AgFONs were prepared by depositing 120, 180 and 240 nm thick Ag layer on the 1000 nm polystyrene spheres and 80, 120, 160 and 200 nm thick Ag layer on the 350 nm spheres as well as on their mixture (350 + 1000 nm). The silver was deposited by electron beam evaporation technique. The best enhancement of the Raman signal for both test molecules was obtained using 180 nm Ag film deposited on the 1000 nm spheres and using 80 nm Ag film deposited on the 350 nm polystyrene spheres. The lowest detectable concentrations of R6G and pyridine were 10-9 mol L-1 and 1.2 × 10-3 mol L-1, respectively. This study has shown that AgFONs could be regarded as good and reproducible SERS substrate for analytical detection of various organic molecules.

Binding of p-mercaptobenzoic acid and adenine to gold-coated electroless etched silicon nanowires studied by surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Mohaček-Grošev, Vlasta; Gebavi, Hrvoje; Bonifacio, Alois; Sergo, Valter; Daković, Marko; Bajuk-Bogdanović, Danica

2018-07-01

Modern diagnostic tools ever aim to reduce the amount of analyte and the time needed for obtaining the result. Surface-enhanced Raman spectroscopy is a method that could satisfy both of these requirements, provided that for each analyte an adequate substrate is found. Here we demonstrate the ability of gold-sputtered silicon nanowires (SiNW) to bind p-mercaptobenzoic acid in 10-3, 10-4 and 10-5 M and adenine in 30 and 100 μM concentrations. Based on the normal mode analysis, presented here for the first time, the binding of p-mercaptobenzoic acid is deduced. The intensity enhancement of the 1106 cm-1 band is explained by involvement of the Csbnd S stretching deformation, and the appearance of the broad 300 cm-1 band attributed to Ssbnd Au stretching mode. Adenine SERS spectra demonstrate the existence of the 7H tautomer since the strongest band observed is at 736 cm-1. The adenine binding is likely to occur in several ways, because the number of observed bands in the 1200-1600 cm-1 interval exceeds the number of observed bands in the normal Raman spectrum of the free molecule.

Combination of surface- and interference-enhanced Raman scattering by CuS nanocrystals on nanopatterned Au structures

PubMed Central

Yeryukov, Nikolay A; Sveshnikova, Larisa L; Duda, Tatyana A; Rodyakina, Ekaterina E; Gridchin, Victor A; Sheremet, Evgeniya S; Zahn, Dietrich R T

2015-01-01

Summary We present the results of a Raman study of optical phonons in CuS nanocrystals (NCs) with a low areal density fabricated through the Langmuir–Blodgett technology on nanopatterned Au nanocluster arrays using a combination of surface- and interference-enhanced Raman scattering (SERS and IERS, respectively). Micro-Raman spectra of one monolayer of CuS NCs deposited on a bare Si substrate reveal only features corresponding to crystalline Si. However, a new relatively strong peak occurs in the Raman spectrum of CuS NCs on Au nanocluster arrays at 474 cm−1. This feature is related to the optical phonon mode in CuS NCs and manifests the SERS effect. For CuS NCs deposited on a SiO2 layer this phonon mode is also observed due to the IERS effect. Its intensity changes periodically with increasing SiO2 layer thickness for different laser excitation lines and is enhanced by a factor of about 30. CuS NCs formed on Au nanocluster arrays fabricated on IERS substrates combine the advantages of SERS and IERS and demonstrate stronger SERS enhancement allowing for the observation of Raman signals from CuS NCs with an ultra-low areal density. PMID:25977845

Non-invasive optical detection of HBV based on serum surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zheng, Zuci; Wang, Qiwen; Weng, Cuncheng; Lin, Xueliang; Lin, Yao; Feng, Shangyuan

2016-10-01

An optical method of surface-enhanced Raman spectroscopy (SERS) was developed for non-invasive detection of hepatitis B surface virus (HBV). Hepatitis B virus surface antigen (HBsAg) is an established serological marker that is routinely used for the diagnosis of acute or chronic hepatitis B virus(HBV) infection. Utilizing SERS to analyze blood serum for detecting HBV has not been reported in previous literature. SERS measurements were performed on two groups of serum samples: one group for 50 HBV patients and the other group for 50 healthy volunteers. Blood serum samples are collected from healthy control subjects and patients diagnosed with HBV. Furthermore, principal components analysis (PCA) combined with linear discriminant analysis (LDA) were employed to differentiate HBV patients from healthy volunteer and achieved sensitivity of 80.0% and specificity of 74.0%. This exploratory work demonstrates that SERS serum analysis combined with PCA-LDA has tremendous potential for the non-invasive detection of HBV.

Theory of hyperbolic stratified nanostructures for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Wong, Herman M. K.; Dezfouli, Mohsen Kamandar; Axelrod, Simon; Hughes, Stephen; Helmy, Amr S.

2017-11-01

We theoretically investigate the enhancement of surface enhanced Raman spectroscopy (SERS) using hyperbolic stratified nanostructures and compare to metal nanoresonators. The photon Green function of each nanostructure within its environment is first obtained from a semianalytical modal theory, which is used in a quantum optics formalism of the molecule-nanostructure interaction to model the SERS spectrum. An intuitive methodology is presented for calculating the single-molecule enhancement factor (SMEF), which is also able to predict known experimental SERS enhancement factors of a gold nanodimer. We elucidate the important figures-of-merit of the enhancement and explore these for different designs. We find that the use of hyperbolic stratified materials can enhance the photonic local density of states (LDOS) by close to two times in comparison to pure metal nanostructures, when both designed to work at the same operating wavelengths. However, the increased LDOS is accompanied by higher electric field concentration within the lossy hyperbolic material, which leads to increased quenching that serves to reduce the overall detected SERS enhancement in the far field. For nanoresonators with resonant localized surface plasmon wavelengths in the near-infrared, the SMEF for the hyperbolic stratified nanostructure is approximately one order of magnitude lower than the pure metal counterpart. Conversely, we show that by detecting the Raman signal using a near-field probe, hyperbolic materials can provide an improvement in SERS enhancement compared to using pure metal nanostructures when the probe is sufficiently close (<50 nm ) to the Raman active molecule at the plasmonic hotspot.

Optical cross-talk and surface characterization of SERS nanoimaging bundle substrates

NASA Astrophysics Data System (ADS)

Kiser, John B.; Cullum, Brian M.

2010-04-01

Due to the narrow vibrational bandwidths and unique molecular fingerprints, Raman spectroscopy can be an information rich transduction technique for chemical imaging. Dynamic systems are often difficult to measure using spontaneous Raman due to the relatively weak scattering cross-sections. Using a Raman enhancement mechanism such as surface enhanced Raman scattering (SERS), exposure times can be reduced to a reasonable level for dynamic imaging, due to the increased Raman signal intensity. This paper will discuss the development of a novel SERS substrate, fabricated on the tips of fiber-optic imaging bundles, which can be integrated into a multispectral imaging system for non-scanning chemical imaging. These substrates are fabricated by mechanically tapering a polished fiber optic imaging bundle consisting of 30,000 individual elements; producing 100-nm or smaller diameter core elements on the distal tip. Chemical etching with hydrofluoric acid creates uniform cladding spikes onto which a SERS active metal is vacuum deposited, forming the SERS active surface. By varying the size of the silver islands deposited on the cladding peaks active, surface plasmons can be tuned to various excitation frequencies. The surface of these tapered fiber optic probes will be evaluated by analysis of the SERS signal, location and shape of the active surface plasmons. The cross talk between the fiber elements will also be evaluated.

Understanding Environmental Stability of Two-Dimensional Materials and Extending Their Shelf Life by Surface Functionalization

NASA Astrophysics Data System (ADS)

Yang, Sijie

Since the discovery of graphene, two dimensional materials (2D materials) have become a focus of interest for material research due to their many unique physical properties embedded in their 2D structure. While they host many exciting potential applications, some of these 2D materials are subject to environmental instability issues induced by interaction between material and gas molecules in air, which poses a barrier to further application and manufacture. To overcome this, it is necessary to understand the origin of material instability and interaction with molecules commonly found in air, as well as developing a reproducible and manufacturing compatible method to post-process these materials to extend their lifetime. In this work, the very first investigation on environmental stability on Te containing anisotropic 2D materials such as GaTe and ZrTe 3 is reported. Experimental results have demonstrated that freshly exfoliated GaTe quickly deteriorate in air, during which the Raman spectrum, surface morphology, and surface chemistry undergo drastic changes. Environmental Raman spectroscopy and XPS measurements demonstrate that H2O molecules in air interact strongly on the surface while O2, N 2, and inert gases don't show any detrimental effects on GaTe surface. Moreover, the anisotropic properties of GaTe slowly disappear during the aging process. To prevent this gas/material interaction based surface transformation, diazonium based surface functionalization is adopted on these Te based 2D materials. Environmental Raman spectroscopy results demonstrate that the stability of functionalized Te based 2D materials exhibit much higher stability both in ambient and extreme conditions. Meanwhile, PL spectroscopy, angle resolved Raman spectroscopy, atomic force microscopy measurements confirm that many attractive physical properties of the material are not affected by surface functionalization. Overall, these findings unveil the degradation mechanism of Te based 2D materials as well as provide a way to significantly enhance their environmental stability through an inexpensive and reproducible surface chemical functionalization route.

Disposable gold coated pyramidal SERS sensor on the plastic platform.

PubMed

Oo, S Z; Siitonen, S; Kontturi, V; Eustace, D A; Charlton, M D B

2016-01-11

In this paper we investigate suitability of arrays of gold coated pyramids for surface-enhanced Raman scattering (SERS) sensing applications. Pyramidarrays composed of 1000 nm pit size with 1250 nm pitch lengthwerereplicated on a plastic substrate by roll-to-roll (R2R) ultraviolet (UV) embossing. The level of SERS enhancement, and qualitative performance provided by the new substrate is investigated by comparing Raman spectrum of benzenethiol (BTh) test molecules to the benchmark Klarite SERS substrate which comprises inverted pyramid arrays(1500 nm pit size with 2000 nm pitch length) fabricated on a silicon substrate. The new substrate is found to provide upto 11 times increase in signal in comparison to the inverted pyramid (IV-pyramid) arrays fabricated on an identical plastic substrate. Numerical simulation and experimental evidence suggest that strongly confined electromagnetic fields close to the base of the pyramids, are mainly responsible for the Raman enhancement factor, instead of the fields localized around the tip. Unusually strong plasmon fields are projected upto 200nm from the sidewalls at the base of the pyramid increasing the cross sectional sensing volume.

Sol-gel chemical sensors for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Vincent Y.; Farquharson, Stuart; Kwon, Hueong-Chan; Shahriari, Mahmoud R.; Rainey, Petrie M.

1999-02-01

Surface-enhanced Raman spectroscopy (SERS) promises to be one of the most sensitive methods for chemical detection. Unfortunately, the inability of SERS to perform quantitative chemical analysis has slowed its general use in laboratories. This is largely due to the difficulty of manufacturing either active surfaces that yield reproducible enhancements, or surfaces that are capable of reversible chemical adsorption, or both. In an effort to meet this need, we have developed metal-doped sol-gels that provide surface-enhancement of Raman scattering. The porous silica network offers a unique environment for stabilizing SER active metal particles and the high surface area increases the interaction between the analyte and metal particles. This eliminates the need to concentrate the analyte on the surface by evaporating the solvent. The sol-gel is easily coated on a variety of surfaces, such as fiber optics, glass slides, or glass tubing, and can be designed into sample flow systems. Here we present the development of both gold- and silver-doped sol-gels, which have been used to coat the inside walls of glass sample vials for SERS applications. The performance of the metal-doped sol-gels was evaluated using p-aminobenzoic acid, to establish enhancement factors, detection limits, dynamic response range, reversibility, reproducibility, and suitability to commercial spectrometers. Measurements of trace chemicals, such as adenine and cocaine, are also presented.

Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

PubMed

Doğan, İlker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C M

2016-07-08

Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

Development of a miRNA surface-enhanced Raman scattering assay using benchtop and handheld Raman systems.

PubMed

Schechinger, Monika; Marks, Haley; Locke, Andrea; Choudhury, Mahua; Cote, Gerard

2018-01-01

DNA-functionalized nanoparticles, when paired with surface-enhanced Raman spectroscopy (SERS), can rapidly detect microRNA. However, widespread use of this approach is hindered by drawbacks associated with large and expensive benchtop Raman microscopes. MicroRNA-17 (miRNA-17) has emerged as a potential epigenetic indicator of preeclampsia, a condition that occurs during pregnancy. Biomarker detection using an SERS point-of-care device could enable prompt diagnosis and prevention as early as the first trimester. Recently, strides have been made in developing portable Raman systems for field applications. An SERS assay for miRNA-17 was assessed and translated from traditional benchtop Raman microscopes to a handheld system. Three different photoactive molecules were compared as potential Raman reporter molecules: a chromophore, malachite green isothiocyanate (MGITC), a fluorophore, tetramethylrhodamine isothiocyanate, and a polarizable small molecule 5,5-dithio-bis-(2-nitrobenzoic acid) (DTNB). For the benchtop Raman microscope, the DTNB-labeled assay yielded the greatest sensitivity under 532-nm laser excitation, but the MGITC-labeled assay prevailed at 785 nm. Conversely, DTNB was preferable for the miniaturized 785-nm Raman system. This comparison showed significant SERS enhancement variation in response to 1-nM miRNA-17, implying that the sensitivity of the assay may be more heavily dependent on the excitation wavelength, instrumentation, and Raman reporter chosen than on the plasmonic coupling from DNA/miRNA-mediated nanoparticle assemblies. (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Single cell analysis using surface enhanced Raman scattering (SERS) tags

PubMed Central

Nolan, John P.; Duggan, Erika; Liu, Er; Condello, Danilo; Dave, Isha; Stoner, Samuel A.

2013-01-01

Fluorescence is a mainstay of bioanalytical methods, offering sensitive and quantitative reporting, often in multiplexed or multiparameter assays. Perhaps the best example of the latter is flow cytometry, where instruments equipped with multiple lasers and detectors allow measurement of 15 or more different fluorophores simultaneously, but increases beyond this number are limited by the relatively broad emission spectra. Surface enhanced Raman scattering (SERS) from metal nanoparticles can produce signal intensities that rival fluorescence, but with narrower spectral features that allow a greater degree of multiplexing. We are developing nanoparticle SERS tags as well as Raman flow cytometers for multiparameter single cell analysis of suspension or adherent cells. SERS tags are based on plasmonically active nanoparticles (gold nanorods) whose plasmon resonance can be tuned to give optimal SERS signals at a desired excitation wavelength. Raman resonant compounds are adsorbed on the nanoparticles to confer a unique spectral fingerprint on each SERS tag, which are then encapsulated in a polymer coating for conjugation to antibodies or other targeting molecules. Raman flow cytometry employs a high resolution spectral flow cytometer capable of measuring the complete SERS spectra, as well as conventional flow cytometry measurements, from thousands of individual cells per minute. Automated spectral unmixing algorithms extract the contributions of each SERS tag from each cell to generate high content, multiparameter single cell population data. SERS-based cytometry is a powerful complement to conventional fluorescence-based cytometry. The narrow spectral features of the SERS signal enables more distinct probes to be measured in a smaller region of the optical spectrum with a single laser and detector, allowing for higher levels of multiplexing and multiparameter analysis. PMID:22498143

Rational design of Raman-labeled nanoparticles for a dual-modality, light scattering immunoassay on a polystyrene substrate.

PubMed

Israelsen, Nathan D; Wooley, Donald; Hanson, Cynthia; Vargis, Elizabeth

2016-01-01

Surface-enhanced Raman scattering (SERS) is a powerful light scattering technique that can be used for sensitive immunoassay development and cell labeling. A major obstacle to using SERS is the complexity of fabricating SERS probes since they require nanoscale characterization and optical uniformity. The light scattering response of SERS probes may also be modulated by the substrate used for SERS analysis. A typical SERS substrate such as quartz can be expensive. Polystyrene is a cheaper substrate option but can decrease the SERS response due to interfering Raman emission peaks and high background fluorescence. The goal of this research is to develop an optimized process for fabricating Raman-labeled nanoparticles for a SERS-based immunoassay on a polystyrene substrate. We have developed a method for fabricating SERS nanoparticle probes for use in a light scattering immunoassay on a polystyrene substrate. The light scattering profile of both spherical gold nanoparticle and gold nanorod SERS probes were characterized using Raman spectroscopy and optical absorbance spectroscopy. The effects of substrate interference and autofluorescence were reduced by selecting a Raman reporter with a strong light scattering response in a spectral region where interfering substrate emission peaks are minimized. Both spherical gold nanoparticles and gold nanorods SERS probes used in the immunoassay were detected at labeling concentrations in the low pM range. This analytical sensitivity falls within the typical dynamic range for direct labeling of cell-surface biomarkers using SERS probes. SERS nanoparticle probes were fabricated to produce a strong light scattering signal despite substrate interference. The optical extinction and inelastic light scattering of these probes was detected by optical absorbance spectroscopy and Raman spectroscopy, respectively. This immunoassay demonstrates the feasibility of analyzing strongly enhanced Raman signals on polystyrene, which is an inexpensive yet non-ideal Raman substrate. The assay sensitivity, which is in the low pM range, suggests that these SERS probe particles could be used for Raman labeling of cell or tissue samples in a polystyrene tissue culture plate. With continued development, this approach could be used for direct labeling of multiple cell surface biomarkers on strongly interfering substrate platforms.

Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates.

PubMed

Choi, Suhee; Ahn, Miri; Kim, Jongwon

2013-05-24

The fabrication of effective surface-enhanced Raman scattering (SERS) substrates has been the subject of intensive research because of their useful applications. In this paper, dendritic gold (Au) rod (DAR) structures prepared by simple one-step electrodeposition in a short time were examined as an effective SERS-active substrate. The SERS activity of the DAR surfaces was compared to that of other nanostructured Au surfaces with different morphologies, and its dependence on the structural variation of DAR structures was examined. These comparisonal investigations revealed that highly faceted sharp edge sites present on the DAR surfaces play a critical role in inducing a high SERS activity. The SERS enhancement factor was estimated to be greater than 10(5), and the detection limit of rhodamine 6G at DAR surfaces was 10(-8)M. The DAR surfaces exhibit excellent spot-to-spot and substrate-to-substrate SERS enhancement reproducibility, and their long-term stability is very good. It was also demonstrated that the DAR surfaces can be effectively utilized in electrochemical SERS systems, wherein a reversible SERS behavior was obtained during the cycling to cathodic potential regions. Considering the straightforward preparation of DAR substrates and the clean nature of SERS-active Au surfaces prepared in the absence of additives, we expect that DAR surfaces can be used as cost-effective SERS substrates in analytical and electrochemical applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Two-Dimensional Titanium Carbide (MXene) as Surface-Enhanced Raman Scattering Substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarycheva, Asia; Makaryan, Taron; Maleski, Kathleen

Here, noble metal (gold or silver) nanoparticles or patterned films are typically used as substrates for surface-enhanced Raman spectroscopy (SERS). Two-dimensional (2D) carbides and nitrides (MXenes) exhibit unique electronic and optical properties, including metallic conductivity and plasmon resonance in the visible or near-infrared range, making them promising candidates for a wide variety of applications. Herein, we show that 2D titanium carbide, Ti 3C 2T x, enhances Raman signal from organic dyes on a substrate and in solution. As a proof of concept, MXene SERS substrates were manufactured by spray-coating and used to detect several common dyes, with calculated enhancement factorsmore » reaching ~10 6. Titanium carbide MXene demonstrates SERS effect in aqueous colloidal solutions, suggesting the potential for biomedical or environmental applications, where MXene can selectively enhance positively charged molecules.« less

Layer-by-layer polyelectrolyte coating for surface-enhanced Raman scattering on gold nanostars inside hollow core photonic crystal fibers

NASA Astrophysics Data System (ADS)

Burmistrova, Natalia A.; Bondarenko, Sergei D.; Bratashov, Daniil N.; Shuvalov, Andrei A.; Chibrova, Anastasiya A.; Khlebtsov, Boris N.; Skibina, Julia S.; Goryacheva, Irina Y.

2018-04-01

Photonic crystal fibers with hollow core (HC PCFs) are a specific class of optical fibers characterized by microstructure with periodic holes oriented along fiber. The combination of HC PCF with Raman spectroscopy for biosensors creation is attractive in the terms of the low sample volume, the possibility to increase the integration time without sample degradation and maintaining constant focus during experiments. Here we propose layer-by-layer polyelectrolyte coating of HC PCF inner surface in order to obtain charge-selective absorption of analyte, stabilization of Surface-Enhanced Raman scattering (SERS)-active gold nanoparticles. Distance between SERS hotspots and glass reduces nonlinear signals from glass, and increases signal-to-noise ratio of SERS spectra.

Development of novel series and parallel sensing system based on nanostructured surface enhanced Raman scattering substrate for biomedical application

NASA Astrophysics Data System (ADS)

Chang, Te-Wei

With the advance of nanofabrication, the capability of nanoscale metallic structure fabrication opens a whole new study in nanoplasmonics, which is defined as the investigation of photon-electron interaction in the vicinity of nanoscale metallic structures. The strong oscillation of free electrons at the interface between metal and surrounding dielectric material caused by propagating surface plasmon resonance (SPR) or localized surface plasmon resonance (LSPR) enables a variety of new applications in different areas, especially biological sensing techniques. One of the promising biological sensing applications by surface resonance polariton is surface enhanced Raman spectroscopy (SERS), which significantly reinforces the feeble signal of traditional Raman scattering by at least 104 times. It enables highly sensitive and precise molecule identification with the assistance of a SERS substrate. Until now, the design of new SERS substrate fabrication process is still thriving since no dominant design has emerged yet. The ideal process should be able to achieve both a high sensitivity and low cost device in a simple and reliable way. In this thesis two promising approaches for fabricating nanostructured SERS substrate are proposed: thermal dewetting technique and nanoimprint replica technique. These two techniques are demonstrated to show the capability of fabricating high performance SERS substrate in a reliable and cost efficient fashion. In addition, these two techniques have their own unique characteristics and can be integrated with other sensing techniques to build a serial or parallel sensing system. The breakthrough of a combination system with different sensing techniques overcomes the inherent limitations of SERS detection and leverages it to a whole new level of systematic sensing. The development of a sensing platform based on thermal dewetting technique is covered as the first half of this thesis. The process optimization, selection of substrate material, and improved deposition technique are discussed in detail. Interesting phenomena have been found including the influence of Raman enhancement on substrate material selection and hot-spot rich bimetallic nanostructures by physical vapor deposition on metallic seed array, which are barely discussed in past literature but significantly affect the performance of SERS substrate. The optimized bimetallic backplane assisted resonating nanoantenna (BARNA) SERS substrate is demonstrated with the enhancement factor (EF) of 5.8 x 108 with 4.7 % relative standard deviation. By serial combination with optical focusing from nanojet effect, the nanojet and surface enhanced Raman scattering (NASERS) are proved to provide more than three orders of enhancement and enable us to perform stable, nearly single molecule detection. The second part of this thesis includes the development of a parallel dual functional nano Lycurgus cup array (nanoLCA) plasmonic device fabricated by nanoimprint replica technique. The unique configuration of the periodic nanoscale cup-shaped substrate enables a novel hybrid resonance coupling between SPR from extraordinary (EOT) and LSPR from dense sidewall metal nanoparticles with only single deposition process. The sub-50nm dense sidewall metal nanoparticles lead to high SERS performance in solution based detection, by which most biological and chemical analyses are typically performed. The SERS EF was calculated as 2.8 x 107 in a solution based environment with 10.2 % RSD, which is so far the highest reported SERS enhancement achieved with similar periodic EOT devices. In addition, plasmonic colorimetric sensing can be achieved in the very same device and the sensitivity was calculated as 796 nm/RIU with the FOM of 12.7. It creates a unique complementary sensing platform with both rapid on-site colorimetric screening and follow-up precise Raman analysis for point of care and resource limited environment applications. The implementations of bifunctional sensing on opto-microfluidic and smartphone platforms are proposed and examined here as well.

Tuning the interaction between propagating and localized surface plasmons for surface enhanced Raman scattering in water for biomedical and environmental applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shioi, Masahiko, E-mail: shioi.masahiko@jp.panasonic.com; Department of Electric and Electronic Engineering, Graduate School of Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501; Jans, Hilde

With a view to biomedical and environmental applications, we investigate the plasmonic properties of a rectangular gold nanodisk array in water to boost surface enhanced Raman scattering (SERS) effects. To control the resonance wavelengths of the surface plasmon polariton and the localized surface plasmon, their dependence on the array period and diameter in water is studied in detail using a finite difference time domain method. A good agreement is obtained between calculated resonant wavelengths and those of gold nanodisk arrays fabricated using electron beam lithography. For the optimized structure, a SERS enhancement factor of 7.8 × 10{sup 7} is achieved in watermore » experimentally.« less

Detection of anions by normal Raman spectroscopy and surface-enhanced Raman spectroscopy of cationic-coated substrates.

PubMed

Mosier-Boss, P A; Lieberman, S H

2003-09-01

The use of normal Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) of cationic-coated silver and gold substrates to detect polyatomic anions in aqueous environments is examined. For normal Raman spectroscopy, using near-infrared excitation, linear concentration responses were observed. Detection limits varied from 84 ppm for perchlorate to 2600 ppm for phosphate. In general, detection limits in the ppb to ppm concentration range for the polyatomic anions were achieved using cationic-coated SERS substrates. Adsorption of the polyatomic anions on the cationic-coated SERS substrates was described by a Frumkin isotherm. The SERS technique could not be used to detect dichromate, as this anion reacted with the coatings to form thiol esters. A competitive complexation method was used to evaluate the interaction of chloride ion with the cationic coatings. Hydrogen bonding and pi-pi interactions play significant roles in the selectivity of the cationic coatings.

Thermally generated metals for plasmonic coloring and surface-enhanced Raman sensing

NASA Astrophysics Data System (ADS)

Huang, Zhenping; Chen, Jian; Liu, Guiqiang; Wang, Yan; Liu, Yi; Tang, Li; Liu, Zhengqi

2018-03-01

Spectral coloring glass and its application on the surface-enhanced Raman scattering are demonstrated experimentally via a simple and moderate heat-treating of the top ultrathin gold film to create discrete nanoparticles, which can produce localized surface plasmon resonances and strong plasmonic near-field coupling effects. Ultrathin metal films with a wide range of thicknesses are investigated by different heat-treatment processes. The annealed metal films have been demonstrated with a series of spectral coloring responses. Moreover, the microscopy images of the metal film structures confirm the formation of distinct geometry features in these operation procedures. Densely packed nanoparticles are observed for the ultrathin metal film with the single-digit level of thickness. With increasing the film thickness over 10 nm, metallic clusters and porous morphologies can be obtained. Importantly, the metallic resonators can provide enhanced Raman scattering with the detection limit down to 10 - 7 molL - 1 of Rhodamine 6G molecules due to the excitation of plasmon resonances and strong near-field coupling effects. These features hold great potential for large-scale and low-cost production of colored glass and Raman substrate.

Metal oxide nanoparticle mediated enhanced Raman scattering and its use in direct monitoring of interfacial chemical reactions.

PubMed

Li, Li; Hutter, Tanya; Finnemore, Alexander S; Huang, Fu Min; Baumberg, Jeremy J; Elliott, Stephen R; Steiner, Ullrich; Mahajan, Sumeet

2012-08-08

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.

High-performance flexible surface-enhanced Raman scattering substrates fabricated by depositing Ag nanoislands on the dragonfly wing

NASA Astrophysics Data System (ADS)

Wang, Yuhong; Wang, Mingli; Shen, Lin; Sun, Xin; Shi, Guochao; Ma, Wanli; Yan, Xiaoya

2018-04-01

Natural dragonfly wing (DW), as a template, was deposited on noble metal sliver (Ag) nanoislands by magnetron sputtering to fabricate a flexible, low-cost, large-scale and environment-friendly surface-enhanced Raman scattering (SERS) substrate (Ag/DW substrate). Generally, materials with regular surface nanostructures are chosen for the templates, the selection of our new material with irregular surface nanostructures for substrates provides a new idea for the preparation of high-performance SERS-active substrates and many biomimetic materials. The optimum sputtering time of metal Ag was also investigated at which the prepared SERS-active substrates revealed remarkable SERS activities to 4-aminothiophenol (4-ATP) and crystal violet (CV). Even more surprisingly, the Ag/DW substrate with such an irregular template had reached the enhancement factor (EF) of ∼1.05 × 105 and the detection limit of 10-10 M to 4-ATP. The 3D finite-different time-domain (3D-FDTD) simulation illustrated that the "hot spots" between neighbouring Ag nanoislands at the top of pillars played a most important role in generating electromagnetic (EM) enhancement and strengthening Raman signals.

Novel One-pot Fabrication of Lab-on-a-Bubble@Ag Substrate without Coupling-agent for Surface Enhanced Raman Scattering

NASA Astrophysics Data System (ADS)

Jiang, Jizhou; Ou-Yang, Lei; Zhu, Lihua; Zou, Jing; Tang, Heqing

2014-02-01

Through in-situ reduction of silver nitrate without using any coupling-agent, a substrate for surface-enhanced Raman scattering (SERS) was prepared by coating silver on hollow buoyant silica microspheres as a lab on a bubble (LoB). The silver coated LoBs (LoBs@Ag) floated on surface of a solution could provide a very convenient platform for the detection of target molecules in the solution. The LoBs@Ag substrate not only immobilized well-distributed Ag nanoparticles on the surface LoBs, but excluded the interference of coupling agents. This yielded high-resolution SERS spectra with excellent reproducibility. The adsorption of crystal violet (CV) on the LoBs@Ag substrate was investigated by means of SERS combined with density functional theory (DFT) calculations. The LoBs@Ag substrate exhibited a remarkable Raman enhancement effect for CV with an enhancement factor of 6.9 × 108 and wide adaptability from dye, pesticide to bio-molecules. On the basis of this substrate, a simple and sensitive SERS method was proposed for the determination of trace organic pollutants or bio-molecules.

Detection of Prohibited Fish Drugs Using Silver Nanowires as Substrate for Surface-Enhanced Raman Scattering

PubMed Central

Song, Jia; Huang, Yiqun; Fan, Yuxia; Zhao, Zhihui; Yu, Wansong; Rasco, Barbara A.; Lai, Keqiang

2016-01-01

Surface-enhanced Raman scattering or surface-enhanced Raman spectroscopy (SERS) is a promising detection technology, and has captured increasing attention. Silver nanowires were synthesized using a rapid polyol method and optimized through adjustment of the molar ratio of poly(vinyl pyrrolidone) and silver nitrate in a glycerol system. Ultraviolet-visible spectrometry, X-ray diffraction, and transmission electron microscopy were used to characterize the silver nanowires. The optimal silver nanowires were used as a SERS substrate to detect prohibited fish drugs, including malachite green, crystal violet, furazolidone, and chloramphenicol. The SERS spectra of crystal violet could be clearly identified at concentrations as low as 0.01 ng/mL. The minimum detectable concentration for malachite green was 0.05 ng/mL, and for both furazolidone and chloramphenicol were 0.1 μg/mL. The results showed that the as-prepared Ag nanowires SERS substrate exhibits high sensitivity and activity. PMID:28335303

Indium nanoparticles for ultraviolet surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Das, Rupali; Soni, R. K.

2018-05-01

Ultraviolet Surface-enhanced Raman spectroscopy (UVSERS) has emerged as an efficient molecular spectroscopy technique for ultra-sensitive and ultra-low detection of analyte concentration. The generic SERS substrates based on gold and silver nanostructures have been extensively explored for high local electric field enhancement only in visible-NIR region of the electromagnetic spectrum. The template synthesis of controlled nanoscale size metallic nanostructures supporting localized surface plasmon resonance (LSPR) in the UV region have been recently explored due to their ease of synthesis and potential applications in optoelectronic, catalysis and magnetism. Indium (In0) nanoparticles exhibit active surface plasmon resonance (SPR) in ultraviolet (UV) and deep-ultaviolet (DUV) region with optimal absorption losses. This extended accessibility makes indium a promising material for UV plasmonic, chemical sensing and more recently in UV-SERS. In this work, spherical indium nanoparticles (In NPs) were synthesized by modified polyol reduction method using NaBH4 having local surface plasmon resonance near 280 nm. The as-synthesized spherical In0 nanoparticles were then coated with thin silica shells of thickness ˜ 5nm by a modified Stober method protecting the nanoparticles from agglomeration, direct contact with the probed molecules as well as prevent oxidation of the nanoparticles. Morphological evolution of In0 nanoparticles and SiO2 coating were characterized by transmission electron microscope (TEM). An enhanced near resonant shell-isolated SERS activity from thin film of tryptophan (Tryp) molecules deposited on indium coated substrates under 325nm UV excitation was observed. Finite difference time domain (FDTD) method is employed to comprehend the experimental results and simulate the electric field contours which showed amplified electromagnetic field localized around the nanostructures. The comprehensive analysis indicates that indium is a promising alternate exogenous contrast agent for efficient Raman spectroscopy from molecules.

Three-Dimensional Hierarchical Plasmonic Nano-Architecture Enhanced Surface-Enhanced Raman Scattering Immuno-Sensor for Cancer Biomarker Detection in Blood Plasma

PubMed Central

Li, Ming; Cushing, Scott K.; Zhang, Jianming; Suri, Savan; Evans, Rebecca; Petros, William P.; Gibson, Laura F.; Ma, Dongling; Liu, Yuxin; Wu, Nianqiang

2013-01-01

A three-dimensional (3D) hierarchical plasmonic nano-architecture has been designed for a sensitive surface-enhanced Raman scattering (SERS) immuno-sensor for protein biomarker detection. The capture antibody molecules are immobilized on a plasmonic gold triangle nano-array pattern. On the other hand, the detection antibody molecules are linked to the gold nano-star@Raman-reporter@silica sandwich nanoparticles. When protein biomarkers are present, the sandwich nanoparticles are captured over the gold triangle nano-array, forming a confined 3D plasmonic field, leading to the enhanced electromagnetic field in intensity and in 3D space. As a result, the Raman reporter molecules are exposed to a high density of “hot spots”, which amplifies the Raman signal remarkably, improving the sensitivity of the SERS immuno-sensor. This SERS immuno-sensor exhibits a wide linear range (0.1 pg/mL to 10 ng/mL), and a low limit of detection (7 fg/mL) toward human immunoglobulin G (IgG) protein in the buffer solution. This biosensor has been successfully used for detection of the vascular endothelial growth factor (VEGF) in the human blood plasma from clinical breast cancer patient samples. PMID:23659430

Development of high-sensitive, reproducible colloidal surface-enhanced Raman spectroscopy active substrate using silver nanocubes for potential biosensing applications

NASA Astrophysics Data System (ADS)

Hasna, Kudilatt; Lakshmi, Kiran; Ezhuthachan Jayaraj, Madambi Kunjukuttan; Kumar, Kumaran Rajeev; Matham, Murukeshan Vadakke

2016-04-01

Surface-enhanced Raman spectroscopy (SERS) has emerged as one of the thrust research areas that could find potential applications in bio and chemical sensing. We developed colloidal SERS active substrate with excellent sensitivity and high reproducibility using silver nanocube (AgNC) synthesized via the solvothermal method. Finite-difference time-domain simulation was carried out in detail to visualize dipole generation in the nanocube during localized surface plasmon resonance and to locate the respective hot spots in AgNC responsible for the huge Raman enhancement. The prediction is verified by the SERS analysis of the synthesized nanocubes using Rhodamine 6G molecule. An excellent sensitivity with a detection limit of 10-17 M and a very high enhancement factor of 1.2×108 confirms the "hot spots" in the nanocube. SERS activity is also carried out for crystal violet and for food adulterant Sudan I molecule. Finally, label-free DNA detection is performed to demonstrate the versatility of SERS as a potential biosensor.

Magnetically Assisted Surface-Enhanced Raman Spectroscopy for the Detection of Staphylococcus aureus Based on Aptamer Recognition.

PubMed

Wang, Junfeng; Wu, Xuezhong; Wang, Chongwen; Shao, Ningsheng; Dong, Peitao; Xiao, Rui; Wang, Shengqi

2015-09-23

A magnetically assisted surface-enhanced Raman scattering (SERS) biosensor for single-cell detection of S. aureus on the basis of aptamer recognition is reported for the first time. The biosensor consists of two basic elements including a SERS substrate (Ag-coated magnetic nanoparticles, AgMNPs) and a novel SERS tag (AuNR-DTNB@Ag-DTNB core-shell plasmonic NPs or DTNB-labeled inside-and-outside plasmonic NPs, DioPNPs). Uniform, monodisperse, and superparamagnetic AgMNPs with favorable SERS activity and magnetic responsiveness are synthesized by using polymer polyethylenimine. AgMNPs use magnetic enrichment instead of repeated centrifugation to prevent sample sedimentation. DioPNPs are designed and synthesized as a novel SERS tag. The Raman signal of DioPNPs is 10 times stronger than that of the commonly used SERS tag AuNR-DTNB because of the double-layer DTNB and the LSPR position adjustment to match the given laser excitation wavelength. Consequently, a strong SERS enhancement is achieved. Under the optimized aptamer density and linker length, capture by aptamer-modified AgMNPs can achieve favorable bacteria arrest (up to 75%). With the conventional Raman spectroscopy, the limit of detection (LOD) is 10 cells/mL for S. aureus detection, and a good linear relationship is also observed between the SERS intensity at Raman peak 1331 cm(-1) and the logarithm of bacteria concentrations ranging from 10(1) to 10(5) cells/mL. With the help of the newly developed SERS mapping technique, single-cell detection of S. aureus is easily achieved.

Toward development of a surface-enhanced Raman scattering (SERS)-based cancer diagnostic immunoassay panel.

PubMed

Granger, Jennifer H; Granger, Michael C; Firpo, Matthew A; Mulvihill, Sean J; Porter, Marc D

2013-01-21

Proteomic analyses of readily obtained human fluids (e.g., serum, urine, and saliva) indicate that the diagnosis of complex diseases will be enhanced by the simultaneous measurement of multiple biomarkers from such samples. This paper describes the development of a nanoparticle-based multiplexed platform that has the potential for simultaneous read-out of large numbers of biomolecules. For this purpose, we have chosen pancreatic adenocarcinoma (PA) as a test bed for diagnosis and prognosis. PA is a devastating form of cancer in which an estimated 86% of diagnoses resulted in death in the United States in 2010. The high mortality rate is due, in part, to the asymptomatic development of the disease and the dearth of sensitive diagnostics available for early detection. One promising route lies in the development of a serum biomarker panel that can generate a signature unique to early stage PA. We describe the design and development of a proof-of-concept PA biomarker immunoassay array coupled with surface-enhanced Raman scattering (SERS) as a sensitive readout method.

Material for surface-enhanced Raman spectroscopy, and SER sensors and method for preparing same

NASA Technical Reports Server (NTRS)

Farquharson, Stuart (Inventor); Nelson, Chad (Inventor); Lee, Yuan-Hsiang (Inventor)

2003-01-01

Metal-doped sol-gel materials, suitable for use as sensors for surface-enhanced Raman spectroscopic analysis for trace chemical detection, are produced by effecting gelation and solvent removal of a doped sol-gel under mild temperature conditions. At least in certain instances reaction and drying will desirably be effected in an oxygen-starved environment. The metal of the sol-gel material functions, when irradiated, to produce a plasmon field for interaction with molecules of an analyte in contact therewith, increasing by orders of magnitude Raman photons that are generate by excitation radiation, and the method allows matching of the metal and metal particle size to a wavelength of light (or incident radiation, e.g., laser radiation) to generate surface plasmons. The porosity of the sol-gel material dramatically increases the surface area, and thereby the amount of metal exposed for analyte interaction. The sensors provided may be in the form of glass vials, fiber optics, multi-well micro-sample plates, etc., having surface coatings of the doped sol-gel material, to provide sampling systems for use in a Raman instrument.

A ternary functional Ag@GO@Au sandwiched hybrid as an ultrasensitive and stable surface enhanced Raman scattering platform

NASA Astrophysics Data System (ADS)

Zhang, Cong-yun; Hao, Rui; Zhao, Bin; Hao, Yao-wu; Liu, Ya-qing

2017-07-01

The graphene-mediated surface enhanced Raman scattering (SERS) substrates by virtues of plasmonic metal nanostructures and graphene or its derivatives have attracted tremendous interests which are expected to make up the deficiency of traditional plasmonic metal substrates. Herein, we designed and fabricated a novel ternary Ag@GO@Au sandwich hybrid wherein the ultrathin graphene oxide (GO) films were seamlessly wrapped around the hierarchical flower-like Ag particle core and meanwhile provided two-dimensional anchoring scaffold for the coating of Au nanoparticles (NPs). The surface coverage density of loading Au NPs could be readily controlled by tuning the dosage amount of Au particle solutions. These features endowed the sandwiched structures high enrichment capability for analytes such as aromatic molecules and astonishing SERS performance. The Raman signals were enormously enhanced with an ultrasensitive detection limit of rhodamine-6G (R6G) as low as 10-13 M based on the chemical enhancement from GO and multi-dimensional plasmonic coupling between the metal nanoparticles. In addition, the GO interlayer as an isolating shell could effectively prevent the metal-molecule direct interaction and suppress the oxidation of Ag after exposure at ambient condition which enabled the substrates excellent reproducibility with less than 6% signal variations and prolonged life-time. To evaluate the feasibility and the practical application for SERS detection in real-world samples based on GO sandwiched hybrid as SERS-active substrate, three different prohibited colorants with a series of concentrations were measured with a minimum detected concentration down to 10-9 M. Furthermore, the prepared GO sandwiched nanostructures can be used to identify different types of colorants existing in red wine, implying the great potential applications for single-particle SERS sensing of biotechnology and on-site monitoring in food security.

Combination of inverted pyramidal nanovoid with silver nanoparticles to obtain further enhancement and its detection for ricin

NASA Astrophysics Data System (ADS)

Wang, Meng; Wang, Bin; Wu, Shixuan; Guo, Tingke; Li, Haoyu; Guo, Zhaoqing; Wu, Junhua; Jia, Peiyuan; Wang, Yuxia; Xu, Xiaoxuan; Wang, Yufang; Zhang, Cunzhou

2015-02-01

We have obtained the surface-enhanced Raman scattering substrate by depositing silver nanoparticles on the surface of the inverted pyramidal nanovoid in order to improve the enhance effects. Experimental results showed that the combined substrate exhibited greater enhancement than the nanovoid substrate or nanoparticles. In order to test the SERS activity of the combined substrates, Rh6G and ricin toxin were used as Raman probes. Finite element method was employed to simulate electric field and induced charge distribution of the substrates, which have been used to explore the interaction between nanoparticles and nanovoid as well as mechanism of the great enhancement.

In situ identification of high-performance thin-layer chromatography spots by fourier transform surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Koglin, Eckhardt; Kramer, Hella; Sawatski, Juergen; Lehner, Carolin; Hellman, Janice L.

1994-01-01

FT-SERS has been used to identify samples supported on high-performance thin-layer chromatography plates. The TLC plates were sprayed with colloidal silver solutions which resulted in enhancement of the FT-Raman scattering of these biologically and environmentally important compounds.

Superhydrophobic Ag decorated ZnO nanostructured thin film as effective surface enhanced Raman scattering substrates

NASA Astrophysics Data System (ADS)

Jayram, Naidu Dhanpal; Sonia, S.; Poongodi, S.; Kumar, P. Suresh; Masuda, Yoshitake; Mangalaraj, D.; Ponpandian, N.; Viswanathan, C.

2015-11-01

The present work is an attempt to overcome the challenges in the fabrication of super hydrophobic silver decorated zinc oxide (ZnO) nanostructure thin films via thermal evaporation process. The ZnO nanowire thin films are prepared without any surface modification and show super hydrophobic nature with a contact angle of 163°. Silver is further deposited onto the ZnO nanowire to obtain nanoworm morphology. Silver decorated ZnO (Ag@ZnO) thin films are used as substrates for surface enhanced Raman spectroscopy (SERS) studies. The formation of randomly arranged nanowire and silver decorated nanoworm structure is confirmed using FESEM, HR-TEM and AFM analysis. Crystallinity and existence of Ag on ZnO are confirmed using XRD and XPS studies. A detailed growth mechanism is discussed for the formation of the nanowires from nanobeads based on various deposition times. The prepared SERS substrate reveals a reproducible enhancement of 3.082 × 107 M for Rhodamine 6G dye (R6G) for 10-10 molar concentration per liter. A higher order of SERS spectra is obtained for a contact angle of 155°. Thus the obtained thin films show the superhydrophobic nature with a highly enhanced Raman spectrum and act as SERS substrates. The present nanoworm morphology shows a new pathway for the construction of semiconductor thin films for plasmonic studies and challenges the orderly arranged ZnO nanorods, wires and other nano structure substrates used in SERS studies.

Tailored surface-enhanced Raman nanopillar arrays fabricated by laser-assisted replication for biomolecular detection using organic semiconductor lasers.

PubMed

Liu, Xin; Lebedkin, Sergei; Besser, Heino; Pfleging, Wilhelm; Prinz, Stephan; Wissmann, Markus; Schwab, Patrick M; Nazarenko, Irina; Guttmann, Markus; Kappes, Manfred M; Lemmer, Uli

2015-01-27

Organic semiconductor distributed feedback (DFB) lasers are of interest as external or chip-integrated excitation sources in the visible spectral range for miniaturized Raman-on-chip biomolecular detection systems. However, the inherently limited excitation power of such lasers as well as oftentimes low analyte concentrations requires efficient Raman detection schemes. We present an approach using surface-enhanced Raman scattering (SERS) substrates, which has the potential to significantly improve the sensitivity of on-chip Raman detection systems. Instead of lithographically fabricated Au/Ag-coated periodic nanostructures on Si/SiO2 wafers, which can provide large SERS enhancements but are expensive and time-consuming to fabricate, we use low-cost and large-area SERS substrates made via laser-assisted nanoreplication. These substrates comprise gold-coated cyclic olefin copolymer (COC) nanopillar arrays, which show an estimated SERS enhancement factor of up to ∼ 10(7). The effect of the nanopillar diameter (60-260 nm) and interpillar spacing (10-190 nm) on the local electromagnetic field enhancement is studied by finite-difference-time-domain (FDTD) modeling. The favorable SERS detection capability of this setup is verified by using rhodamine 6G and adenosine as analytes and an organic semiconductor DFB laser with an emission wavelength of 631.4 nm as the external fiber-coupled excitation source.

SERS substrate based on silver nanoparticles and graphene: Dependence on the layer number of graphene

NASA Astrophysics Data System (ADS)

Garg, Preeti; Soni, R. K.; Raman, R.

2018-05-01

In this report, we describe a low-cost fabrication process for highly sensitive SERS substrate by using thermal evaporation technique. The SERS substrate structure consists of silver nanoparticles deposited on monolayer, bilayer and few layer graphene. The fabricated SERS substrates are investigated by field emission scanning electron microscope (FE-SEM), atomic force microscope (AFM), and confocal Raman spectroscope. From the surface morphology we have verified that the fabricated SERS substrate consist of high-density of silver nanoparticles with their size distribution varies from 10 to 150 nm. The surface-enhanced Raman scattering activities of these nanostructures is highest for monolayer graphene.

Non-plasmonic nanoantennas for surface enhanced spectroscopies with ultra-low heat conversion

PubMed Central

Caldarola, Martín; Albella, Pablo; Cortés, Emiliano; Rahmani, Mohsen; Roschuk, Tyler; Grinblat, Gustavo; Oulton, Rupert F.; Bragas, Andrea V.; Maier, Stefan A.

2015-01-01

Nanoplasmonics has recently revolutionized our ability to control light on the nanoscale. Using metallic nanostructures with tailored shapes, it is possible to efficiently focus light into nanoscale field ‘hot spots'. High field enhancement factors have been achieved in such optical nanoantennas, enabling transformative science in the areas of single molecule interactions, highly enhanced nonlinearities and nanoscale waveguiding. Unfortunately, these large enhancements come at the price of high optical losses due to absorption in the metal, severely limiting real-world applications. Via the realization of a novel nanophotonic platform based on dielectric nanostructures to form efficient nanoantennas with ultra-low light-into-heat conversion, here we demonstrate an approach that overcomes these limitations. We show that dimer-like silicon-based single nanoantennas produce both high surface enhanced fluorescence and surface enhanced Raman scattering, while at the same time generating a negligible temperature increase in their hot spots and surrounding environments. PMID:26238815

Non-plasmonic nanoantennas for surface enhanced spectroscopies with ultra-low heat conversion.

PubMed

Caldarola, Martín; Albella, Pablo; Cortés, Emiliano; Rahmani, Mohsen; Roschuk, Tyler; Grinblat, Gustavo; Oulton, Rupert F; Bragas, Andrea V; Maier, Stefan A

2015-08-04

Nanoplasmonics has recently revolutionized our ability to control light on the nanoscale. Using metallic nanostructures with tailored shapes, it is possible to efficiently focus light into nanoscale field 'hot spots'. High field enhancement factors have been achieved in such optical nanoantennas, enabling transformative science in the areas of single molecule interactions, highly enhanced nonlinearities and nanoscale waveguiding. Unfortunately, these large enhancements come at the price of high optical losses due to absorption in the metal, severely limiting real-world applications. Via the realization of a novel nanophotonic platform based on dielectric nanostructures to form efficient nanoantennas with ultra-low light-into-heat conversion, here we demonstrate an approach that overcomes these limitations. We show that dimer-like silicon-based single nanoantennas produce both high surface enhanced fluorescence and surface enhanced Raman scattering, while at the same time generating a negligible temperature increase in their hot spots and surrounding environments.

[Application of surface-enhanced Raman spectra to the analysis of Chinese Ephedra soup medicines].

PubMed

Zhang, J; Wang, Y

1998-06-01

A new method was developed to analyse the spectra of ephedrine in Chinese ephedra soup medicines, using surface-enhanced technique to combine thin layer chromatographic (TLC) technique with surface-enhanced Raman spectroscopy (SERS). The study indicates that the main vibrant characteristic spec tral band of the ephedrine molecules can be obtained by TLC in the samples of about 8 microg, and expounds char acteristics of the sample molecules and the silica gel. Therefore, it is clarified that the main chemical composi tion of Chinese medicines can be carried as finger-print type appraisal by combining TLC and SERS.

Application of surface-enhanced Raman spectroscopy (SERS) for cleaning verification in pharmaceutical manufacture.

PubMed

Corrigan, Damion K; Cauchi, Michael; Piletsky, Sergey; Mccrossen, Sean

2009-01-01

Cleaning verification is the process by which pharmaceutical manufacturing equipment is determined as sufficiently clean to allow manufacture to continue. Surface-enhanced Raman spectroscopy (SERS) is a very sensitive spectroscopic technique capable of detection at levels appropriate for cleaning verification. In this paper, commercially available Klarite SERS substrates were employed in order to obtain the necessary enhancement of signal for the identification of chemical species at concentrations of 1 to 10 ng/cm2, which are relevant to cleaning verification. The SERS approach was combined with principal component analysis in the identification of drug compounds recovered from a contaminated steel surface.

Microfluidic Channels on Nanopatterned Substrates: Monitoring Protein Binding to Lipid Bilayers with Surface-Enhanced Raman Spectroscopy

PubMed Central

Banerjee, Amrita; Perez-Castillejos, R.; Hahn, D.; Smirnov, Alex I.; Grebel, H.

2013-01-01

We used Surface Enhanced Raman Spectroscopy (SERS) to detect binding events between streptavidin and biotinylated lipid bilayers. The binding events took place at the surface between microfluidic channels and anodized aluminum oxide (AAO) with the latter serving as substrates. The bilayers were incorporated in the substrate pores. It was revealed that non-bound molecules were easily washed away and that large suspended cells (Salmonella enterica) are less likely to interfere with the monitoring process: when focusing to the lower surface of the channel, one may resolve mostly the bound molecules. PMID:24932024

Enhanced Raman spectroscopic study of the coordination chemistry of malononitrile on copper surfaces - Removal of nu(C=N) degeneracy through pi-coordination

NASA Technical Reports Server (NTRS)

Loo, B. H.; Lee, Y. G.; Frazier, D. O.

1985-01-01

Surface-enhanced Raman spectroscopy has been used to study the molecular interactions of malononitrile with copper electrode surfaces. The doubly degenerate CN stretching frequency at 2263/cm is removed when malononitrile adsorbs on copper. Two nu(CN) bands are observed at 2096 and 2204/cm at -0.6 V(SCE). The result shows that only one CN group is pi-coordinated with Cu, which contributes to the observed large shift (-167/cm) in nu(CN). The other CN group is not coordinated to the metal surface.

Micro-fluidic channels on nanopatterned substrates: Monitoring protein binding to lipid bilayers with surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Banerjee, Amrita; Perez-Castillejos, R.; Hahn, D.; Smirnov, Alex I.; Grebel, H.

2010-04-01

We used surface-enhanced Raman spectroscopy (SERS) to detect binding events between streptavidin and biotinylated lipid bilayers. The binding events took place at the surface between micro-fluidic channels and anodized aluminum oxide (AAO) with the latter serving as substrates. The bilayers were incorporated in the substrate pores. It was revealed that non-bound molecules were easily washed away and that large suspended cells ( Salmonella enterica) are less likely to interfere with the monitoring process: when focusing to the lower surface of the channel, one may resolve mostly the bound molecules.

Surface-enhanced Raman spectroscopy and homeland security: a perfect match?

PubMed

Golightly, Rebecca S; Doering, William E; Natan, Michael J

2009-10-27

This Nano Focus article reviews recent developments in surface-enhanced Raman spectroscopy (SERS) and its application to homeland security. It is based on invited talks given at the "Nanorods and Microparticles for Homeland Security" symposium, which was organized by one of the authors and presented at the 238th ACS National Meeting and Exhibition in Washington, DC. The three-day symposium included approximately 25 experts from academia, industry, and national laboratories and included both SERS and non-SERS approaches to detection of chemical and biological substances relevant to homeland security, as well as fundamental advances. Here, we focus on SERS and how it is uniquely positioned to have an impact in a field whose importance is increasing rapidly. We describe some technical challenges that remain and offer a glimpse of what form solutions might take.

A New Smart Surface-Enhanced Raman Scattering Sensor Based on pH-Responsive Polyacryloyl Hydrazine Capped Ag Nanoparticles

NASA Astrophysics Data System (ADS)

Yuan, Shuai; Ge, Fengyan; Zhou, Man; Cai, Zaisheng; Guang, Shanyi

2017-08-01

A novel pH-responsive Ag@polyacryloyl hydrazide (Ag@PAH) nanoparticle for the first time as a surface-enhanced Raman scattering (SERS) substrate was prepared without reducing agent and end-capping reagent. Ag@PAH nanoparticles exhibited an excellent tunable detecting performance in the range from pH = 4 to pH = 9. This is explained that the swelling-shrinking behavior of responsive PAH can control the distance between Ag NPs and the target molecules under external pH stimuli, resulting in the tunable LSPR and further controlled SERS. Furthermore, Ag@PAH nanoparticles possessed an ultra-sensitive detecting ability and the detection limit of Rhodamine 6G reduced to 10-12 M. These advantages qualified Ag@PAH NP as a promising smart SERS substrate in the field of trace analysis and sensors.

Raman spectroscopy: Watching a molecule breathe

NASA Astrophysics Data System (ADS)

Piatkowski, Lukasz; Hugall, James T.; van Hulst, Niek F.

2014-08-01

Marrying the single-molecule detection ability of surface-enhanced Raman scattering with the extreme time resolution of ultrafast coherent spectroscopy enables the vibrations of a single molecule to be observed.

Plasmon-enhanced Raman detection of body-fluid components

NASA Astrophysics Data System (ADS)

Matteini, Paolo; Banchelli, Martina; De Angelis, Marella; D'Andrea, Cristiano; Pini, Roberto

2018-02-01

Plasmon-enhanced spectroscopies such as surface-enhanced Raman spectroscopy (SERS) concern the detection of enhanced optical responses of molecules in close proximity to plasmonic structures, which results in a strong increase in sensitivity. Recent advancements in nanofabrication methods have paved the way for a controlled design of tailor-made nanostructures with fine-tuning of their optical and surface properties. Among these, silver nanocubes (AgNCs) represent a convenient choice in SERS owing to intense electromagnetic fields localized at their extremities, which are further intensified in the gap regions between closely spaced nanoparticles. The integration of AgNCs assemblies within an optofluidic platform may confer potential for superior optical investigation due to a molecular enrichment on the plasmonic structures to collect an enhanced photonic response. We developed a novel sensing platform based on an optofluidic system involving assembled silver nanocubes of 50 nm in size for ultrasensitive SERS detection of biomolecules in wet conditions. The proposed system offers the perspective of advanced biochemical and biological characterizations of molecules as well as of effective detection of body fluid components and other molecules of biomedical interest in their own environment.

Surface-enhanced raman spectroscopy substrate for arsenic sensing in groundwater

DOEpatents

Yang, Peidong; Mulvihill, Martin; Tao, Andrea R.; Sinsermsuksakul, Prasert; Arnold, John

2015-06-16

A surface-enhanced Raman spectroscopy (SERS) substrate formed from a plurality of monolayers of polyhedral silver nanocrystals, wherein at least one of the monolayers has polyvinypyrrolidone (PVP) on its surface, and thereby configured for sensing arsenic is described. Highly active SERS substrates are formed by assembling high density monolayers of differently shaped silver nanocrystals onto a solid support. SERS detection is performed directly on this substrate by placing a droplet of the analyte solution onto the nanocrystal monolayer. Adsorbed polymer, polyvinypyrrolidone (PVP), on the surface of the nanoparticles facilitates the binding of both arsenate and arsenite near the silver surface, allowing for highly accurate and sensitive detection capabilities.

Zirconium(IV) oxide: New coating material for nanoresonators for shell-isolated nanoparticle-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Krajczewski, Jan; Abdulrahman, Heman Burhanalden; Kołątaj, Karol; Kudelski, Andrzej

2018-03-01

One tool that can be used for determining the structure and composition of surfaces of various materials (even in in situ conditions) is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In SHINERS measurements, the surface under investigation is covered with a layer of surface-protected plasmonic nanoparticles, and then the Raman spectrum of the surface analysed is recorded. The plasmonic cores of the used core-shell structures act as electromagnetic nanoresonators, significantly locally enhancing the intensity of the electric field of the incident radiation, leading to a large increase in the efficiency of the generation of the Raman signal from molecules in the close proximity to the deposited SHINERS nanoresonators. A protective layer (from transparent dielectrics such as SiO2, Al2O3 or TiO2) prevents direct interaction between the plasmonic metal and the analysed surface (such interactions may lead to changes in the structure of the surface) and, in the case of plasmonic cores other than gold cores, the dielectric layer increases the chemical stability of the metal core. In this contribution, we show for the first time that core-shell nanoparticles having a silver core (both a solid and hollow one) and a shell of zirconium(IV) oxide are very efficient SHINERS nanoresonators that are significantly more stable in acidic and alkaline media than the silver-silica core-shell structures typically used for SHINERS experiments.

Surface-enhanced Raman scattering active gold nanoparticle/nanohole arrays fabricated through electron beam lithography

NASA Astrophysics Data System (ADS)

Wu, Tsunghsueh; Lin, Yang-Wei

2018-03-01

Effective surface-enhanced Raman scattering (SERS)-active substrates from gold nanoparticle and gold nanohole arrays were successfully fabricated through electron beam lithography with precise computer-aided control of the unit size and intergap distance. Their SERS performance was evaluated using 4-mercaptobenzoic acid (4-MBA). These gold arrays yielded strong SERS signals under 785 nm laser excitation. The enhancement factors for 4-MBA molecules on the prepared gold nanoparticle and nanohole arrays maxed at 1.08 × 107 and 8.61 × 106, respectively. The observed increase in SERS enhancement was attributed to the localized surface plasmon resonance (LSPR) wavelength shifting toward the near-infrared regime when the gold nanohole diameter increased, in agreement with the theoretical prediction in this study. The contribution of LSPR to the Raman enhancement from nanohole arrays deposited on fluorine-doped tin oxide glass was elucidated by comparing SERS and transmission spectra. This simple fabrication procedure, which entails employing electron beam lithography and the controllability of the intergap distance, suggests highly promising uses of nanohole arrays as functional components in sensing and photonic devices.

Properties of ordered titanium templates covered with Au thin films for SERS applications

NASA Astrophysics Data System (ADS)

Grochowska, Katarzyna; Siuzdak, Katarzyna; Sokołowski, Michał; Karczewski, Jakub; Szkoda, Mariusz; Śliwiński, Gerard

2016-12-01

Currently, roughened metal nanostructures are widely studied as highly sensitive Raman scattering substrates that show application potential in biochemistry, food safety or medical diagnostic. In this work the structural properties and the enhancement effect due to surface enhanced Raman scattering (SERS) of highly ordered nano-patterned titanium templates covered with thin (5-20 nm) gold films are reported. The templates are formed by preparation of a dense structure of TiO2 nanotubes on a flat Ti surface (2 × 2 cm2) and their subsequent etching down to the substrate. SEM images reveal the formation of honeycomb nanostructures with the cavity diameter of 80 nm. Due to the strongly inhomogeneous distribution of the electromagnetic field in the vicinity of the Au film discontinuities the measured average enhancement factor (107-108) is markedly higher than observed for bare Ti templates. The enhancement factor and Raman signal intensity can be optimized by adjusting the process conditions and thickness of the deposited Au layer. Results confirm that the obtained structures can be used in surface enhanced sensing.

Chromatographic separation and detection of contaminants from whole milk powder using a chitosan-modified silver nanoparticles surface-enhanced Raman scattering device.

PubMed

Li, Dan; Lv, Di Y; Zhu, Qing X; Li, Hao; Chen, Hui; Wu, Mian M; Chai, Yi F; Lu, Feng

2017-06-01

Methods for the on-site analysis of food contaminants are in high demand. Although portable Raman spectroscopy is commonly used to test food on-site, it can be challenge to achieve this goal with rapid detection and inexpensive substrate. In this study, we detected trace food contaminants in samples of whole milk powder using the methods that combined chromatography with surface-enhanced Raman scattering detection (SERS). We developed a simple and efficient technique to fabricate the paper with chitosan-modified silver nanoparticles as a SERS-active substrate. The soaking time of paper and the concentration of chitosan solution were optimized for chromatographic separation and SERS detection. We then studied the separation properties for real applications including complex sample matrices, and detected melamine at 1mg/L, dicyandiamide at 100mg/L and sodium sulfocyanate at 10mg/L in whole milk powder. As such, our methods have great potential for field-based detection of milk contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rough SERS substrate based on gold coated porous silicon layer prepared on the silicon backside surface

NASA Astrophysics Data System (ADS)

Dridi, H.; Haji, L.; Moadhen, A.

2017-04-01

We report in this paper a novel method to elaborate rough Surface Enhanced Raman Scattering (SERS) substrate. A single layer of porous silicon was formed on the silicon backside surface. Morphological characteristics of the porous silicon layer before and after gold deposition were influenced by the rough character (gold size). The reflectance measurements showed a dependence of the gold nano-grains size on the surface nature, through the Localized Surface Plasmon (LSP) band properties. SERS signal of Rhodamine 6G used as a model analyte, adsorbed on the rough porous silicon layer revealed a marked enhancement of its vibrational modes intensities.

Periodic silver nanocluster arrays over large-area silica nanosphere template as highly sensitive SERS substrate

NASA Astrophysics Data System (ADS)

Hou, Xu; Wang, Qi; Mao, Guoming; Liu, Hao; Yu, Rongdi; Ren, Xiaomin

2018-04-01

Periodic Ag nanocluster arrays for surface enhanced Raman spectroscopy (SERS) were fabricated through magnetron sputtering Ag over a large-area monolayer template which is based on silica (SiO2) nanospheres. High-density nanogaps between the adjacent Ag nanoclusters acted as "hot-spots", making a dominant contribution to the high-performance SERS detection. Moreover, the nanospheres and Ag nanoclusters effectively increased the surface roughness and also enlarged the surface area of as-obtained SERS substrate, which resulted in a further enhancement in Raman signals. As-prepared SERS substrates showed very high sensitivity with the enhancement factor (EF) value of 4.1 × 1012 for Rhodamine 6G (R6G), allowing the corresponding detection limit as low as 10-16 M. Additionally, SERS signal of melamine was still strong even though its concentration was lowered to 10-7 M. Our results show that preparing highly sensitive SERS substrate with periodic Ag nanoclusters over SiO2 nanosphere template is a convenient and promising pathway for chemical and biologic sensing.

Surface enhanced Raman spectroscopy (SERS) for the discrimination of Arthrobacter strains based on variations in cell surface composition.

PubMed

Stephen, Kate E; Homrighausen, Darren; DePalma, Glen; Nakatsu, Cindy H; Irudayaraj, Joseph

2012-09-21

Surface enhanced Raman spectroscopy (SERS) is a rapid and highly sensitive spectroscopic technique that has the potential to measure chemical changes in bacterial cell surface in response to environmental changes. The objective of this study was to determine whether SERS had sufficient resolution to differentiate closely related bacteria within a genus grown on solid and liquid medium, and a single Arthrobacter strain grown in multiple chromate concentrations. Fourteen closely related Arthrobacter strains, based on their 16S rRNA gene sequences, were used in this study. After performing principal component analysis in conjunction with Linear Discriminant Analysis, we used a novel, adapted cross-validation method, which more faithfully models the classification of spectra. All fourteen strains could be classified with up to 97% accuracy. The hierarchical trees comparing SERS spectra from the liquid and solid media datasets were different. Additionally, hierarchical trees created from the Raman data were different from those obtained using 16S rRNA gene sequences (a phylogenetic measure). A single bacterial strain grown on solid media culture with three different chromate levels also showed significant spectral distinction at discrete points identified by the new Elastic Net regularized regression method demonstrating the ability of SERS to detect environmentally induced changes in cell surface composition. This study demonstrates that SERS is effective in distinguishing between a large number of very closely related Arthrobacter strains and could be a valuable tool for rapid monitoring and characterization of phenotypic variations in a single population in response to environmental conditions.

Formation of silver nanoparticle at phospholipid template using Langmuir-Blodgett technique and its Surface-enhanced Raman Spectroscopy application

NASA Astrophysics Data System (ADS)

Mahato, M.; Sarkar, R.; Pal, P.; Talapatra, G. B.

2015-10-01

The biosynthesis of metal nanoparticle and their suitable assembly has recently gained tremendous interest for its application in biomedical arena such as substrates for surface-enhanced Raman scattering and others. In this article, an easy, low-cost, fast, bio-friendly and toxic-reducing agent free protocol has been described for the preparation of silver nanoparticle film using biocompatible 1,2-dipalmitoyl-sn-glycero-3-phosphocholine phospholipid Langmuir monolayer template. Interactions, docking and attachment of silver ions to the above-mentioned phospholipid monolayer have been studied by surface pressure-area isotherm and compressibility analysis at the air-water interface. We have deposited the Langmuir-Blodgett monolayer/multilayer containing silver nanoparticle onto glass/SiO2/quartz substrates. The formation of phospholipid-silver nanoparticle complex in Langmuir-Blodgett film has been characterized by field emission-scanning electron microscopy and high-resolution tunneling electron microscopy images. We have applied this deposited film as a substrate for surface-enhanced Raman scattering application using rhodamine 123 to understand the existence of the surface plasmon activity of silver nanoparticle.

Towards field malaria diagnosis using surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Keren; Xiong, Aoli; Yuen, Clement; Preiser, Peter; Liu, Quan

2016-04-01

We report three strategies of surface enhanced Raman spectroscopy (SERS) for β-hematin and hemozoin detection in malaria infected human blood, which can be potentially developed for field malaria diagnosis. In the first strategy, we used silver coated magnetic nanoparticles (Fe3O4@Ag) in combination with an external magnetic field to enhance the Raman signal of β-hematin. Then we developed two SERS methods without the requirement of magnetic field for malaria infection diagnosis. In Method 1, silver nanoparticles were synthesized separately and then mixed with lysed blood just like in traditional SERS measurements; while in Method 2, we developed an ultrasensitive SERS method by synthesizing silver nanoparticles directly inside the parasites of Plasmodium falciparum. Method 2 can be also used to detect single parasites in the ring stage.

Three-dimensional nanoporous MoS2 framework decorated with Au nanoparticles for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Sheng, Yingqiang; Jiang, Shouzhen; Yang, Cheng; Liu, Mei; Liu, Aihua; Zhang, Chao; Li, Zhen; Huo, Yanyan; Wang, Minghong; Man, Baoyuan

2017-08-01

The three-dimensional (3D) MoS2 decorated with Au nanoparticles (Au NPs) hybrids (3D MoS2-Au NPs) for surface-enhanced Raman scattering (SERS) sensing was demonstrated in this paper. SEM, Raman spectroscopy, TEM, SAED, EDX and XRD were performed to characterize 3D MoS2-Au NPs hybrids. Rhodamine 6G (R6G), fluorescein and gallic acid molecules were used as the probe for the SERS detection of the 3D MoS2-Au NPs hybrids. In addition, we modeled the enhancement of the electric field of MoS2-Au NPs hybrids using Finite-difference time-domain (FDTD) analysis, which can further give assistance to the mechanism understanding of the SERS activity.

Novel surface-enhanced Raman scattering-based assays for ultra-sensitive detection of human pluripotent stem cells.

PubMed

Han, Jingjia; Qian, Ximei; Wu, Qingling; Jha, Rajneesh; Duan, Jinshuai; Yang, Zhou; Maher, Kevin O; Nie, Shuming; Xu, Chunhui

2016-10-01

Human pluripotent stem cells (hPSCs) are a promising cell source for regenerative medicine, but their derivatives need to be rigorously evaluated for residual stem cells to prevent teratoma formation. Here, we report the development of novel surface-enhanced Raman scattering (SERS)-based assays that can detect trace numbers of undifferentiated hPSCs in mixed cell populations in a highly specific, ultra-sensitive, and time-efficient manner. By targeting stem cell surface markers SSEA-5 and TRA-1-60 individually or simultaneously, these SERS assays were able to identify as few as 1 stem cell in 10(6) cells, a sensitivity (0.0001%) which was ∼2000 to 15,000-fold higher than that of flow cytometry assays. Using the SERS assay, we demonstrate that the aggregation of hPSC-based cardiomyocyte differentiation cultures into 3D spheres significantly reduced SSEA-5(+) and TRA-1-60(+) cells compared with parallel 2D cultures. Thus, SERS may provide a powerful new technology for quality control of hPSC-derived products for preclinical and clinical applications. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Enhanced optical coupling and Raman scattering via microscopic interface engineering

NASA Astrophysics Data System (ADS)

Thompson, Jonathan V.; Hokr, Brett H.; Kim, Wihan; Ballmann, Charles W.; Applegate, Brian E.; Jo, Javier A.; Yamilov, Alexey; Cao, Hui; Scully, Marlan O.; Yakovlev, Vladislav V.

2017-11-01

Spontaneous Raman scattering is an extremely powerful tool for the remote detection and identification of various chemical materials. However, when those materials are contained within strongly scattering or turbid media, as is the case in many biological and security related systems, the sensitivity and range of Raman signal generation and detection is severely limited. Here, we demonstrate that through microscopic engineering of the optical interface, the optical coupling of light into a turbid material can be substantially enhanced. This improved coupling facilitates the enhancement of the Raman scattering signal generated by molecules within the medium. In particular, we detect at least two-orders of magnitude more spontaneous Raman scattering from a sample when the pump laser light is focused into a microscopic hole in the surface of the sample. Because this approach enhances both the interaction time and interaction region of the laser light within the material, its use will greatly improve the range and sensitivity of many spectroscopic techniques, including Raman scattering and fluorescence emission detection, inside highly scattering environments.

Resonant enhancement of Raman scattering in metamaterials with hybrid electromagnetic and plasmonic resonances

NASA Astrophysics Data System (ADS)

Guddala, Sriram; Narayana Rao, D.; Ramakrishna, S. Anantha

2016-06-01

A tri-layer metamaterial perfect absorber of light, consisting of (Al/ZnS/Al) films with the top aluminum layer patterned as an array of circular disk nanoantennas, is investigated for resonantly enhancing Raman scattering from C60 fullerene molecules deposited on the metamaterial. The metamaterial is designed to have resonant bands due to plasmonic and electromagnetic resonances at the Raman pump frequency (725 nm) as well as Stokes emission bands. The Raman scattering from C60 on the metamaterial with resonantly matched bands is measured to be enhanced by an order of magnitude more than C60 on metamaterials with off-resonant absorption bands peaking at 1090 nm. The Raman pump is significantly enhanced due to the resonance with a propagating surface plasmon band, while the highly impedance-matched electromagnetic resonance is expected to couple out the Raman emission efficiently. The nature and hybridization of the plasmonic and electromagnetic resonances to form compound resonances are investigated by numerical simulations.

High Surface-Enhanced Raman Scattering (SERS) Amplification Factor Obtained with Silver Printed Circuit Boards and the Influence of Phenolic Resins for the Characterization of the Pesticide Thiram.

PubMed

Silva de Almeida, Francylaine; Bussler, Larissa; Marcio Lima, Sandro; Fiorucci, Antonio Rogério; da Cunha Andrade, Luis Humberto

2016-07-01

In this work, low-cost substrates with rough silver surfaces were prepared from commercial copper foil-covered phenolic board (CPB) and an aqueous solution of AgNO3, and were used for surface-enhanced Raman scattering (SERS) and surface-enhanced resonance Raman scattering (SERRS) measurements. A maximum SERS amplification factor of 1.2 × 10(7) was obtained for Rhodamine 6G (R6G), and use of the CPB resulted in a detection limit for Thiram pesticide of 0.5 µmol L(-1) The minimum detection level was limited by residual traces of phenolic groups that originated from the substrate resin, which became solubilized in the aqueous Ag(+) solution. It was found that the bands corresponding to the impurities had less influence in the Thiram analysis, which could be explained by the high affinity of sulfur for Ag surfaces. The influence of impurities in the SERS analyses therefore depended on the linkage between the rough silver surface and the analyte. The findings demonstrated the ease and effectiveness of using CPB to prepare a nanostructured surface for SERS. © The Author(s) 2016.

Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Meng-Lei; Gao, Yu; Li, Yali; Li, Xueliang; Zhang, Huanjie; Han, Xiao Xia; Zhao, Bing; Su, Liang

2018-05-01

Glyphosate is one of the most commonly-used and non-selective herbicides in agriculture, which may directly pollute the environment and threaten human health. A simple and effective approach to assessment of its damage to the natural environment is thus quite necessary. However, traditional chromatography-based detection methods usually suffer from complex pretreatment procedures. Herein, we propose a simple and sensitive method for the determination of glyphosate by combining ninhydrin reaction and surface-enhanced Raman scattering (SERS) spectroscopy. The product (purple color dye, PD) of the ninhydrin reaction is found to SERS-active and directly correlate with the glyphosate concentration. The limit of detection of the proposed method for glyphosate is as low as 1.43 × 10- 8 mol·L- 1 with a relatively wider linear concentration range (1.0 × 10- 7-1.0 × 10- 4 mol·L- 1), which demonstrates its great potential in rapid, highly sensitive concentration determination of glyphosate in practical applications for safety assessment of food and environment.

Extraction and identification of mixed pesticides’ Raman signal and establishment of their prediction models

USDA-ARS?s Scientific Manuscript database

A nondestructive and sensitive method was developed to detect the presence of mixed pesticides of acetamiprid, chlorpyrifos and carbendazim on apples by surface-enhanced Raman spectroscopy (SERS). Self-modeling mixture analysis (SMA) was used to extract and identify the Raman spectra of individual p...

Based on surface-enhanced Raman spectroscopy analysis of serum albumin in different stages of liver disease for early screening primary liver cancer

NASA Astrophysics Data System (ADS)

Liao, Fadian; Ruan, Qiuyong; Lin, Juqiang; Lin, Jinyong; Zeng, Yongyi; Li, Ling; Huang, Zufang; Liu, Nenrong; Chen, Rong

2014-09-01

Despite the introduction of high-technology methods of detection and diagnosis, screening of primary liver cancer (PLC) remains imperfect. To diagnosis PLC earlier, Surface-enhanced Raman spectroscopy (SERS) coupled with cellulose-acetate membrane electrophoresis were introduced to separate human serum albumin and SERS spectra. Three groups (15 normal persons' samples, 17 hepatitis/cirrhosis samples, 15 cases of PLC) of serum albumin were tested. Silver colloid was used to obtain SERS spectra of human serum albumin. Principal component analysis (PCA) and linear discriminant analysis (LDA) were also employed for statistical analysis. The mean Raman spectra of three groups and the difference spectra of any two suggested that the albumin has changed in liver patients. Compared to normal groups, some Raman peaks have shifted or even disappeared in hepatitis/cirrhosis and PLCs groups. The sensitivity and specificity between PLCs and normal groups is 80% and 93.3%. Among hepatitis/cirrhosis and normal groups, the sensitivity is 88.2% and specificity is also 93.3%. Besides, the sensitivity and specificity between PLCs and hepatitis/cirrhosis groups is 86.7% and 76.5%. All the above data and results indicated that early screening of PLC is potential by SERS in different stages of liver disease before cancer occurs.

Probing the Sulfur-Modified Capping Layer of Gold Nanoparticles Using Surface Enhanced Raman Spectroscopy (SERS) Effects.

PubMed

Prado, Adilson R; Souza, Danilo Oliveira de; Oliveira, Jairo P; Pereira, Rayssa H A; Guimarães, Marco C C; Nogueira, Breno V; Dixini, Pedro V; Ribeiro, Moisés R N; Pontes, Maria J

2017-12-01

Gold nanoparticles (AuNP) exhibit particular plasmonic properties when stimulated by visible light, which makes them a promising tool to many applications in sensor technology and biomedical applications, especially when associated to sulfur-based compounds. Sulfur species form a great variety of self-assembled structures that cap AuNP and this interaction rules the optical and plasmonic properties of the system. Here, we report the behavior of citrate-stabilized gold nanospheres in two distinct sulfur colloidal solutions, namely, thiocyanate and sulfide ionic solutions. Citrate-capped gold nanospheres were characterized using ultraviolet-visible (UV-Vis) absorption, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM). In the presence of sulfur species, we have observed the formation of NP clusters and chain-like structures, giving rise to surface-enhanced effects. Surface-enhanced Raman spectroscopy (SERS) pointed to a modification in citrate vibrational modes, which suggests substitution of citrate by either thiocyanate or sulfide ions with distinct dynamics, as showed by in situ fluorescence. Moreover, we report the emergence of surface-enhanced infrared absorption (SEIRA) effect, which corroborates SERS conclusions. Further, SEIRA shows a great potential as a tool for specification of sulfur compounds in colloidal solutions, which is particularly useful when dealing with sensor technology.

Surface-enhanced Raman scattering (SERS) of riboflavin on nanostructured Ag surfaces: The role of excitation wavelength, plasmon resonance and molecular resonance.

PubMed

Šubr, Martin; Kuzminova, Anna; Kylián, Ondřej; Procházka, Marek

2018-05-15

Optimization of surface-enhanced Raman scattering (SERS)-based sensors for (bio)analytical applications has received much attention in recent years. For optimum sensitivity, both the nanostructure fabrication process and the choice of the excitation wavelength used with respect to the specific analyte studied are of crucial importance. In this contribution, detailed SERS intensity profiles were measured using gradient nanostructures with the localized surface-plasmon resonance (LSPR) condition varying across the sample length and using riboflavin as the model biomolecule. Three different excitation wavelengths (633 nm, 515 nm and 488 nm) corresponding to non-resonance, pre-resonance and resonance excitation with respect to the studied molecule, respectively, were tested. Results were interpreted in terms of a superposition of the enhancement provided by the electromagnetic mechanism and intrinsic properties of the SERS probe molecule. The first effect was dictated mainly by the degree of spectral overlap between the LSPR band, the excitation wavelength along with the scattering cross-section of the nanostructures, while the latter was influenced by the position of the molecular resonance with respect to the excitation wavelength. Our experimental findings contribute to a better understanding of the SERS enhancement mechanism. Copyright © 2018. Published by Elsevier B.V.

Surface-enhanced resonant Raman spectroscopy (SERRS) of single-walled carbon nanotubes absorbed on the Ag-coated anodic aluminum oxide (AAO) surface

NASA Astrophysics Data System (ADS)

Dou, X. Y.; Zhou, Z. P.; Tan, P. H.; Song, L.; Liu, L. F.; Zhao, X. W.; Luo, S. D.; Yan, X. Q.; Liu, D. F.; Wang, J. X.; Gao, Y.; Zhang, Z. X.; Yuan, H. J.; Zhou, W. Y.; Xie, S. S.

2005-05-01

In this paper, we developed a new kind of substrate, the silver-coated anodic aluminum oxide (AAO), to investigate the characters of surface-enhanced resonant Raman scattering (SERRS) of the dilute single-walled carbon nanotubes. Homogeneous Ag-coated AAO substrate was obtained by decomposing the AgNO 3 on the surface of AAO. single-walled carbon nanotubes (SWNTs) were directly grown onto this substrate through floating catalyst chemical vapor deposition method (CVD). SERRS of SWNTs was carried out using several different wavelength lasers. The bands coming from metallic SWNTs were significantly enhanced. The two SERRS mechanisms, the “electromagnetic” and “chemical” mechanism, were mainly responsible for the experiment results.

Highly narrow nanogap-containing Au@Au core-shell SERS nanoparticles: size-dependent Raman enhancement and applications in cancer cell imaging

NASA Astrophysics Data System (ADS)

Hu, Chongya; Shen, Jianlei; Yan, Juan; Zhong, Jian; Qin, Weiwei; Liu, Rui; Aldalbahi, Ali; Zuo, Xiaolei; Song, Shiping; Fan, Chunhai; He, Dannong

2016-01-01

Cellular imaging technologies employing metallic surface-enhanced Raman scattering (SERS) tags have gained much interest toward clinical diagnostics, but they are still suffering from poor controlled distribution of hot spots and reproducibility of SERS signals. Here, we report the fabrication and characterization of high narrow nanogap-containing Au@Au core-shell SERS nanoparticles (GCNPs) for the identification and imaging of proteins overexpressed on the surface of cancer cells. First, plasmonic nanostructures are made of gold nanoparticles (~15 nm) coated with gold shells, between which a highly narrow and uniform nanogap (~1.1 nm) is formed owing to polyA anchored on the Au cores. The well controlled distribution of Raman reporter molecules, such as 4,4'-dipyridyl (44DP) and 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB), are readily encoded in the nanogap and can generate strong, reproducible SERS signals. In addition, we have investigated the size-dependent SERS activity of GCNPs and found that with the same laser wavelength, the Raman enhancement discriminated between particle sizes. The maximum Raman enhancement was achieved at a certain threshold of particle size (~76 nm). High narrow nanogap-containing Au@Au core-shell SERS tags (GCTs) were prepared via the functionalization of hyaluronic acid (HA) on GCNPs, which recognized the CD44 receptor, a tumor-associated surface biomarker. And it was shown that GCTs have a good targeting ability to tumour cells and promising prospects for multiplex biomarker detection.Cellular imaging technologies employing metallic surface-enhanced Raman scattering (SERS) tags have gained much interest toward clinical diagnostics, but they are still suffering from poor controlled distribution of hot spots and reproducibility of SERS signals. Here, we report the fabrication and characterization of high narrow nanogap-containing Au@Au core-shell SERS nanoparticles (GCNPs) for the identification and imaging of proteins overexpressed on the surface of cancer cells. First, plasmonic nanostructures are made of gold nanoparticles (~15 nm) coated with gold shells, between which a highly narrow and uniform nanogap (~1.1 nm) is formed owing to polyA anchored on the Au cores. The well controlled distribution of Raman reporter molecules, such as 4,4'-dipyridyl (44DP) and 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB), are readily encoded in the nanogap and can generate strong, reproducible SERS signals. In addition, we have investigated the size-dependent SERS activity of GCNPs and found that with the same laser wavelength, the Raman enhancement discriminated between particle sizes. The maximum Raman enhancement was achieved at a certain threshold of particle size (~76 nm). High narrow nanogap-containing Au@Au core-shell SERS tags (GCTs) were prepared via the functionalization of hyaluronic acid (HA) on GCNPs, which recognized the CD44 receptor, a tumor-associated surface biomarker. And it was shown that GCTs have a good targeting ability to tumour cells and promising prospects for multiplex biomarker detection. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06919j

In Vivo and Ex Vivo Transcutaneous Glucose Detection Using Surface-Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Ma, Ke

Diabetes mellitus is widely acknowledged as a large and growing health concern. The lack of practical methods for continuously monitoring glucose levels causes significant difficulties in successful diabetes management. Extensive validation work has been carried out using surface-enhanced Raman spectroscopy (SERS) for in vivo glucose sensing. This dissertation details progress made towards a Raman-based glucose sensor for in vivo, transcutaneous glucose detection. The first presented study combines spatially offset Raman spectroscopy (SORS) with SERS (SESORS) to explore the possibility of in vivo, transcutaneous glucose sensing. A SERS-based glucose sensor was implanted subcutaneously in Sprague-Dawley rats. SERS spectra were acquired transcutaneously and analyzed using partial least-squares (PLS). Highly accurate and consistent results were obtained, especially in the hypoglycemic range. Additionally, the sensor demonstrated functionality at least17 days after implantation. A subsequent study further extends the application of SESORS to the possibility of in vivo detection of glucose in brain through skull. Specifically, SERS nanoantennas were buried in an ovine tissue behind a bone with 8 mm thickness and detected by using SESORS. In addition, quantitative detection through bones by using SESORS was also demonstrated. A device that could measure glucose continuously as well as noninvasively would be of great use to patients with diabetes. The inherent limitation of the SESORS approach may prevent this technique from becoming a noninvasive method. Therefore, the prospect of using normal Raman spectroscopy for glucose detection was re-examined. Quantitative detection of glucose and lactate in the clinically relevant range was demonstrated by using normal Raman spectroscopy with low power and short acquisition time. Finally, a nonlinear calibration method called least-squares support vector machine regression (LS-SVR) was investigated for analyzing spectroscopic data sets of glucose detection. Comparison studies were demonstrated between LS-SVR and PLS. LS-SVR demonstrated significant improvements in accuracy over PLS for glucose detection, especially when a global calibration model was required. The improvements imparted by LS-SVR open up the possibility of developing an accurate prediction algorithm for Raman-based glucose sensing applicable to a large human population. Overall, these studies show the high promise held by the Raman-based sensor for the challenge of optimal glycemic control.

Shell-Isolated Tip-Enhanced Raman and Fluorescence Spectroscopy.

PubMed

Huang, Ya-Ping; Huang, Sheng-Chao; Wang, Xiang-Jie; Bodappa, Nataraju; Li, Chao-Yu; Yin, Hao; Su, Hai-Sheng; Meng, Meng; Zhang, Hua; Ren, Bin; Yang, Zhi-Lin; Zenobi, Renato; Tian, Zhong-Qun; Li, Jian-Feng

2018-06-18

Tip-enhanced Raman spectroscopy can provide molecular fingerprint information with ultrahigh spatial resolution, but the tip will be easily contaminated, thus leading to artifacts. It also remains a great challenge to establish tip-enhanced fluorescence because of the quenching resulting from the proximity of the metal tip. Herein, we report shell-isolated tip-enhanced Raman and fluorescence spectroscopies by employing ultrathin shell-isolated tips fabricated by atomic layer deposition. Such shell-isolated tips not only show outstanding electromagnetic field enhancement in TERS but also exclude interference by contaminants, thus greatly promoting applications in solution. Tip-enhanced fluorescence has also been achieved using these shell-isolated tips, with enhancement factors of up to 1.7×10 3 , consistent with theoretical simulations. Furthermore, tip-enhanced Raman and fluorescence signals are acquired simultaneously, and their relative intensities can be manipulated by changing the shell thickness. This work opens a new avenue for ultrahigh resolution surface analysis using plasmon-enhanced spectroscopies. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Large-area, uniform and low-cost dual-mode plasmonic naked-eye colorimetry and SERS sensor with handheld Raman spectrometer

NASA Astrophysics Data System (ADS)

Xu, Zhida; Jiang, Jing; Wang, Xinhao; Han, Kevin; Ameen, Abid; Khan, Ibrahim; Chang, Te-Wei; Liu, Gang Logan

2016-03-01

We demonstrated a highly-sensitive, wafer-scale, highly-uniform plasmonic nano-mushroom substrate based on plastic for naked-eye plasmonic colorimetry and surface-enhanced Raman spectroscopy (SERS). We gave it the name FlexBrite. The dual-mode functionality of FlexBrite allows for label-free qualitative analysis by SERS with an enhancement factor (EF) of 108 and label-free quantitative analysis by naked-eye colorimetry with a sensitivity of 611 nm RIU-1. The SERS EF of FlexBrite in the wet state was found to be 4.81 × 108, 7 times stronger than in the dry state, making FlexBrite suitable for aqueous environments such as microfluid systems. The label-free detection of biotin-streptavidin interaction by both SERS and colorimetry was demonstrated with FlexBrite. The detection of trace amounts of the narcotic drug methamphetamine in drinking water by SERS was implemented with a handheld Raman spectrometer and FlexBrite. This plastic-based dual-mode nano-mushroom substrate has the potential to be used as a sensing platform for easy and fast analysis in chemical and biological assays.We demonstrated a highly-sensitive, wafer-scale, highly-uniform plasmonic nano-mushroom substrate based on plastic for naked-eye plasmonic colorimetry and surface-enhanced Raman spectroscopy (SERS). We gave it the name FlexBrite. The dual-mode functionality of FlexBrite allows for label-free qualitative analysis by SERS with an enhancement factor (EF) of 108 and label-free quantitative analysis by naked-eye colorimetry with a sensitivity of 611 nm RIU-1. The SERS EF of FlexBrite in the wet state was found to be 4.81 × 108, 7 times stronger than in the dry state, making FlexBrite suitable for aqueous environments such as microfluid systems. The label-free detection of biotin-streptavidin interaction by both SERS and colorimetry was demonstrated with FlexBrite. The detection of trace amounts of the narcotic drug methamphetamine in drinking water by SERS was implemented with a handheld Raman spectrometer and FlexBrite. This plastic-based dual-mode nano-mushroom substrate has the potential to be used as a sensing platform for easy and fast analysis in chemical and biological assays. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08357e

Green preparation of gold nanoparticles with Tremella fuciformis for surface enhanced Raman scattering sensing

NASA Astrophysics Data System (ADS)

Tang, Bin; Liu, Jun; Fan, Linpeng; Li, Daili; Chen, Xinzhu; Zhou, Ji; Li, Jingliang

2018-01-01

A simple in-situ synthesis method was developed to fabricate complex of Tremella fuciformis (TF) and gold nanoparticles (Au NPs). TF, one of the most popular fungi in the cuisine and medicine, acted as a biomass reducing agent and scaffold in the preparation of Au NPs. The intensities of the localized surface plasmon resonance (LSPR) of the complex of TF and Au NPs (Au@TFs) increased as the complex shrunk due to drying. The textures of TF prevent the aggregation of Au NPs during the drying process. The TFs show strong adsorption capacity for cationic dyes. It is suggested that the adsorption of the dyes onto TFs are achieved through electrostatic interactions between the TF and the dyes. Kinetics studies indicated that adsorption process could be well described by a pseudo-second-order model. Furthermore, the as-prepared Au@TFs were used as surface enhanced Raman scattering (SERS) substrates for analyzing trace dye molecules. The shrinkage of the TFs caused by drying concentrated dyes on their fruiting bodies, which led to the enhancement of Raman signals of dyes. The Au NPs on TF further enhanced the Raman signals. In-situ synthesis of Au NPs on TF may promote the applications of fungus materials in optical sensing of targets.

Enhancement of Raman scattering signal of a few molecules using photonic nanojet mediated SERS technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, G. M.; Parit, M. K.; Laha, R.

2016-05-06

Now a days, single molecule surface enhanced Raman spectroscopy (SMSERS) has become a fascinating tool for studying the structural properties, static and dynamic events of single molecules (instead of ensemble average), with the help of efficient plasmonic nanostructures. This is extremely useful in the field of proteomics because the structural properties of protein molecules are heterogeneous. Even though, SMSERS provides wealthy information about single molecules, it demands high quality surface enhanced Raman scattering (SERS) substrates. So far, a very few researchers succeeded in demonstrating the single molecule Raman scattering using conventional SERS technique. However, the experimental S/N of the Ramanmore » signal has been found to be very poor. Recently, with the help of photonic nanojet of an optical microsphere, we were able to enhance the SERS signal of a few molecules adsorbed on the SERS substrates (gold symmetric and asymmetric nanodimers and trimers dispersed on a glass slide). Herein, we report a few details about photonic nanojet mediated SERS technique, a few experimental results and a detailed theoretical study on symmetric and asymmetric nanosphere dimers to understand the dependence of localised surface plasmon resonance (LSPR) wavelength of a nanodimer on the nanogap size and polarization of the excitation light.« less

Amide I vibrational mode suppression in surface (SERS) and tip (TERS) enhanced Raman spectra of protein specimens

PubMed Central

Kurouski, Dmitry; Postiglione, Thomas; Deckert-Gaudig, Tanja; Deckert, Volker; Lednev, Igor K.

2013-01-01

Surface- and tip-enhanced Raman spectroscopy (SERS and TERS) are modern spectroscopic techniques, which are becoming widely used and show a great potential for the structural characterisation of biological systems. Strong enhancement of the Raman signal through localised surface plasmon resonance enables chemical detection at the single-molecule scale. Enhanced Raman spectra collected from biological specimens, such as peptides, proteins or microorganisms, were often observed to lack the amide I band, which is commonly used as a marker for the interpretation of secondary protein structure. The cause of this phenomenon was unclear for many decades. In this work, we investigated this phenomenon for native insulin and insulin fibrils using both TERS and SERS and compared these spectra to the spectra of well-defined homo peptides. The results indicate that the appearance of the amide I Raman band does not correlate with the protein aggregation state, but is instead determined by the size of the amino acid side chain. For short model peptides, the absence of the amide I band in TERS and SERS spectra correlates with the presence of a bulky side chain. Homo-glycine and -alanine, which are peptides with small side chain groups (H and CH3, respectively), exhibited an intense amide I band in almost 100% of the acquired spectra. Peptides with bulky side chains, such as tyrosine and tryptophan, exhibited the amide I band in 70% and 31% of the acquired spectra, respectively. PMID:23330149

Enhanced Raman scattering of biological molecules

NASA Astrophysics Data System (ADS)

Montoya, Joseph R.

The results presented in this thesis, originate from the aspiration to develop an identification algorithm for Salmonella enterica Serovar Enteritidis (S. enterica), Escherichia coli (E. coli), Bacillus globigii ( B. globigii), and Bacillus megaterium ( B. megaterium) using "enhanced" Raman scattering. We realized our goal, with a method utilizing an immunoassay process in a spectroscopic technique, and the direct use of the enhanced spectral response due to bacterial surface elements. The enhanced Raman signal originates from Surface Enhanced Raman Scattering (SERS) and/or Morphological Dependent Resonances (MDR's). We utilized a modified Lee-Meisel colloidal production method to produce a SERS active substrate, which was applied to a SERS application for the amino acid Glycine. The comparison indicates that the SERS/FRACTAL/MDR process can produce an increase of 107 times more signal than the bulk Raman signal from Glycine. In the extension of the Glycine results, we studied the use of SERS related to S. enterica, where we have shown that the aromatic amino acid contribution from Phenylalanine, Tyrosine, and Tryptophan produces a SERS response that can be used to identify the associated SERS vibrational modes of a S. enterica one or two antibody complexes. The "fingerprint" associated with the spectral signature in conjunction with an enhanced Raman signal allows conclusions to be made: (1) about the orientation of the secondary structure on the metal; (2) whether bound/unbound antibody can be neglected; (3) whether we can lower the detection limit. We have lowered the detection limit of S. enterica to 106 bacteria/ml. We also show a profound difference between S. enterica and E. coli SERS spectra even when there exists non-specific binding on E. coli indicating a protein conformation change induced by the addition of the antigen S. enterica. We confirm TEM imagery data, indicating that the source of the aromatic amino acid SERS response is originating from fractal structures on the surface of the bacteria with appropriate associated absorption spectra. In addition, we show that SERS may be used by directly detecting cell surface chemistry, with a report of a SERS response from gram-positive bacteria, B. globigii and B. megaterium combined, with silver fractal aggregates.

Noninvasively Imaging Subcutaneous Tumor Xenograft by a Handheld Raman Detector, with the Assistance of an Optical Clearing Agent.

PubMed

Zhang, Yunfei; Liu, Haoran; Tang, Jiali; Li, Zhuoyun; Zhou, Xingyu; Zhang, Ren; Chen, Liang; Mao, Ying; Li, Cong

2017-05-31

A handheld Raman detector with operational convenience, high portability, and rapid acquisition rate has been applied in clinics for diagnostic purposes. However, the inherent weakness of Raman scattering and strong scattering of the turbid tissue restricts its utilization to superficial locations. To extend the applications of a handheld Raman detector to deep tissues, a gold nanostar-based surface-enhanced Raman scattering (SERS) nanoprobe with robust colloidal stability, a fingerprint-like spectrum, and extremely high sensitivity (5.0 fM) was developed. With the assistance of FPT, a multicomponent optical clearing agent (OCA) efficiently suppressing light scattering from the turbid dermal tissues, the handheld Raman detector noninvasively visualized the subcutaneous tumor xenograft with a high target-to-background ratio after intravenous injection of the gold nanostar-based SERS nanoprobe. To the best of our knowledge, this work is the first example to introduce the optical clearing technique in assisting SERS imaging in vivo. The combination of optical clearing technology and SERS is a promising strategy for the extension of the clinical applications of the handheld Raman detector from superficial tissues to subcutaneous or even deeper lesions that are usually "concealed" by the turbid dermal tissue.

Surface enhanced Raman spectroscopy in the presence of hydroquinone assisted by gold nanorods

NASA Astrophysics Data System (ADS)

Cabrera Alonso, R.; Guevara, Edgar; Ramírez Elías, Miguel G.; González, Francisco Javier

2017-08-01

Hydroquinone is an aromatic organic molecule found in skin lightening creams for dermatological melasma treatment. The absorbance of this substance at high concentrations can be the cause of skin diseases. Nowadays most of the methods used for medical diagnosis for dermatological diseases consist on invasive methods such as biopsies. In recent years non-invasive techniques based on the properties of light and the interaction with biological samples have come to a new way for medical diagnosis. By means of Raman spectroscopy is of great interest the detection of hydroquinone for future medical applications. Due to the low Raman signal that the biological samples present, it is necessary to make use of nanotechnology. Making biosensors (SERS substrates) that allow us to amplify the electromagnetic field for the biological Raman signals.

Application of Raman spectroscopy, surface-enhanced Raman scattering (SERS), and density functional theory for the identification of phenethylamines.

PubMed

Taplin, Francis; O'Donnell, Deanna; Kubic, Thomas; Leona, Marco; Lombardi, John

2013-10-01

We evaluated the normal Raman (NR) and the surface-enhanced Raman scattering (SERS) of three sympathomimetic amines: phenethylamine, ephedrine, and 3,4-methylenedioxymethamphetamine (MDMA). In addition, quantum mechanical calculations-geometry optimization and calculations of the harmonic vibrational frequencies-were performed using the density functional theory (DFT) approach. Vibrational assignments were made by comparing the experimental and calculated spectra. The study found that both NR and SERS provided excellent spectra for the drugs tested. Certain conditions, such as response to various laser wavelengths and background fluorescence of the analyte, could be easily managed using SERS techniques. The DFT-calculated spectra could be correlated with the experimental spectra without the aid of a scaling factor. We also present a set of discriminant bands, useful for distinguishing the three compounds, despite their structural similarities.

Adsorption and sub-nanomolar sensing of thioflavin T on colloidal gold nanoparticles, silver nanoparticles and silver-coated films studied using surface-enhanced Raman scattering.

PubMed

Maiti, Nandita; Chadha, Ridhima; Das, Abhishek; Kapoor, Sudhir

2015-01-01

Raman and surface-enhanced Raman scattering (SERS) studies of thioflavin T (ThT) in solid, solution, gold nanoparticles (GNPs), silver nanoparticles (SNPs) and silver-coated films (SCFs) were investigated. Concentration-dependent SERS spectrum of ThT in GNPs and SNPs indicated the existence of two possible structures, one with the torsional angle (φ) between benzothiazole and dimethylaminobenzene rings being 37° and the other with φ=90°. The SERS spectrum of ThT in SCFs were similar to the Raman spectrum of solid and solution that suggests φ=37°. In this paper, the high sensitivity of the SERS technique was employed for sub-nanomolar (picomolar) sensing of ThT. Copyright © 2015 Elsevier B.V. All rights reserved.

m-Cresol purple functionalized surface enhanced Raman scattering paper chips for highly sensitive detection of pH in the neutral pH range.

PubMed

Zou, Xinxin; Wang, Yunqing; Liu, Wanhui; Chen, Lingxin

2017-06-26

Herein, a pH sensitive paper SERS chip was prepared by selecting m-cresol purple, a molecule with halochromic properties in the neutral pH range as a Raman reporter. The adsorbed m-cresol purple underwent a reversible change in its electronic configuration from a non-resonant species to a resonant species, which resulted in a significant Raman signal intensity variation due to the transformation of the sensing mode from SERS to surface-enhanced resonance Raman scattering (SERRS). The chips have a sensitive pH range of 6.0 to 8.0 and exhibited good performance for the detection of natural water samples with detection precision of approximately 0.03 pH units, suggesting great potential for environmental pH monitoring applications.

From near-infrared and Raman to surface-enhanced Raman spectroscopy: progress, limitations and perspectives in bioanalysis.

PubMed

Dumont, Elodie; De Bleye, Charlotte; Sacré, Pierre-Yves; Netchacovitch, Lauranne; Hubert, Philippe; Ziemons, Eric

2016-05-01

Over recent decades, spreading environmental concern entailed the expansion of green chemistry analytical tools. Vibrational spectroscopy, belonging to this class of analytical tool, is particularly interesting taking into account its numerous advantages such as fast data acquisition and no sample preparation. In this context, near-infrared, Raman and mainly surface-enhanced Raman spectroscopy (SERS) have thus gained interest in many fields including bioanalysis. The two former techniques only ensure the analysis of concentrated compounds in simple matrices, whereas the emergence of SERS improved the performances of vibrational spectroscopy to very sensitive and selective analyses. Complex SERS substrates were also developed enabling biomarker measurements, paving the way for SERS immunoassays. Therefore, in this paper, the strengths and weaknesses of these techniques will be highlighted with a focus on recent progress.

Sensitive determination of dopamine levels via surface-enhanced Raman scattering of Ag nanoparticle dimers.

PubMed

Yu, Xiantong; He, XiaoXiao; Yang, Taiqun; Zhao, Litao; Chen, Qichen; Zhang, Sanjun; Chen, Jinquan; Xu, Jianhua

2018-01-01

Dopamine (DA) is an important neurotransmitter in the hypothalamus and pituitary gland, which can produce a direct influence on mammals' emotions in midbrain. Additionally, the level of DA is highly related with some important neurologic diseases such as schizophrenia, Parkinson, and Huntington's diseases, etc. In light of the important roles that DA plays in the disease modulation, it is of considerable significance to develop a sensitive and reproducible approach for monitoring DA. The objective of this study was to develop an efficient approach to quantitatively monitor the level of DA using Ag nanoparticle (NP) dimers and enhanced Raman spectroscopy. Ag NP dimers were synthesized for the sensitive detection of DA via surface-enhanced Raman scattering (SERS). Citrate was used as both the capping agent of NPs and sensing agent to DA, which is self-assembled on the surface of Ag NP dimers by reacting with the surface carboxyl group to form a stable amide bond. To improve accuracy and precision, the multiplicative effects model for surface-enhanced Raman spectroscopy was utilized to analyze the SERS assays. A low limits of detection (LOD) of 20 pM and a wide linear response range from 30 pM to 300 nM were obtained for DA quantitative detection. The SERS enhancement factor was theoretically valued at approximately 10 7 by discrete dipole approximation. DA was self-assembled on the citrate capped surface of Ag NPs dimers through the amide bond. The adsorption energy was estimated to be 256 KJ/mol using the Langmuir isotherm model. The density functional theory was used to simulate the spectral characteristics of SERS during the adsorption of DA on the surface of the Ag dimers. Furthermore, to improve the accuracy and precision of quantitative analysis of SERS assays with a multiplicative effects model for surface-enhanced Raman spectroscopy. A LOD of 20 pM DA-level was obtained, and the linear response ranged from 30 pM to 300 nM for quantitative DA detection. The absolute relative percentage error was 4.22% between the real and predicted DA concentrations. This detection scheme is expected to have good applications in the prevention and diagnosis of certain diseases caused by disorders in the DA level.

Sensitive determination of dopamine levels via surface-enhanced Raman scattering of Ag nanoparticle dimers

PubMed Central

Yu, Xiantong; He, XiaoXiao; Yang, Taiqun; Zhao, Litao; Chen, Qichen; Zhang, Sanjun; Chen, Jinquan; Xu, Jianhua

2018-01-01

Background Dopamine (DA) is an important neurotransmitter in the hypothalamus and pituitary gland, which can produce a direct influence on mammals’ emotions in midbrain. Additionally, the level of DA is highly related with some important neurologic diseases such as schizophrenia, Parkinson, and Huntington’s diseases, etc. In light of the important roles that DA plays in the disease modulation, it is of considerable significance to develop a sensitive and reproducible approach for monitoring DA. Purpose The objective of this study was to develop an efficient approach to quantitatively monitor the level of DA using Ag nanoparticle (NP) dimers and enhanced Raman spectroscopy. Methods Ag NP dimers were synthesized for the sensitive detection of DA via surface-enhanced Raman scattering (SERS). Citrate was used as both the capping agent of NPs and sensing agent to DA, which is self-assembled on the surface of Ag NP dimers by reacting with the surface carboxyl group to form a stable amide bond. To improve accuracy and precision, the multiplicative effects model for surface-enhanced Raman spectroscopy was utilized to analyze the SERS assays. Results A low limits of detection (LOD) of 20 pM and a wide linear response range from 30 pM to 300 nM were obtained for DA quantitative detection. The SERS enhancement factor was theoretically valued at approximately 107 by discrete dipole approximation. DA was self-assembled on the citrate capped surface of Ag NPs dimers through the amide bond. The adsorption energy was estimated to be 256 KJ/mol using the Langmuir isotherm model. The density functional theory was used to simulate the spectral characteristics of SERS during the adsorption of DA on the surface of the Ag dimers. Furthermore, to improve the accuracy and precision of quantitative analysis of SERS assays with a multiplicative effects model for surface-enhanced Raman spectroscopy. Conclusion A LOD of 20 pM DA-level was obtained, and the linear response ranged from 30 pM to 300 nM for quantitative DA detection. The absolute relative percentage error was 4.22% between the real and predicted DA concentrations. This detection scheme is expected to have good applications in the prevention and diagnosis of certain diseases caused by disorders in the DA level. PMID:29713165

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse

NASA Astrophysics Data System (ADS)

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-01

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10‑9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse.

PubMed

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-18

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10 -9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Highly uniform and reproducible surface-enhanced Raman scattering from DNA-tailorable nanoparticles with 1-nm interior gap

NASA Astrophysics Data System (ADS)

Lim, Dong-Kwon; Jeon, Ki-Seok; Hwang, Jae-Ho; Kim, Hyoki; Kwon, Sunghoon; Suh, Yung Doug; Nam, Jwa-Min

2011-07-01

An ideal surface-enhanced Raman scattering (SERS) nanostructure for sensing and imaging applications should induce a high signal enhancement, generate a reproducible and uniform response, and should be easy to synthesize. Many SERS-active nanostructures have been investigated, but they suffer from poor reproducibility of the SERS-active sites, and the wide distribution of their enhancement factor values results in an unquantifiable SERS signal. Here, we show that DNA on gold nanoparticles facilitates the formation of well-defined gold nanobridged nanogap particles (Au-NNP) that generate a highly stable and reproducible SERS signal. The uniform and hollow gap (~1 nm) between the gold core and gold shell can be precisely loaded with a quantifiable amount of Raman dyes. SERS signals generated by Au-NNPs showed a linear dependence on probe concentration (R2 > 0.98) and were sensitive down to 10 fM concentrations. Single-particle nano-Raman mapping analysis revealed that >90% of Au-NNPs had enhancement factors greater than 1.0 × 108, which is sufficient for single-molecule detection, and the values were narrowly distributed between 1.0 × 108 and 5.0 × 109.

Maximizing the electromagnetic and chemical resonances of surface-enhanced Raman scattering for nucleic acids.

PubMed

Freeman, Lindsay M; Pang, Lin; Fainman, Yeshaiahu

2014-08-26

Although surface-enhanced Raman spectroscopy (SERS) has previously been performed with nucleic acids, the measured intensities for each nucleic acid have varied significantly depending on the SERS substrate and excitation wavelength. We have demonstrated that the charge-transfer (CT) mechanism, also known as the chemical enhancement of SERS, is responsible for the discrepancies previously reported in literature. The electronic states of cytosine and guanine attached to silver atoms are computationally calculated and experimentally measured to be in the visible range, which leads to a resonance Raman effect at the corresponding maximum wavelengths. The resulting SERS measurements are in good agreement with the simulated values, in which cytosine-silver shows stronger enhancement at 532 nm and guanine-silver shows stronger enhancement at 785 nm. An atomic layer of aluminum oxide is deposited on substrates to prevent charge-transfer, and corresponding measurements show weaker Raman signals caused by the suppression of the chemical resonance. These findings suggest the optimal SERS signal can be achieved by tuning the excitation wavelength to match both the electromagnetic and chemical resonances, paving the way for future single molecule detection of nucleic acids other than adenine.

Development of chitosan-coated gold nanoflowers as SERS-active probes

NASA Astrophysics Data System (ADS)

Xu, Dan; Gu, Jiangjiang; Wang, Weina; Yu, Xuehai; Xi, Kai; Jia, Xudong

2010-09-01

Surface-enhanced Raman scattering (SERS) has been intensely researched for many years as a potential technique for highly sensitive detection. This work, through the reduction of HAuCl4 with pyrrole in aqueous solutions, investigated a facile one-pot synthesis of flower-like Au nanoparticles with rough surfaces. The formation process of the Au nanoflowers (AuNFs) was carefully studied, and a spontaneous assembly mechanism was proposed based on the time-course experimental results. The key synthesis strategy was to use pyrrole as a weak particle stabilizing and reducing agent to confine crystal growth in the limited ligand protection region. The nanometer-scale surface roughness of AuNFs provided several hot spots on a single particle, which significantly increased SERS enhancement. Good biocompatible stable Raman-active probes were synthesized by coating AuNFs with chitosan. The conservation of the SERS effects in living cells suggested that the chitosan-capped AuNFs could be suitable for highly sensitive detection and have potential for targeting of tumors in vivo.

Reversible Gating of Plasmonic Coupling for Optical Signal Amplification.

PubMed

Khoury, Christopher G; Fales, Andrew M; Vo-Dinh, Tuan

2016-07-20

Amplification of optical signals is useful for a wide variety of applications, ranging from data signal transmission to chemical sensing and biomedical diagnostics. One such application in chemical sensing is surface-enhanced Raman scattering (SERS), an important technique for increasing the Raman signal using the plasmonic effect of enhanced electromagnetic fields associated with metallic nanostructures. One of the most important limitations of SERS-based amplification is the difficulty to reproducibly control the SERS signal. Here, we describe the design and implementation of a unique hybrid system capable of producing reversible gating of plasmonic coupling for Raman signal amplification. The hybrid system is composed of two subsystems: (1) colloidal magneto-plasmonic nanoparticles for SERS enhancement and (2) a micromagnet substrate with an externally applied magnetic field to modulate the colloidal nanoparticles. For this proof of concept demonstration, the nanoparticles were labeled with a Raman-active dye, and it was shown that the detected SERS signal could be reproducibly modulated by controlling the externally applied magnetic field. The developed system provides a simple, robust, inexpensive, and reusable device for SERS signal modulation. These properties will open up new possibilities for optical signal amplification and gating as well for high-throughput, reproducible SERS detection.

Live-Cell Pyrophosphate Imaging by in Situ Hot-Spot Generation.

PubMed

Li, Mingmin; Li, Jin; Di, Huixia; Liu, Huiqiao; Liu, Dingbin

2017-03-21

Controlling the electromagnetic hot-spot generation is essential for surface-enhanced Raman scattering (SERS) assays. Current hot-spot-based SERS assays have been extensively studied in solutions or on substrates. However, probing biospecies by controlling the hot-spot assembly in living systems has not been demonstrated thus far. Herein, we report a background-free SERS probe for imaging pyrophosphate (PPi), a biochemically significant anion, in living cells. Intracellular PPi is able to induce the nanoparticle dimerization, thus creating an intense electromagnetic hot spot and dramatically enhancing the signal of the Raman reporters residing in the hot spot. More impressively, the reporter we used in this study provides a strong and sharp single peak in the cellular Raman-silent region (1800-2800 cm -1 ), thus eliminating the possible background interference. This strategy could be readily extended to detect other biomarkers by only replacing the recognition ligands.

Nanomaterial strategies for immunodetection

NASA Astrophysics Data System (ADS)

Porter, M. D.; Granger, M. C.; Siperko, L. M.; Lipert, R. J.

2011-06-01

Metallic nanoparticles are playing increasingly important roles in biodiagnostic platforms. This emergence reflects the need to detect disease indicating entities at increasingly lower levels in human and veterinary diagnostics, homeland security, and food and water safety. To establish this perspective, this paper overviews our recent work using surface enhanced Raman scattering for detection of proteins, viruses, and microorganisms in heterogeneous immunoassays. It describes the assay platform, which is comprised of an antibody-modified capture substrate and gold nanoparticle-based label. The latter draws on the ability to reproducibly construct gold nanoparticles modified with a monolayer of an intrinsically strong Raman scatterer that is then coated with a layer of antibodies. This construct, referred to as an extrinsic Raman label, takes advantage of the signal enhancement of scatterers when coated on nanometer-sized gold particles and the antigenic binding specificity of the immobilized antibody layer. Challenges related to nonspecific adsorption, particle stability, and measurement reproducibility are also briefly examined.

Fabrication of porous nanostructures for Raman signal amplification

NASA Astrophysics Data System (ADS)

Mitsai, E. V.; Syubaev, S. A.; Kuchmizhak, A. A.

2018-01-01

Pulsed-laser dry printing of noble-metal microrings with a tunable internal porous structure, which can be revealed via an ion-beam etching post-procedure, was demonstrated. Average size of the pores inside the microrings were shown to be tuned in a wide range by varying the incident pulse energy and a nitrogen doping level controlled in the process of magnetron deposition of the gold film in the appropriate gaseous environment. The fabricated porous microrings were shown to provide many-fold near-field enhancement of incident electromagnetic fields, which was confirmed by mapping of the characteristic Raman band of a nanometer-thick covering layer of Rhodamine 6G molecules and supporting calculations. The proposed laser-printing/ion-beam etching approach is demonstrated to be a unique tool aimed at designing and fabricating multifunctional plasmonic structures and metasurfaces for spectroscopic bioidentification based on surface-enhanced Raman scattering and photoluminescence detection schemes.

Blood test using surface-enhanced Raman spectroscopy with colloidal silver nanoparticle substrate to detect polyps and colorectal cancer (Conference Presentation)

NASA Astrophysics Data System (ADS)

Wang, Wenbo; Feng, Shangyuan; Tai, Isabella T.; Chen, Guannan; Chen, Rong; Zeng, Haishan

2016-03-01

Colorectal cancer (CRC) is the third most common type of cancer and forth leading cause of cancer-related death. Early diagnosis is the key to long-term patient survival. Programmatic screening for the general population has shown to be cost-effective in reducing the incidence and mortality from CRC. Current CRC screening strategy relies on a broad range of test techniques such as fecal based tests and endoscopic exams. Occult blood tests like fecal immunochemical test is a cost effective way to detect CRC but have limited diagnostic values in detecting adenomatous polyp, the most treatable precursor to CRC. In the present work, we proposed the use of surface enhanced Raman spectroscopy (SERS) with silver nanoparticles as substrate to analyze blood plasma for detecting both CRC and adenomatous polyps. Blood plasma samples collected from healthy subjects and patients diagnosed with adenomas and CRC were prepared with nanoparticles and measured using a real-time fiber optic probe based Raman system. The collected SERS spectra are analyzed with partial least squares-discriminant analysis. Classification of normal versus CRC plus adenomatous polyps achieved diagnostic sensitivity of 86.4% and specificity of 80%. This exploratory study suggests that blood plasma SERS analysis has potential to become a screening test for detecting both CRC and adenomas.

Plasmon Mapping in Metallic Nanostructures and its Application to Single Molecule Surface Enhanced Raman Scattering: Imaging Electromagnetic Hot-Spots and Analyte Location

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camden, Jon P.

2013-07-12

A major component of this proposal is to elucidate the connection between optical and electron excitation of plasmon modes in metallic nanostructures. These accomplishments are reported: developed a routine protocol for obtaining spatially resolved, low energy EELS spectra, and resonance Rayleigh scattering spectra from the same nanostructures; correlated optical scattering spectra and plasmon maps obtained using STEM/EELS; and imaged electromagnetic hot spots responsible for single-molecule surface-enhanced Raman scattering (SMSERS).

[Study on the surface-enhanced Raman spectrum of trimethoprim].

PubMed

Zhang, Jin-zhi; Wang, Yuan

2003-02-01

A new method is given in this paper to study the spectra of trimethoprim by using the surface-enhanced Raman spectrum (SERS) technology and the highly efficient thin layer chromatography (TLC) dissociation technology. The results of SERS indicate that the main vibrant spectral band can be obtained by TLC in the samples of about 6 micrograms. The expansion and contraction of pyrimidine ring can be obviously increased and the molecule information can be exactly presented under the action of silver particles.

Surface Enhanced Raman Scattering Monitoring of Chain Alignment in Freely Suspended Nanomembranes

NASA Astrophysics Data System (ADS)

Jiang, Chaoyang; Lio, Wilber Y.; Tsukruk, Vladimir V.

2005-09-01

The molecular chain reorganization in freely standing membranes with encapsulated gold nanoparticles was studied with surface enhanced Raman scattering (SERS) in the course of their elastic deformations. The efficient SERS was enabled by optimizing the design of gold nanoparticle forming chainlike aggregates, thus creating an exceptional ability to conduct in situ monitoring. Small deformations resulted in the radial orientation of side phenyl rings of polymer backbones while larger deflections led to the polymer chains bridging adjacent nanoparticles within one-dimensional aggregates.

Spectroscopic study of surface enhanced Raman scattering of caffeine on borohydride-reduced silver colloids

NASA Astrophysics Data System (ADS)

Chen, Xiaomin; Gu, Huaimin; Shen, Gaoshan; Dong, Xiao; Kang, Jian

2010-06-01

The surface enhanced Raman scattering (SERS) of caffeine on borohydride-reduced silver colloids system under different aqueous solution environment has been studied in this paper. The relative intensity of SERS of caffeine significantly varies with different concentrations of sodium chloride and silver particles. However, at too high or too low concentration of sodium chloride and silver particle, the enhancement of SERS spectra is not evident. The SERS spectra of caffeine suggest that the contribution of the charge transfer mechanism to SERS may be dominant. The chloride ions can significantly enhance the efficiency of SERS, while the enhancement is selective, as the efficiency in charge transfer enhancement is higher than in electromagnetic enhancement. Therefore, it can be concluded that the active site of chloride ion locates on the bond between the caffeine and the silver surface. In addition, the SERS spectra of caffeine on borohydride-reduced and citrate-reduced silver colloids are different, which may be due to different states caffeine adsorbed on silver surface under different silver colloids.

Surface plasmon resonance induced enhancement of photoluminescence and Raman line intensity in SnS quantum dot-Sn nanoparticle hybrid structure.

PubMed

Warrier, Anita R; Gandhimathi, R

2018-04-27

In this article, we report on enhancement in photoluminescence and Raman line intensity of SnS quantum dots embedded in a mesh of Sn nanostructures. SnS nanoparticles synthesized by homogenous precipitation method show strong quantum confinement with a band gap of ∼2.7 eV (blue shift of ∼1 eV compared to bulk SnS particles). The optical band gap of SnS quantum dots is controlled by varying the pH (∼0 to 2.25), ageing time (24 to 144 h) and molarity (0 to 2 M) of the precursors. These SnS nanoparticles are embedded in a mesh of Sn nanostructures which are synthesized from tin chloride by using sodium borohydride as reducing agent. The Sn nanostructures have a morphology dependent, tunable surface plasmon resonance (SPR), ranging from UV (∼295 nm) to visible region (∼400 nm) of the electromagnetic spectrum. In the SnS-Sn nanohybrids, the excitons are strongly coupled with plasmons leading to a shift in the excitonic binding energy (∼400 meV). The pure SnS quantum dots have a very weak photoluminescence peak at ∼560 nm and Raman shift of low intensity at 853.08 cm -1 , 1078.17 cm -1 , 1255.60 cm -1 , 1466.91 cm -1 . The coupling of SnS nanoparticles with Sn nanoparticles results in strong exciton-plasmon interactions leading to enhanced photoluminescence and Raman line intensity. The nanohybrids formed using Sn nanosheets whose SPR matches with absorption onset of the SnS nanoparticles shows an enhancement of ∼10 4 times higher than pure SnS nanoparticles. Thus, Sn nanosheet with surface plasmon resonance in visible region (400 nm) like Au and Ag is a promising material for surface enhanced Raman spectroscopy, plasmon assisted fluorescence imaging and for enhancing the emission intensity of semiconductors with weak emission intensity.

Surface plasmon resonance induced enhancement of photoluminescence and Raman line intensity in SnS quantum dot-Sn nanoparticle hybrid structure

NASA Astrophysics Data System (ADS)

Warrier, Anita R.; Gandhimathi, R.

2018-07-01

In this article, we report on enhancement in photoluminescence and Raman line intensity of SnS quantum dots embedded in a mesh of Sn nanostructures. SnS nanoparticles synthesized by homogenous precipitation method show strong quantum confinement with a band gap of ∼2.7 eV (blue shift of ∼1 eV compared to bulk SnS particles). The optical band gap of SnS quantum dots is controlled by varying the pH (∼0 to 2.25), ageing time (24 to 144 h) and molarity (0 to 2 M) of the precursors. These SnS nanoparticles are embedded in a mesh of Sn nanostructures which are synthesized from tin chloride by using sodium borohydride as reducing agent. The Sn nanostructures have a morphology dependent, tunable surface plasmon resonance (SPR), ranging from UV (∼295 nm) to visible region (∼400 nm) of the electromagnetic spectrum. In the SnS-Sn nanohybrids, the excitons are strongly coupled with plasmons leading to a shift in the excitonic binding energy (∼400 meV). The pure SnS quantum dots have a very weak photoluminescence peak at ∼560 nm and Raman shift of low intensity at 853.08 cm‑1, 1078.17 cm‑1, 1255.60 cm‑1, 1466.91 cm‑1. The coupling of SnS nanoparticles with Sn nanoparticles results in strong exciton-plasmon interactions leading to enhanced photoluminescence and Raman line intensity. The nanohybrids formed using Sn nanosheets whose SPR matches with absorption onset of the SnS nanoparticles shows an enhancement of ∼104 times higher than pure SnS nanoparticles. Thus, Sn nanosheet with surface plasmon resonance in visible region (400 nm) like Au and Ag is a promising material for surface enhanced Raman spectroscopy, plasmon assisted fluorescence imaging and for enhancing the emission intensity of semiconductors with weak emission intensity.

Sensitive detection of point mutation using exponential strand displacement amplification-based surface enhanced Raman spectroscopy.

PubMed

Huang, Si-Qiang; Hu, Juan; Zhu, Guichi; Zhang, Chun-Yang

2015-03-15

Accurate identification of point mutation is particularly imperative in the field of biomedical research and clinical diagnosis. Here, we develop a sensitive and specific method for point mutation assay using exponential strand displacement amplification (SDA)-based surface enhanced Raman spectroscopy (SERS). In this method, a discriminating probe and a hairpin probe are designed to specifically recognize the sequence of human K-ras gene. In the presence of K-ras mutant target (C→T), the 3'-terminal of discriminating probe and the 5'-terminal of hairpin probe can be ligated to form a SDA template. Subsequently, the 3'-terminal of hairpin probe can function as a primer to initiate the SDA reaction, producing a large amount of triggers. The resultant triggers can further hybridize with the discriminating probes to initiate new rounds of SDA reaction, leading to an exponential amplification reaction. With the addition of capture probe-modified gold nanoparticles (AuNPs) and the Rox-labeled reporter probes, the amplified triggers can be assembled on the surface of AuNPs through the formation of sandwich hybrids of capture probe-trigger-reporter probe, generating a strong Raman signal. While in the presence of K-ras wild-type target (C), neither ligation nor SDA reaction can be initiated and no Raman signal is observed. The proposed method exhibits high sensitivity with a detection limit of 1.4pM and can accurately discriminate as low as 1% variant frequency from the mixture of mutant target and wild-type target. Importantly, this method can be further applied to analyze the mutant target in the spiked HEK293T cell lysate, holding great potential for genetic analysis and disease prognosis. Copyright © 2014 Elsevier B.V. All rights reserved.

On the chemical enhancement in SERS

NASA Astrophysics Data System (ADS)

Jensen, Lasse

2012-12-01

In Surface-enhanced Raman scattering (SERS), the Raman signal of a molecule adsorbed on a metal surface is enhanced by many orders of magnitude. This provides a "finger-print" of molecules which can be used in ultrasensitive sensing devises. Here we present a time-dependent density functional theory (TDDFT) study of the molecule-surface chemical coupling in SERS. A systematic study of the chemical enhancement (CHEM) of meta-and para-substituted pyridines interacting with a small silver cluster (Ag20) is presented. We find that the magnitude of chemical enhancement is governed to a large extent by the energy difference between the highest occupied energy level (HOMO) of the metal and the lowest unoccupied energy level (LUMO) of the molecule. A two-state approximation shows that the enhancement scales roughly as (ωX/ω¯e)4, where accent="true">ω¯e is an average excitation energy between the HOMO of the metal and the LUMO of the molecule and wX the HOMO-LUMO gap of the free molecule. Furthermore, we demonstrate that it is possible to control the CHEM enhancement by switching a dithienylethene photoswitch from its closed form to its open form. The open form of the photoswitch is found to be the strongest Raman scatterer when adsorbed on the surface whereas the opposite is found for the free molecule. This trend is explained using the simple two-state approximation.