Development of an optical biosensor based on surface-enhanced Raman scattering for DNA analysis

NASA Astrophysics Data System (ADS)

Yigit, Tugce; Akdogan, Ebru; Karagoz, Isık. Didem; Kahraman, Mehmet

2016-03-01

Rapid, accurate and sensitive DNA analysis is critically important for the diagnostic of genetic diseases. The most common method preferred in practice is fluorescence based microarrays to analyze the DNA. However, there exist some disadvantages related to the above-mentioned method such as the overlapping of the fluorescence emission wavelengths that can diminish in the performance of multiplexing, needed to obtain fluorescence spectra from each dye and photo degradation. In this study, a novel SERS based DNA analysis approach, which is Raman active dye-free and independent of SERS substrate properties, is developed. First, the single strand DNA probe is attached to the SERS substrate and half of the complimentary DNA is attached to gold nanoparticles, as well. We hypothesize that in the presence of target DNA, the complimentary DNA coupled colloids will bind to the SERS substrate surface via hybridization of single strand target DNA. To test this hypothesis, we used UV/Vis spectroscopy, atomic for microscopy (AFM) and dynamic light scattering (DLS). DNA analysis is demonstrated by a peak shift of the certain peak of the small molecules attached to the SERS substrate surface instead of SERS spectrum obtained in the presence of target DNA from the Raman reporter molecules. The degree of peak shifting will be used for the quantification of the target DNA in the sample. Plasmonic properties of SERS substrates and reproducibility issues will not be considerable due to the use of peak shifting instead of peak intensity for the qualitative analysis.

Fabrication of Gold-Coated Ultra-Thin Anodic Porous Alumina Substrates for Augmented SERS

PubMed Central

Toccafondi, Chiara; Proietti Zaccaria, Remo; Dante, Silvia; Salerno, Marco

2016-01-01

Anodic porous alumina (APA) is a nanostructured material used as a template in several nanotechnological applications. We propose the use of APA in ultra-thin form (<100 nm) for augmented surface-enhanced Raman scattering (SERS). Here, the effect of in-depth thinning of the APA nanostructures for possible maximization of SERS was addressed. Anodization was carried out on ultra-thin films of aluminum on glass and/or silicon, followed by pore-opening. Gold (Au) was overcoated and micro-Raman/SERS measurements were carried out on test target analytes. Finite integration technique simulations of the APA-Au substrate were used both for the experimental design and simulations. It was observed that, under optimized conditions of APA and Au thickness, the SERS enhancement is higher than on standard APA-Au substrates based on thin (~100 nm) APA by up to a factor of ~20 for test molecules of mercaptobenzoic acid. The agreement between model and experimental results confirms the current understanding of SERS as being mainly due to the physical origin of plasmon resonances. The reported results represent one step towards micro-technological, integrated, disposable, high-sensitivity SERS chemical sensors and biosensors based on similar substrates. PMID:28773525

Rich variety of substrates for surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Nguyen, Bich Ha; Hieu Nguyen, Van; Nhung Tran, Hong

2016-09-01

The efficiency of the application of surface enhanced Raman spectroscopy (SERS) technique to each specified purpose significantly depends on the choice of the SERS substrate with an appropriate structure as well as on its performance. Until the present time a rich variety of SERS substrates was fabricated. They can be classified according to their structures. The present work is a review of main types of SERS substrates for using in the trace analysis application. They can be classified into 4 groups: (1) Substrates using gold nanoparticles (AuNPs) with spherical shape such as colloidal AuNPs, AuNPs fabricated by pulsed laser deposition, by sputtering or by capillary force assembly (CFA), substrates fabricated by electrospinning technique, substrates using metallic nanoparticle arrays fabricated by electron beam lithography combined with CFA method, substrates using silver nanoparticle (AgNP) arrays grain by chemical seeded method, substrates with tunable surface plasmon resonance, substrates based on precies subnanometer plasmonic junctions within AuNP assemblies, substrates fabricated by simultaneously immobilizing both AuNPs and AgNPs on the same glass sides etc. (2) Substrates using nanostructures with non-spherical shapes such as gold nanowire (NW), or highly anisotropic nickel NW together with large area, free-standing carpets, substrates with obviously angular, quasi-vertically aligned cuboid-shaped TiO2 NW arrays decorated with AgNPs, substrates using gold nanoprism monolayer films, substrates using silver nanocube dimmers or monodisperse close-packed gold nanotriangle monolayers. (3) Substrates using multiparticle complex nanostructure such as nanoparticle cluster arrays, gold nanoflowers and nanodendrites. (4) Flexible substrate such as paper-based swab with gold nanorods, adhesive polymer tapes fabricated by inkjet printing method and flexible and adhesive SERS tapes fabricated by decorating AuNPs via the conventional drop-dry method.

High-Performance, Large Format Surfaces for Surface-Enhanced Raman Spectroscopy: Increasing the Accessibility of an Analytical Platform

NASA Astrophysics Data System (ADS)

Kanipe, Katherine Nicole

Although surface-enhanced Raman spectroscopy (SERS) is a spectroscopic technique with unusually high sensitivity and molecular specificity, few practical analytical applications have been implemented that take advantage of its power. Based on what is understood about SERS from the experimental and theoretical research of the past forty years, we developed a few well-defined design principles on the basis of which a reliable and reproducibly manufacturable SERS-active substrate could be fabricated that is highly enhancing, highly uniform, stable, and based on a broad range of metals so that various chemical processes could be probed. Finally, we restricted ourselves to using only readily scalable fabrication techniques. The resulting SERS-active device was a metal over silica, two-dimensional nano-grating that was shown to produce enhancements of ˜107 when compared to a smooth surface of the same metal. This SERS substrate also shows unprecedented signal uniformity over square centimeters, and is fabricated using commonly-available foundry-based approaches exclusively. Initially, we explored the properties of a gold-coated substrates in which a first-order grating resonance due to long-range symmetry is augmented by a local resonance due to the individual core-shell grating elements. The SERS properties of such grating systems were systematically studied as a function of various structural parameters such as the grating pitch, the inter-element gap and the thickness of the metal layer. The most enhancing substrates were found to have a grating parameter with a radiative, rather than evanescent, first-order resonance; a sufficiently small gap between nearest neighbor grating elements to produce near-field interactions; and a gold layer whose thickness was larger than the electronic mean-free-path of the conduction electrons, so as to ensure a high conductivity for the metal layer to sustain strong surface plasmons. We applied these same architectural principles to metals other than gold, and concluded that every workable metal (and virtually any material with sufficiently high electrical conductivity) when appropriately nanostructured, has the potential to be an efficient SERS substrate. The use of materials for SERS beyond silver and gold, has significant advantages, most importantly, allowing SERS to be used to study the surface chemistry and catalysis taking place on metals with more interesting chemistries than those of Au and Ag. Additionally, SERS substrates can be fabricated from high natural abundance, low cost materials. This was illustrated by producing SERS substrates using copper, aluminum, and nickel in addition to silver and gold which were used as benchmarks. All five metals were found to yield high SERS intensities. The variation of the SERS enhancement among them is ascribed mainly to local field effects, with the (larger) grating-based enhancement making an approximately equivalent contribution to the SERS enhancement of the five metals. This conclusion is supported by local electric field simulations. The utility of these new grating-based SERS substrates was demonstrated by implementing them in chemical analysis in both aqueous and gas phases for which, for example, we were able to readily detect opioids such as fentanyl and morphine at concentrations as low as less than one part per billion. Additionally, we have made good progress toward integration of this substrate architecture into a microfluidic channel for a higher degree of sample workup and control.

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.

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.

Fabrication of novel compound SERS substrates composed of silver nanoparticles and porous gold nanoclusters: A study on enrichment detection of urea

NASA Astrophysics Data System (ADS)

Li, Yali; Li, Qianwen; Sun, Chengbin; Jin, Sila; Park, Yeonju; Zhou, Tieli; Wang, Xu; Zhao, Bing; Ruan, Weidong; Jung, Young Mee

2018-01-01

A new type of surface-enhanced Raman scattering (SERS) substrate was fabricated through the layer-by-layer self-assembly of silver nanoparticles (AgNPs, av. 45 nm in diameter) and porous gold nanoclusters/nanoparticles (AuNPs, av. 143 nm in diameter). The development of the porosity of the AuNPs was investigated, and successful SERS applications of the porous AuNPs were also examined. As compared with AgNP films, the enhancement factor of Ag-Au compound substrates is increased 6 times at the concentration of 10-6 M. This additional enhancement contributes to the trace-amount-detection of target molecules enormously. The contribution is generated through the increase of the usable surface area arising from the nanoscale pores distributed three-dimensionally in the porous AuNPs, which enrich the adsorption sites and hot spots for the adsorption of probe molecules, making the developed nanofilms highly sensitive SERS substrates. The substrates were used for the detection of a physiological metabolite of urea molecules. The results reached to a very low concentration of 1 mM and exhibited good quantitative character over the physiological concentration range (1 ∼ 20 mM) under mimicking biophysical conditions. These results show that the prepared substrate has great potential in the ultrasensitive SERS-based detection and in SERS-based biosensors.

Flexible SERS Substrates: Challenges and Opportunities

DTIC Science & Technology

2016-01-28

interactions between the analyte, silver nanoparticles , and a salt. This system has also been applied to detection of trace antibiotics for food safety...Cleanable SERS Substrates Based on Silver Nanoparticle Decorated Electrospun Nano-fibrous Membranes Chaoyang Jiang Porous electrospun nanofibrous...present our recent work on the preparation, characterization, and SERS activity of silver nanoparticle decorated polymeric electrospun nanofibers

SERS activity with tenfold detection limit optimization on a type of nanoporous AAO-based complex multilayer substrate

NASA Astrophysics Data System (ADS)

Sui, Chaofan; Wang, Kaige; Wang, Shuang; Ren, Junying; Bai, Xiaohong; Bai, Jintao

2016-03-01

Most of SERS applications are constricted by heterogeneous hotspots and aggregates of nanostructure, which result in low sensitivity and poor reproducibility of characteristic signals. This work intends to introduce SERS properties of a type of SERS-active substrate, Au-CuCl2-AAO, which is innovatively developed on a porous anodic alumina oxide (AAO) template. Spectral measuring results of Rhodamine 6G (R6G) on this substrate optimized by controlling morphology and gold thickness showed that enhancement factor (2.30 × 107) and detection limit (10-10 M) were both improved and represented better performance than its template AAO. Homogenous hot spots across the region of interest were achieved by scanning SERS intensity distribution for the band at 1505 cm-1 in 5 × 5 μm2 area. Furthermore, the promising SERS activity of the flower-patterned substrate was theoretically explained through simulation of the electromagnetic field distribution. In addition, this SERS substrate is proposed for applications within the field of chemical and biochemical analyses.Most of SERS applications are constricted by heterogeneous hotspots and aggregates of nanostructure, which result in low sensitivity and poor reproducibility of characteristic signals. This work intends to introduce SERS properties of a type of SERS-active substrate, Au-CuCl2-AAO, which is innovatively developed on a porous anodic alumina oxide (AAO) template. Spectral measuring results of Rhodamine 6G (R6G) on this substrate optimized by controlling morphology and gold thickness showed that enhancement factor (2.30 × 107) and detection limit (10-10 M) were both improved and represented better performance than its template AAO. Homogenous hot spots across the region of interest were achieved by scanning SERS intensity distribution for the band at 1505 cm-1 in 5 × 5 μm2 area. Furthermore, the promising SERS activity of the flower-patterned substrate was theoretically explained through simulation of the electromagnetic field distribution. In addition, this SERS substrate is proposed for applications within the field of chemical and biochemical analyses. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06771e

Functional paper-based SERS substrate for rapid and sensitive detection of Sudan dyes in herbal medicine

NASA Astrophysics Data System (ADS)

Wu, Mianmian; Li, Pan; Zhu, Qingxia; Wu, Meiran; Li, Hao; Lu, Feng

2018-05-01

There has been an increasing demand for rapid and sensitive techniques for the identification of Sudan compounds that emerged as the most often illegally added fat-soluble dyes in herbal medicine. In this report, we have designed and fabricated a functionalized filter paper consisting of gold nanorods (GNRs) and mono-6-thio-cyclodextrin (HS-β-CD) as a surface-enhanced Raman spectroscopy (SERS) substrate, in which the GNR provides sufficient SERS enhancement, and the HS-β-CD with strong chemical affinity toward GNR provides the inclusion compound to capture hydrophobic molecules. Moreover, the CD-GNR were uniformly assembled on filter paper cellulose through the electrostatic adsorption and hydrogen bond, so that the CD-GNR paper-based SERS substrate (CD-GNR-paper) demonstrated higher sensitivity for the determination of Sudan III (0.1 μM) and Sudan IV (0.5 μM) than GNRs paper-based SERS substrate (GNR-paper), with high stability after the storage in the open air for 90 days. Importantly, CD-GNR-paper can effectively collect the Sudan dyes from illegally adulterated onto samples of Resina Draconis with a simple operation, further open up new exciting opportunity for SERS detection of more compounds illegally added with high sensitivity and fast signal responses.

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.

Hotspots engineering by grafting Au@Ag core-shell nanoparticles on the Au film over slightly etched nanoparticles substrate for on-site paraquat sensing.

PubMed

Wang, Chaoguang; Wu, Xuezhong; Dong, Peitao; Chen, Jian; Xiao, Rui

2016-12-15

Paraquat (PQ) pollutions are ultra-toxic to human beings and hard to be decomposed in the environment, thus requiring an on-site detection strategy. Herein, we developed a robust and rapid PQ sensing strategy based on the surface-enhanced Raman scattering (SERS) technique. A hybrid SERS substrate was prepared by grafting the Au@Ag core-shell nanoparticles (NPs) on the Au film over slightly etched nanoparticles (Au FOSEN). Hotspots were engineered at the junctions as indicated by the finite difference time domain calculation. SERS performance of the hybrid substrate was explored using p-ATP as the Raman probe. The hybrid substrate gives higher enhancement factor comparing to either the Au FOSEN substrate or the Au@Ag core-shell NPs, and exhibits excellent reproducibility, homogeneity and stability. The proposed SERS substrates were prepared in batches for the practical PQ sensing. The total analysis time for a single sample, including the pre-treatment and measurement, was less than 5min with a PQ detection limit of 10nM. Peak intensities of the SERS signal were plotted as a function of the PQ concentrations to calibrate the sensitivity by fitting the Hill's equation. The plotted calibration curve showed a good log-log linearity with the coefficient of determination of 0.98. The selectivity of the sensing proposal was based on the "finger print" Raman spectra of the analyte. The proposed substrate exhibited good recovery when it applied to real water samples, including lab tap water, bottled water, and commercially obtained apple juice and grape juice. This SERS-based PQ detection method is simple, rapid, sensitive and selective, which shows great potential in pesticide residue and additives abuse monitoring. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Porous Silicon Covered with Silver Nanoparticles as Surface-Enhanced Raman Scattering (SERS) Substrate for Ultra-Low Concentration Detection.

PubMed

Kosović, Marin; Balarin, Maja; Ivanda, Mile; Đerek, Vedran; Marciuš, Marijan; Ristić, Mira; Gamulin, Ozren

2015-12-01

Microporous and macro-mesoporous silicon templates for surface-enhanced Raman scattering (SERS) substrates were produced by anodization of low doped p-type silicon wafers. By immersion plating in AgNO3, the templates were covered with silver metallic film consisting of different silver nanostructures. Scanning electron microscopy (SEM) micrographs of these SERS substrates showed diverse morphology with significant difference in an average size and size distribution of silver nanoparticles. Ultraviolet-visible-near-infrared (UV-Vis-NIR) reflection spectroscopy showed plasmonic absorption at 398 and 469 nm, which is in accordance with the SEM findings. The activity of the SERS substrates was tested using rhodamine 6G (R6G) dye molecules and 514.5 nm laser excitation. Contrary to the microporous silicon template, the SERS substrate prepared from macro-mesoporous silicon template showed significantly broader size distribution of irregular silver nanoparticles as well as localized surface plasmon resonance closer to excitation laser wavelength. Such silver morphology has high SERS sensitivity that enables ultralow concentration detection of R6G dye molecules up to 10(-15) M. To our knowledge, this is the lowest concentration detected of R6G dye molecules on porous silicon-based SERS substrates, which might even indicate possible single molecule detection.

Gold nanochestnut arrays as ultra-sensitive SERS substrate for detecting trace pesticide residue.

PubMed

Geng, Fei; Zhao, Huaping; Fu, Qun; Mi, Yan; Miao, Likun; Li, Wei; Dong, Yulian; Wu, Minghong; Lei, Yong

2018-07-20

In comparison to conventional spectroscopic techniques based on chromatography, surface-enhanced Raman spectroscopy (SERS) enables the rapid identification and detection of trace pesticide residues present in trace amounts in the environment and foods. Herein, a facile approach to fabricate unique gold nanochestnuts (GNCs) as an ultra-sensitive SERS substrate for detecting trace pesticide residues has been developed based on anodic aluminum oxide (AAO) templates. The GNCs are synthesized through the galvanic replacement of Ag on the top of Ni nanorod arrays. The as-prepared GNCs have well-controlled structural parameters, and importantly have unique anisotropic morphologies that benefit the enhancement in SERS performance. As a result, rhodamine 6 G (R6G) can be efficiently detected with GNCs as the SERS substrate even with a concentration of only 10 -12 M, and the Raman enhancement factor reaches up to 5.4 × 10 9 at this concentration. Further SERS measurement of thiram indicates a remarkable SERS-active sensitivity of the as-prepared GNCs with a detection limit of thiram up to 10 -14 M. The GNCs also exhibit a high signal-to-noise ratio.

Nanoarchitecture Based SERS for Biomolecular Fingerprinting and Label-Free Disease Markers Diagnosis.

PubMed

Sinha, Sudarson Sekhar; Jones, Stacy; Pramanik, Avijit; Ray, Paresh Chandra

2016-12-20

Surface-enhanced Raman spectroscopy (SERS) fingerprinting is highly promising for identifying disease markers from complex mixtures of clinical sample, which has the capability to take medical diagnoses to the next level. Although vibrational frequency in Raman spectra is unique for each biomolecule, which can be used as fingerprint identification, it has not been considered to be used routinely for biosensing due to the fact that the Raman signal is very weak. Contemporary SERS has been demonstrated to be an excellent analytical tool for practical label-free sensing applications due its ability to enhance Raman signals by factors of up to 10 8 -10 14 orders of magnitude. Although SERS was discovered more than 40 years ago, its applications are still rare outside the spectroscopy community and it is mainly due to the fact that how to control, manipulate and amplify light on the "hot spots" near the metal surface is in the infancy stage. In this Account, we describe our contribution to develop nanoachitecture based highly reproducible and ultrasensitive detection capability SERS platform via low-cost synthetic routes. Using one-dimensional (1D) carbon nanotube (CNT), two-dimensional (2D) graphene oxide (GO), and zero-dimensional (0D) plasmonic nanoparticle, 0D to 3D SERS substrates have been designed, which represent highly powerful platform for biological diagnosis. We discuss the major design criteria we have used to develop robust SERS substrate to possess high density "hot spots" with very good reproducibility. SERS enhancement factor for 3D SERS substrate is about 5 orders of magnitude higher than only plasmonic nanoparticle and more than 9 orders of magnitude higher than 2D GO. Theoretical finite-difference time-domain (FDTD) stimulation data show that the electric field enhancement |E| 2 can be more than 2 orders of magnitude in "hot spots", which suggests that SERS enhancement factors can be greater than 10 4 due to the formation of high density "hot spots" in 3D substrate. Next, we discuss the utilization of nanoachitecture based SERS substrate for ultrasensitive and selective diagnosis of infectious disease organisms such as drug resistance bacteria and mosquito-borne flavi-viruses that cause significant health problems worldwide. SERS based "whole-organism fingerprints" has been used to identify infectious disease organisms even when they are so closely related that they are difficult to distinguish. The detection capability can be as low as 10 CFU/mL for methicillin-resistant Staphylococcus aureus (MRSA) and 10 PFU/mL for Dengue virus (DENV) and West Nile virus (WNV). After that, we introduce exciting research findings by our group on the applications of nanoachitecture based SERS substrate for the capture and fingerprint detection of rotavirus from water and Alzheimer's disease biomarkers from whole blood sample. The SERS detection limit for β-amyloid (Aβ proteins) and tau protein using 3D SERS platform is several orders of magnitude higher than the currently used technology in clinics. Finally, we highlight the promises, major challenges and prospect of nanoachitecture based SERS in biomedical diagnosis field.

Nanoarchitecture Based SERS for Biomolecular Fingerprinting and Label-Free Disease Markers Diagnosis

PubMed Central

2016-01-01

Conspectus Surface-enhanced Raman spectroscopy (SERS) fingerprinting is highly promising for identifying disease markers from complex mixtures of clinical sample, which has the capability to take medical diagnoses to the next level. Although vibrational frequency in Raman spectra is unique for each biomolecule, which can be used as fingerprint identification, it has not been considered to be used routinely for biosensing due to the fact that the Raman signal is very weak. Contemporary SERS has been demonstrated to be an excellent analytical tool for practical label-free sensing applications due its ability to enhance Raman signals by factors of up to 108–1014 orders of magnitude. Although SERS was discovered more than 40 years ago, its applications are still rare outside the spectroscopy community and it is mainly due to the fact that how to control, manipulate and amplify light on the “hot spots” near the metal surface is in the infancy stage. In this Account, we describe our contribution to develop nanoachitecture based highly reproducible and ultrasensitive detection capability SERS platform via low-cost synthetic routes. Using one-dimensional (1D) carbon nanotube (CNT), two-dimensional (2D) graphene oxide (GO), and zero-dimensional (0D) plasmonic nanoparticle, 0D to 3D SERS substrates have been designed, which represent highly powerful platform for biological diagnosis. We discuss the major design criteria we have used to develop robust SERS substrate to possess high density “hot spots” with very good reproducibility. SERS enhancement factor for 3D SERS substrate is about 5 orders of magnitude higher than only plasmonic nanoparticle and more than 9 orders of magnitude higher than 2D GO. Theoretical finite-difference time-domain (FDTD) stimulation data show that the electric field enhancement |E|2 can be more than 2 orders of magnitude in “hot spots”, which suggests that SERS enhancement factors can be greater than 104 due to the formation of high density “hot spots” in 3D substrate. Next, we discuss the utilization of nanoachitecture based SERS substrate for ultrasensitive and selective diagnosis of infectious disease organisms such as drug resistance bacteria and mosquito-borne flavi-viruses that cause significant health problems worldwide. SERS based “whole-organism fingerprints” has been used to identify infectious disease organisms even when they are so closely related that they are difficult to distinguish. The detection capability can be as low as 10 CFU/mL for methicillin-resistant Staphylococcus aureus (MRSA) and 10 PFU/mL for Dengue virus (DENV) and West Nile virus (WNV). After that, we introduce exciting research findings by our group on the applications of nanoachitecture based SERS substrate for the capture and fingerprint detection of rotavirus from water and Alzheimer’s disease biomarkers from whole blood sample. The SERS detection limit for β-amyloid (Aβ proteins) and tau protein using 3D SERS platform is several orders of magnitude higher than the currently used technology in clinics. Finally, we highlight the promises, major challenges and prospect of nanoachitecture based SERS in biomedical diagnosis field. PMID:27993003

Numerical study on the mechanisms of the SERS of gold-coated pyramidal tip substrates.

PubMed

Li, Rui; Wang, Qiao; Li, Hong; Liu, Kun; Pan, Shi; Zhan, Weishen; Chen, Maodu

2016-06-29

In this paper, the physical enhancement mechanisms of the surface-enhanced Raman scattering (SERS) of pyramidal tip substrates are studied theoretically. We structure the periodic square-based arrays of adjacent nanometer pyramidal gold-coated tips on silicon. In order to determine the contribution of plasmonic or diffraction effects on the SERS, three-dimensional (3D) numerical simulations are implemented by taking into account the substrate coated with a gold thin film or a perfect electrical conductor thin film. The tip distance, metal coating thickness and incident light polarization angle are also optimized to investigate whether the further SERS signal can be enhanced.

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.

Reproducible and recyclable SERS substrates: Flower-like Ag structures with concave surfaces formed by electrodeposition

NASA Astrophysics Data System (ADS)

Bian, Juncao; Shu, Shiwei; Li, Jianfu; Huang, Chao; Li, Yang Yang; Zhang, Rui-Qin

2015-04-01

Direct synthesis of three-dimensional Ag structures on solid substrates for the purposes of producing reproducible and recyclable surface-enhanced Raman scattering (SERS) applications remains challenging. In this work, flower-like Ag structures with concave surfaces (FACS) were successfully electrodeposited onto ITO glass using the double-potentiostatic method. The FACS, with an enhancement factor of the order of 108, exhibited a SERS signal intensity 3.3 times stronger than that measured from Ag nanostructures without concave surfaces. A cleaning procedure involving lengthy immersion of the sample in ethanol and KNO3 was proposed to recycle the substrate and confirmed by using rhodamine 6G, adenine, and 4-aminothiophenol as target molecules. The findings can help to advance the practical applications of Ag nanostructure-based SERS substrates.

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.

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.

1998-07-21

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.

High-performance SERS substrate based on hybrid structure of graphene oxide/AgNPs/Cu film@pyramid Si

NASA Astrophysics Data System (ADS)

Li, Zhe; Xu, Shi Cai; Zhang, Chao; Liu, Xiao Yun; Gao, Sai Sai; Hu, Li Tao; Guo, Jia; Ma, Yong; Jiang, Shou Zhen; Si, Hai Peng

2016-12-01

We present a novel surface-enhanced Raman scattering (SERS) substrate based on graphene oxide/silver nanoparticles/copper film covered silicon pyramid arrays (GO/AgNPs/PCu@Si) by a low-cost and simple method. The GO/AgNPs/PCu@Si substrate presents high sensitivity, good homogeneity and well stability with R6G molecules as a probe. The detected concentration of Rhodamine 6 G (R6G) is as low as 10-15 M. These sensitive SERS behaviors are also confirmed in theory via a commercial COMSOL software, the electric field enhancement is not only formed between the AgNPs, but also formed between the AgNPs and Cu film. And the GO/AgNPs/PCu@Si substrates also present good property on practical application for the detection of methylene blue (MB) and crystal violet (CV). This work may offer a novel and practical method to facilitate the SERS applications in areas of medicine, food safety and biotechnology.

High-performance SERS substrate based on hybrid structure of graphene oxide/AgNPs/Cu film@pyramid Si.

PubMed

Li, Zhe; Xu, Shi Cai; Zhang, Chao; Liu, Xiao Yun; Gao, Sai Sai; Hu, Li Tao; Guo, Jia; Ma, Yong; Jiang, Shou Zhen; Si, Hai Peng

2016-12-07

We present a novel surface-enhanced Raman scattering (SERS) substrate based on graphene oxide/silver nanoparticles/copper film covered silicon pyramid arrays (GO/AgNPs/PCu@Si) by a low-cost and simple method. The GO/AgNPs/PCu@Si substrate presents high sensitivity, good homogeneity and well stability with R6G molecules as a probe. The detected concentration of Rhodamine 6 G (R6G) is as low as 10 -15 M. These sensitive SERS behaviors are also confirmed in theory via a commercial COMSOL software, the electric field enhancement is not only formed between the AgNPs, but also formed between the AgNPs and Cu film. And the GO/AgNPs/PCu@Si substrates also present good property on practical application for the detection of methylene blue (MB) and crystal violet (CV). This work may offer a novel and practical method to facilitate the SERS applications in areas of medicine, food safety and biotechnology.

High-performance SERS substrate based on hybrid structure of graphene oxide/AgNPs/Cu film@pyramid Si

PubMed Central

Li, Zhe; Xu, Shi Cai; Zhang, Chao; Liu, Xiao Yun; Gao, Sai Sai; Hu, Li Tao; Guo, Jia; Ma, Yong; Jiang, Shou Zhen; Si, Hai Peng

2016-01-01

We present a novel surface-enhanced Raman scattering (SERS) substrate based on graphene oxide/silver nanoparticles/copper film covered silicon pyramid arrays (GO/AgNPs/PCu@Si) by a low-cost and simple method. The GO/AgNPs/PCu@Si substrate presents high sensitivity, good homogeneity and well stability with R6G molecules as a probe. The detected concentration of Rhodamine 6 G (R6G) is as low as 10−15 M. These sensitive SERS behaviors are also confirmed in theory via a commercial COMSOL software, the electric field enhancement is not only formed between the AgNPs, but also formed between the AgNPs and Cu film. And the GO/AgNPs/PCu@Si substrates also present good property on practical application for the detection of methylene blue (MB) and crystal violet (CV). This work may offer a novel and practical method to facilitate the SERS applications in areas of medicine, food safety and biotechnology. PMID:27924863

Progress in the Development of SERS-Active Substrates Based on Metal-Coated Porous Silicon

PubMed Central

Girel, Kseniya V.; Panarin, Andrei; Terekhov, Sergei N.

2018-01-01

The present work gives an overview of the developments in surface-enhanced Raman scattering (SERS) with metal-coated porous silicon used as an active substrate. We focused this review on the research referenced to SERS-active materials based on porous silicon, beginning from the patent application in 2002 and enclosing the studies of this year. Porous silicon and metal deposition technologies are discussed. Since the earliest studies, a number of fundamentally different plasmonic nanostructures including metallic dendrites, quasi-ordered arrays of metallic nanoparticles (NPs), and metallic nanovoids have been grown on porous silicon, defined by the morphology of this host material. SERS-active substrates based on porous silicon have been found to combine a high and well-reproducible signal level, storage stability, cost-effective technology and handy use. They make it possible to identify and study many compounds including biomolecules with a detection limit varying from milli- to femtomolar concentrations. The progress reviewed here demonstrates the great prospects for the extensive use of the metal-coated porous silicon for bioanalysis by SERS-spectroscopy. PMID:29883382

Progress in the Development of SERS-Active Substrates Based on Metal-Coated Porous Silicon.

PubMed

Bandarenka, Hanna V; Girel, Kseniya V; Zavatski, Sergey A; Panarin, Andrei; Terekhov, Sergei N

2018-05-21

The present work gives an overview of the developments in surface-enhanced Raman scattering (SERS) with metal-coated porous silicon used as an active substrate. We focused this review on the research referenced to SERS-active materials based on porous silicon, beginning from the patent application in 2002 and enclosing the studies of this year. Porous silicon and metal deposition technologies are discussed. Since the earliest studies, a number of fundamentally different plasmonic nanostructures including metallic dendrites, quasi-ordered arrays of metallic nanoparticles (NPs), and metallic nanovoids have been grown on porous silicon, defined by the morphology of this host material. SERS-active substrates based on porous silicon have been found to combine a high and well-reproducible signal level, storage stability, cost-effective technology and handy use. They make it possible to identify and study many compounds including biomolecules with a detection limit varying from milli- to femtomolar concentrations. The progress reviewed here demonstrates the great prospects for the extensive use of the metal-coated porous silicon for bioanalysis by SERS-spectroscopy.

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.

Performance-Enhancing Methods for Au Film over Nanosphere Surface-Enhanced Raman Scattering Substrate and Melamine Detection Application

PubMed Central

Wang, Jun Feng; Wu, Xue Zhong; Xiao, Rui; Dong, Pei Tao; Wang, Chao Guang

2014-01-01

A new high-performance surface-enhanced Raman scattering (SERS) substrate with extremely high SERS activity was produced. This SERS substrate combines the advantages of Au film over nanosphere (AuFON) substrate and Ag nanoparticles (AgNPs). A three order enhancement of SERS was observed when Rhodamine 6G (R6G) was used as a probe molecule to compare the SERS effects of the new substrate and commonly used AuFON substrate. These new SERS substrates can detect R6G down to 1 nM. The new substrate was also utilized to detect melamine, and the limit of detection (LOD) is 1 ppb. A linear relationship was also observed between the SERS intensity at Raman peak 682 cm−1 and the logarithm of melamine concentrations ranging from 10 ppm to 1 ppb. This ultrasensitive SERS substrate is a promising tool for detecting trace chemical molecules because of its simple and effective fabrication procedure, high sensitivity and high reproducibility of the SERS effect. PMID:24886913

Performance-enhancing methods for Au film over nanosphere surface-enhanced Raman scattering substrate and melamine detection application.

PubMed

Wang, Jun Feng; Wu, Xue Zhong; Xiao, Rui; Dong, Pei Tao; Wang, Chao Guang

2014-01-01

A new high-performance surface-enhanced Raman scattering (SERS) substrate with extremely high SERS activity was produced. This SERS substrate combines the advantages of Au film over nanosphere (AuFON) substrate and Ag nanoparticles (AgNPs). A three order enhancement of SERS was observed when Rhodamine 6G (R6G) was used as a probe molecule to compare the SERS effects of the new substrate and commonly used AuFON substrate. These new SERS substrates can detect R6G down to 1 nM. The new substrate was also utilized to detect melamine, and the limit of detection (LOD) is 1 ppb. A linear relationship was also observed between the SERS intensity at Raman peak 682 cm(-1) and the logarithm of melamine concentrations ranging from 10 ppm to 1 ppb. This ultrasensitive SERS substrate is a promising tool for detecting trace chemical molecules because of its simple and effective fabrication procedure, high sensitivity and high reproducibility of the SERS effect.

Plasmonic crystal based solid substrate for biomedical application of SERS

NASA Astrophysics Data System (ADS)

Morasso, Carlo F.; Mehn, Dora; Picciolini, Silvia; Vanna, Renzo; Bedoni, Marzia; Gramatica, Furio; Pellacani, Paola; Frangolho, Ana; Marchesini, Gerardo; Valsesia, Andrea

2014-02-01

Surface Enhanced Raman Spectroscopy is a powerful analytical technique that combines the excellent chemical specificity of Raman spectroscopy with the good sensitivity provided by the enhancement of the signal observed when a molecule is located on (or very close to) the surface of suitable nanostructured metallic materials. The availability of cheap, reliable and easy to use SERS substrates would pave the road to the development of bioanalytical tests that can be used in clinical practice. SERS, in fact, is expected to provide not only higher sensitivity and specificity, but also the simultaneous and markedly improved detection of several targets at the same time with higher speed compared to the conventional analytical methods. Here, we present the SERS activity of 2-D plasmonic crystals made by polymeric pillars embedded in a gold matrix obtained through the combination of soft-lithography and plasma deposition techniques on a transparent substrates. The use of a transparent support material allowed us to perform SERS detection from support side opening the possibility to use these substrates in combination with microfluidic devices. In order to demonstrate the potentialities for bioanalytical applications, we used our SERS active gold surface to detect the oxidation product of apomorphine, a well-known drug molecule used in Parkinson's disease which has been demonstrated being difficult to study by traditional HPLC based approaches.

Flexible and mechanical strain resistant large area SERS active substrates

NASA Astrophysics Data System (ADS)

Singh, J. P.; Chu, Hsiaoyun; Abell, Justin; Tripp, Ralph A.; Zhao, Yiping

2012-05-01

We report a cost effective and facile way to synthesize flexible, uniform, and large area surface enhanced Raman scattering (SERS) substrates using an oblique angle deposition (OAD) technique. The flexible SERS substrates consist of 1 μm long, tilted silver nanocolumnar films deposited on flexible polydimethylsiloxane (PDMS) and polyethylene terephthalate (PET) sheets using OAD. The SERS enhancement activity of these flexible substrates was determined using 10-5 M trans-1,2-bis(4-pyridyl) ethylene (BPE) Raman probe molecules. The in situ SERS measurements on these flexible substrates under mechanical (tensile/bending) strain conditions were performed. Our results show that flexible SERS substrates can withstand a tensile strain (ε) value as high as 30% without losing SERS performance, whereas the similar bending strain decreases the SERS performance by about 13%. A cyclic tensile loading test on flexible PDMS SERS substrates at a pre-specified tensile strain (ε) value of 10% shows that the SERS intensity remains almost constant for more than 100 cycles. These disposable and flexible SERS substrates can be integrated with biological substances and offer a novel and practical method to facilitate biosensing applications.

SERS substrates for in-situ biosensing (Conference Presentation)

NASA Astrophysics Data System (ADS)

Venugopalan, Priyamvada; Quilis, Nestor; Jakub, Dostalek; Wolfgang, Knoll

2017-06-01

Abstract: Recent years have seen a rapid progress in the field of surface-enhanced Raman spectroscopy (SERS) which is attributed to the thriving field of plasmonics [1]. SERS is a susceptible technique that can address basic scientific questions and technological problems. In both cases, it is highly dependent upon the plasmonic substrate, where excitation of the localized surface plasmon resonance enhances the vibrational scattering signal of the analyte molecules adsorbed on to the surface [2]. In this work, using finite difference time domain (FDTD) method we investigate the optical properties of plasmonic nanostructures with tuned plasmonic resonances as a function of dielectric environment and geometric parameters. An optimized geometry will be discussed based on the plasmonic resonant position and the SERS intensity. These SERS substrates will be employed for the detection of changes in conformation caused by interactions between an aptamer and analyte molecules. This will be done by using a microfluidic channel designed within the configuration of the lab-on-a-chip concept based on the intensity changes of the SERS signal. More efficient and reproducible results are obtained for such a quantitative measurement of analytes at low concentration levels. We will also demonstrate that the plasmonic substrates fabricated by top down approach such as e-beam lithography (EBL) and laser interference lithography (LIL) are highly reproducible, robust and can result in high electric field enhancement. Our results demonstrate the potential to use SERS substrates for highly sensitive detection schemes opening up the window for a wide range of applications including biomedical diagnostics, forensic investigation etc. Acknowledgement: This work was supported by the Austrian Science Fund (FWF), project NANOBIOSENSOR (I 2647). References: [1] J. N. Anker, W. P. Hall, O. Lyandres, N. C. Shah, J. Zhao and R. P. V. Duyne., " Biosensing with plasmonic nanosensors," Nature materials, 308(7), 2008. [2] T. Y. Jeon1, D. J. Kim, S. Park, S. Kim and D. Kim., "Nanostructured plasmonic substrates for use as SERS sensors," Nanocovergence, 3(18), 2016.

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

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.

Versatile gold based SERS substrates fabricated by ultrafast laser ablation for sensing picric acid and ammonium nitrate

NASA Astrophysics Data System (ADS)

Byram, Chandu; Moram, Sree Sathya Bharathi; Shaik, Abdul Kalam; Soma, Venugopal Rao

2017-10-01

We demonstrate the detection of picric acid (PA) and ammonium nitrate (AN) at μM concentrations by utilizing gold (Au) nanostructures (NSs) as surface enhanced Raman scattering (SERS) substrates fabricated using the technique of ultrafast laser ablation in liquids. Au NPs and NSs were also utilized for detecting Rhodamine 6G (Rh6G) and methylene blue (MB). Detection of all the molecules using the same substrates (NPs and NSs) demonstrated their versatility. Detection limits of 10-5, 10-6, 10-7, 10-8 M were achieved for AN, PA, Rh6G and MB, respectively. Reproducibility of the SERS intensity using NSs and NPs as substrates demonstrate their efficacy.

Fundamentals and applications of SERS-based bioanalytical sensing

NASA Astrophysics Data System (ADS)

Kahraman, Mehmet; Mullen, Emma R.; Korkmaz, Aysun; Wachsmann-Hogiu, Sebastian

2017-03-01

Plasmonics is an emerging field that examines the interaction between light and metallic nanostructures at the metal-dielectric interface. Surface-enhanced Raman scattering (SERS) is a powerful analytical technique that uses plasmonics to obtain detailed chemical information of molecules or molecular assemblies adsorbed or attached to nanostructured metallic surfaces. For bioanalytical applications, these surfaces are engineered to optimize for high enhancement factors and molecular specificity. In this review we focus on the fabrication of SERS substrates and their use for bioanalytical applications. We review the fundamental mechanisms of SERS and parameters governing SERS enhancement. We also discuss developments in the field of novel SERS substrates. This includes the use of different materials, sizes, shapes, and architectures to achieve high sensitivity and specificity as well as tunability or flexibility. Different fundamental approaches are discussed, such as label-free and functional assays. In addition, we highlight recent relevant advances for bioanalytical SERS applied to small molecules, proteins, DNA, and biologically relevant nanoparticles. Subsequently, we discuss the importance of data analysis and signal detection schemes to achieve smaller instruments with low cost for SERS-based point-of-care technology developments. Finally, we review the main advantages and challenges of SERS-based biosensing and provide a brief outlook.

A flexible and stable surface-enhanced Raman scattering (SERS) substrate based on Au nanoparticles/Graphene oxide/Cicada wing array

NASA Astrophysics Data System (ADS)

Shi, Guochao; Wang, Mingli; Zhu, Yanying; Shen, Lin; Wang, Yuhong; Ma, Wanli; Chen, Yuee; Li, Ruifeng

2018-04-01

In this work, we presented an eco-friendly and low-cost method to fabricate a kind of flexible and stable Au nanoparticles/graphene oxide/cicada wing (AuNPs/GO/CW) substrate. By controlling the ratio of reactants, the optimum SERS substrate with average AuNPs size of 65 nm was obtained. The Raman enhancement factor for rhodamine 6G (R6G) was 1.08 ×106 and the limit of detection (LOD) was as low as 10-8 M. After calibrating the Raman peak intensities of R6G, it could be quantitatively detected. In order to better understand the experimental results, the 3D finite-different time-domain simulation was used to simulate the AuNPs/GO/CW-1 (the diameter of the AuNPs was 65 nm) to further investigate the SERS enhancement effect. More importantly, the AuNPs/GO/CW-1 substrates not only can provide strong enhancement factors but also can be stable and reproducible. This SERS substrates owned a good stability for the SERS intensity which was reduced only by 25% after the aging time of 60 days and the relative standard deviation was lower than 20%, revealing excellent uniformity and reproducibility. Our positive findings can pave a new way to optimize the application of SERS substrate as well as provide more SERS platforms for quantitative detection of organic contaminants vestige, which makes it very promising in the trace detection of biological molecules.

Fabrication of a large-area, flexible micro-pyramid PET film SERS substrate and its application in the detection of dye in herbal tea

NASA Astrophysics Data System (ADS)

Liu, Xi; Huang, Meizhen; Chen, Jie; Kong, Lili; Wang, Keihui

2018-05-01

A simple method, based on a roll-to-roll ultraviolet micro-pyramid imprinting technique and a nanoparticle self-assembling process in aqueous solution, to fabricate a large-area, flexible surface-enhanced Raman scattering (SERS) polyethylene glycol terephthalate substrate is proposed. The SERS substrate is demonstrated to be of high sensitivity. The detection concentration of Rhodamine 6G (R6G) measured by a portable Raman spectrometer is down to 10-9 mol l-1. The relative standard deviation values of different spots and different substrates are less than 13%. In addition, the feasibility for rapid detection of dye in herbal tea based on this SERS substrate and a portable Raman spectrometer is investigated. Three industrial dyes are employed to simulate the dyeing process. It is presented that R6G of 4.8× {{10}-7} g ml-1, malachite green of 10-6 g ml-1 and Auramine O of 10-6 g ml-1 in herbal tea could be detected rapidly. The experimental results imply that this method could be potentially applied in the field of dyed herbal tea detection.

Use of Single-Layer g-C3N4/Ag Hybrids for Surface-Enhanced Raman Scattering (SERS)

PubMed Central

Jiang, Jizhou; Zou, Jing; Wee, Andrew Thye Shen; Zhang, Wenjing

2016-01-01

Surface-enhanced Raman scattering (SERS) substrates with high activity and stability are desirable for SERS sensing. Here, we report a new single atomic layer graphitic-C3N4 (S-g-C3N4) and Ag nanoparticles (NPs) hybrid as high-performance SERS substrates. The SERS mechanism of the highly stable S-g-C3N4/Ag substrates was systematically investigated by a combination of experiments and theoretical calculations. From the results of XPS and Raman spectroscopies, it was found that there was a strong interaction between S-g-C3N4 and Ag NPs, which facilitates the uniform distribution of Ag NPs over the edges and surfaces of S-g-C3N4 nanosheets, and induces a charge transfer from S-g-C3N4 to the oxidizing agent through the silver surface, ultimately protecting Ag NPs from oxidation. Based on the theoretical calculations, we found that the net surface charge of the Ag atoms on the S-g-C3N4/Ag substrates was positive and the Ag NPs presented high dispersibility, suggesting that the Ag atoms on the S-g-C3N4/Ag substrates were not likely to be oxidized, thereby ensuring the high stability of the S-g-C3N4/Ag substrate. An understanding of the stability mechanism in this system can be helpful for developing other effective SERS substrates with long-term stability. PMID:27687573

Inkjet Printed Surface Enhanced Raman Spectroscopy Array on Cellulose Paper

PubMed Central

Yu, Wei W.; White, Ian M.

2011-01-01

A novel, ultra low-cost surface enhanced Raman spectroscopy (SERS) substrate has been developed by modifying the surface chemistry of cellulose paper and patterning nanoparticle arrays, all with a consumer inkjet printer. Micro/nanofabrication of SERS substrates for on-chip chemical and biomolecular analysis has been under intense investigation. However, the high cost of producing these substrates and the limited shelf life severely limit their use, especially for routine laboratory analysis and for point-of-sample analysis in the field. Paper-based microfluidic biosensing systems have shown great potential as low-cost disposable analysis tools. In this work, this concept is extended to SERS-based detection. Using an inexpensive consumer inkjet printer, cellulose paper substrates are modified to be hydrophobic in the sensing regions. Synthesized silver nanoparticles are printed onto this hydrophobic paper substrate with microscale precision to form sensing arrays. The hydrophobic surface prevents the aqueous sample from spreading throughout the paper and thus concentrates the analyte within the sensing region. A SERS fingerprint signal for Rhodamine 6G dye was observed for samples with as low as 10 femtomoles of analyte in a total sample volume of 1 μL. This extraordinarily simple technique can be used to construct SERS microarrays immediately before sample analysis, enabling ultra low-cost chemical and biomolecular detection in the lab as well as in the field at the point of sample collection. PMID:21058689

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.

Superhydrophobic SERS substrates based on silicon hierarchical nanostructures

NASA Astrophysics Data System (ADS)

Chen, Xuexian; Wen, Jinxiu; Zhou, Jianhua; Zheng, Zebo; An, Di; Wang, Hao; Xie, Weiguang; Zhan, Runze; Xu, Ningsheng; Chen, Jun; She, Juncong; Chen, Huanjun; Deng, Shaozhi

2018-02-01

Silicon nanostructures have been cultivated as promising surface enhanced Raman scattering (SERS) substrates in terms of their low-loss optical resonance modes, facile functionalization, and compatibility with today’s state-of-the-art CMOS techniques. However, unlike their plasmonic counterparts, the electromagnetic field enhancements induced by silicon nanostructures are relatively small, which restrict their SERS sensing limit to around 10-7 M. To tackle this problem, we propose here a strategy for improving the SERS performance of silicon nanostructures by constructing silicon hierarchical nanostructures with a superhydrophobic surface. The hierarchical nanostructures are binary structures consisted of silicon nanowires (NWs) grown on micropyramids (MPs). After being modified with perfluorooctyltriethoxysilane (PFOT), the nanostructure surface shows a stable superhydrophobicity with a high contact angle of ˜160°. The substrate can allow for concentrating diluted analyte solutions into a specific area during the evaporation of the liquid droplet, whereby the analytes are aggregated into a small volume and can be easily detected by the silicon nanostructure SERS substrate. The analyte molecules (methylene blue: MB) enriched from an aqueous solution lower than 10-8 M can be readily detected. Such a detection limit is ˜100-fold lower than the conventional SERS substrates made of silicon nanostructures. Additionally, the detection limit can be further improved by functionalizing gold nanoparticles onto silicon hierarchical nanostructures, whereby the superhydrophobic characteristics and plasmonic field enhancements can be combined synergistically to give a detection limit down to ˜10-11 M. A gold nanoparticle-functionalized superhydrophobic substrate was employed to detect the spiked melamine in liquid milk. The results showed that the detection limit can be as low as 10-5 M, highlighting the potential of the proposed superhydrophobic SERS substrate in practical food safety inspection applications.

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.

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.

Crystal structure of the NADP+ and tartrate-bound complex of L-serine 3-dehydrogenase from the hyperthermophilic archaeon Pyrobaculum calidifontis.

PubMed

Yoneda, Kazunari; Sakuraba, Haruhiko; Araki, Tomohiro; Ohshima, Toshihisa

2018-05-01

A gene encoding L-serine dehydrogenase (L-SerDH) that exhibits extremely low sequence identity to the Agrobacterium tumefaciens L-SerDH was identified in the hyperthermophilic archaeon Pyrobaculum calidifontis. The predicted amino acid sequence showed 36% identity with that of Pseudomonas aeruginosa L-SerDH, suggesting that P. calidifontis L-SerDH is a novel type of L-SerDH, like Ps. aeruginosa L-SerDH. The overexpressed enzyme appears to be the most thermostable L-SerDH described to date, and no loss of activity was observed by incubation for 30 min at temperatures up to 100 °C. The enzyme showed substantial reactivity towards D-serine, in addition to L-serine. Two different crystal structures of P. calidifontis L-SerDH were determined using the Se-MAD and MR method: the structure in complex with NADP + /sulfate ion at 1.18 Å and the structure in complex with NADP + /L-tartrate (substrate analog) at 1.57 Å. The fold of the catalytic domain showed similarity with that of Ps. aeruginosa L-SerDH. However, the active site structure significantly differed between the two enzymes. Based on the structure of the tartrate, L- and D-serine and 3-hydroxypropionate molecules were modeled into the active site and the substrate binding modes were estimated. A structural comparison suggests that the wide cavity at the substrate binding site is likely responsible for the high reactivity of the enzyme toward both L- and D-serine enantiomers. This is the first description of the structure of the novel type of L-SerDH with bound NADP + and substrate analog, and it provides new insight into the substrate binding mechanism of L-SerDH. The results obtained here may be very informative for the creation of L- or D-serine-specific SerDH by protein engineering.

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

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

Continuous fabrication of nanostructure arrays for flexible surface enhanced Raman scattering substrate

PubMed Central

Zhang, Chengpeng; Yi, Peiyun; Peng, Linfa; Lai, Xinmin; Chen, Jie; Huang, Meizhen; Ni, Jun

2017-01-01

Surface-enhanced Raman spectroscopy (SERS) has been a powerful tool for applications including single molecule detection, analytical chemistry, electrochemistry, medical diagnostics and bio-sensing. Especially, flexible SERS substrates are highly desirable for daily-life applications, such as real-time and in situ Raman detection of chemical and biological targets, which can be used onto irregular surfaces. However, it is still a major challenge to fabricate the flexible SERS substrate on large-area substrates using a facile and cost-effective technique. The roll-to-roll ultraviolet nanoimprint lithography (R2R UV-NIL) technique provides a solution for the continuous fabrication of flexible SERS substrate due to its high-speed, large-area, high-resolution and high-throughput. In this paper, we presented a facile and cost-effective method to fabricate flexible SERS substrate including the fabrication of polymer nanostructure arrays and the metallization of the polymer nanostructure arrays. The polymer nanostructure arrays were obtained by using R2R UV-NIL technique and anodic aluminum oxide (AAO) mold. The functional SERS substrates were then obtained with Au sputtering on the surface of the polymer nanostructure arrays. The obtained SERS substrates exhibit excellent SERS and flexibility performance. This research can provide a beneficial direction for the continuous production of the flexible SERS substrates. PMID:28051175

An improved method to unravel phosphoacceptors in Ser/Thr protein kinase-phosphorylated substrates.

PubMed

Molle, Virginie; Leiba, Jade; Zanella-Cléon, Isabelle; Becchi, Michel; Kremer, Laurent

2010-11-01

Identification of the phosphorylated residues of bacterial Ser/Thr protein kinase (STPK) substrates still represents a challenging task. Herein, we present a new strategy allowing the rapid determination of phosphoacceptors in kinase substrates, essentially based on the dual expression of the kinase with its substrate in the surrogate E. coli, followed by MS analysis in a single-step procedure. The performance of this strategy is illustrated using two distinct proteins from Mycobacterium tuberculosis as model substrates, the GroEL2 and HspX chaperones. A comparative analysis with a standard method that includes mass spectrometry analysis of in vitro phosphorylated substrates is also addressed.

Efficient Surface Enhanced Raman Scattering substrates from femtosecond laser based fabrication

NASA Astrophysics Data System (ADS)

Parmar, Vinod; Kanaujia, Pawan K.; Bommali, Ravi Kumar; Vijaya Prakash, G.

2017-10-01

A fast and simple femtosecond laser based methodology for efficient Surface Enhanced Raman Scattering (SERS) substrate fabrication has been proposed. Both nano scaffold silicon (black silicon) and gold nanoparticles (Au-NP) are fabricated by femtosecond laser based technique for mass production. Nano rough silicon scaffold enables large electromagnetic fields for the localized surface plasmons from decorated metallic nanoparticles. Thus giant enhancement (approximately in the order of 104) of Raman signal arises from the mixed effects of electron-photon-phonon coupling, even at nanomolar concentrations of test organic species (Rhodamine 6G). Proposed process demonstrates the low-cost and label-less application ability from these large-area SERS substrates.

A wide range optical pH sensor for living cells using Au@Ag nanoparticles functionalized carbon nanotubes based on SERS signals.

PubMed

Chen, Peng; Wang, Zhuyuan; Zong, Shenfei; Chen, Hui; Zhu, Dan; Zhong, Yuan; Cui, Yiping

2014-10-01

p-Aminothiophenol (pATP) functionalized multi-walled carbon nanotubes (MWCNTs) have been demonstrated as an efficient pH sensor for living cells. The proposed sensor employs gold/silver core-shell nanoparticles (Au@Ag NPs) functionalized MWCNTs hybrid structure as the surface-enhanced Raman scattering (SERS) substrate and pATP molecules as the SERS reporters, which possess a pH-dependent SERS performance. By using MWCNTs as the substrate to be in a state of aggregation, the pH sensing range could be extended to pH 3.0∼14.0, which is much wider than that using unaggregated Au@Ag NPs without MWCNTs. Furthermore, the pH-sensitive performance was well retained in living cells with a low cytotoxicity. The developed SERS-active MWCNTs-based nanocomposite is expected to be an efficient intracellular pH sensor for bio-applications.

Material optimization of multi-layered enhanced nanostructures

NASA Astrophysics Data System (ADS)

Strobbia, Pietro

The employment of surface enhanced Raman scattering (SERS)-based sensing in real-world scenarios will offer numerous advantages over current optical sensors. Examples of these advantages are the intrinsic and simultaneous detection of multiple analytes, among many others. To achieve such a goal, SERS substrates with throughput and reproducibility comparable to commonly used fluorescence sensors have to be developed. To this end, our lab has discovered a multi-layer geometry, based on alternating films of a metal and a dielectric, that amplifies the SERS signal (multi-layer enhancement). The advantage of these multi-layered structures is to amplify the SERS signal exploiting layer-to-layer interactions in the volume of the structures, rather than on its surface. This strategy permits an amplification of the signal without modifying the surface characteristics of a substrate, and therefore conserving its reproducibility. Multi-layered structures can therefore be used to amplify the sensitivity and throughput of potentially any previously developed SERS sensor. In this thesis, these multi-layered structures were optimized and applied to different SERS substrates. The role of the dielectric spacer layer in the multi-layer enhancement was elucidated by fabricating spacers with different characteristics and studying their effect on the overall enhancement. Thickness, surface coverage and physical properties of the spacer were studied. Additionally, the multi-layered structures were applied to commercial SERS substrates and to isolated SERS probes. Studies on the dependence of the multi-layer enhancement on the thickness of the spacer demonstrated that the enhancement increases as a function of surface coverage at sub-monolayer thicknesses, due to the increasing multi-layer nature of the substrates. For fully coalescent spacers the enhancement decreases as a function of thickness, due to the loss of interaction between proximal metallic films. The influence of the physical properties of the spacer on the multi-layer enhancement were also studied. The trends in Schottky barrier height, interfacial potential and dielectric constant were isolated by using different materials as spacers (i.e., TiO2, HfO2, Ag 2O and Al2O3). The results show that the bulk dielectric constant of the material can be used to predict the relative magnitude of the multi-layer enhancement, with low dielectric constant materials performing more efficiently as spacers. Optimal spacer layers were found to be ultrathin coalescent films (ideally a monolayer) of low dielectric constant materials. Finally, multi-layered structures were observed to be employable to amplify SERS in drastically different substrate geometries. The multi-layered structures were applied to disposable commercial SERS substrates (i.e., Klarite). This project involved the regeneration of the used substrates, by stripping and redepositing the gold coating layer, and their amplification, by using the multi-layer geometry. The latter was observed to amplify the sensitivity of the substrates. Additionally, the multi-layered structures were applied to probes dispersed in solution. Such probes were observed to yield stronger SERS signal when optically trapped and to reduce the background signal. The application of the multi-layered structures on trapped probes, not only further amplified the SERS signal, but also increased the maximum number of applicable layers for the structures.

Flexible, transparent and highly sensitive SERS substrates with cross-nanoporous structures for fast on-site detection.

PubMed

Wang, Yingcheng; Jin, Yuanhao; Xiao, Xiaoyang; Zhang, Tianfu; Yang, Haitao; Zhao, Yudan; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Li, Qunqing

2018-05-30

A flexible and transparent film assembled from the cross-nanoporous structures of Au on PET (CNS of Au@PET) is developed as a versatile and effective SERS substrate for rapid, on-site trace analysis with high sensitivity. The fabrication of the CNS of Au can be achieved on a large scale at low cost by employing an etching process with super-aligned carbon nanotubes as a mask, followed by metal deposition. A strongly enhanced Raman signal with good uniformity can be obtained, which is attributed to the excitation of "hot spots" around the metal nanogaps and sharp edges. Using the CNS of Au@PET film as a SERS platform, real-time and on-site SERS detection of the food contaminant crystal violet (CV) is achieved, with a detection limit of CV solution on a tomato skin of 10-7 M. Owing to its ability to efficiently extract trace analytes, the resulting substrate also achieves detection of 4-ATP contaminants and thiram pesticides by swabbing the skin of an apple. A SERS detection signal for 4-ATP has a relative standard deviation of less than 10%, revealing the excellent reproducibility of the substrate. The flexible, transparent and highly sensitive substrates fabricated using this simple and cost-effective strategy are promising for practical application in rapid, on-site SERS-based detection.

A high-performance and low cost SERS substrate of plasmonic nanopillars on plastic film fabricated by nanoimprint lithography with AAO template

NASA Astrophysics Data System (ADS)

Liu, Long; Zhang, Qian; Lu, Yuanshen; Du, Wei; Li, Bin; Cui, Yushuang; Yuan, Changsheng; Zhan, Peng; Ge, Haixiong; Wang, Zhenling; Chen, Yanfeng

2017-06-01

As a powerful spectroscopy technique, surface-enhanced Raman scattering (SERS) can provide non-destructive and sensitive characterization down to a single molecular level. Aiming to the main challenges of high-performance SERS-active substrates for their real-world applications involving the ultra-sensitive and reproducible signals detection and signal uniformity with large-area, herein, a facile and reliable strategy based on combination of thermal imprinting polycarbonate (PC) film with porous anodic aluminum oxide (AAO) mold and E-beam evaporation of gold is provided to fabricate a high-quality SERS-active substrate consisting of ultra-dense hot-spots with large-area uniformity. Two kinds of sub-10 nm gaps were obtained, including the nanogaps between the neighboring gold coated PC-nanopillars and those between gold on the top of the nanopillars and that on the base, which actually build up a three-dimensional (3D) hot-spot network for high-performance SERS detection. The effect of structural parameters on SERS enhancement was investigated numerically and experimentally, and by optimizing the structural parameters, a remarkable average SERS enhancement factor up to of 1.4×108 is achieved and it shows an excellent reproducibility with a relative standard deviation of 18%, which allows for enhanced practicability in the application of quantitative biochemical detection.

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.

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.

Highly sensitive, reproducible and stable SERS substrate based on reduced graphene oxide/silver nanoparticles coated weighing paper

NASA Astrophysics Data System (ADS)

Xiao, Guina; Li, Yunxiang; Shi, Wangzhou; Shen, Leo; Chen, Qi; Huang, Lei

2017-05-01

Paper-based surface-enhanced Raman scattering (SERS) substrates receive a great deal of attention due to low cost and high flexibility. Herein, we developed an efficient SERS substrate by gravure printing of sulfonated reduced graphene-oxide (S-RGO) thin film and inkjet printing of silver nanoparticles (AgNPs) on weighing paper successively. Malachite green (MG) and rhodamine 6G (R6G) were chosen as probe molecules to evaluate the enhanced performance of the fabricated SERS-active substrates. It was found that the S-RGO/AgNPs composite structure possessed higher enhancement ability than the pure AgNPs. The Raman enhancement factor of S-RGO/AgNPs was calculated to be as large as 109. The minimum detection limit for MG and R6G was down to 10-7 M with good linear responses (R2 = 0.9996, 0.9983) range from 10-4 M to 10-7 M. In addition, the S-RGO/AgNPs exhibited good uniformity with a relative standard deviation (RSD) of 7.90% measured by 572 points, excellent reproducibility with RSD smaller than 3.36%, and long-term stability with RSD less than 7.19%.

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.

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.

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

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.

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...

Phosphorylation of Parkin at Serine65 is essential for activation: elaboration of a Miro1 substrate-based assay of Parkin E3 ligase activity

PubMed Central

Kazlauskaite, Agne; Kelly, Van; Johnson, Clare; Baillie, Carla; Hastie, C. James; Peggie, Mark; Macartney, Thomas; Woodroof, Helen I.; Alessi, Dario R.; Pedrioli, Patrick G. A.; Muqit, Miratul M. K.

2014-01-01

Mutations in PINK1 and Parkin are associated with early-onset Parkinson's disease. We recently discovered that PINK1 phosphorylates Parkin at serine65 (Ser65) within its Ubl domain, leading to its activation in a substrate-free activity assay. We now demonstrate the critical requirement of Ser65 phosphorylation for substrate ubiquitylation through elaboration of a novel in vitro E3 ligase activity assay using full-length untagged Parkin and its putative substrate, the mitochondrial GTPase Miro1. We observe that Parkin efficiently ubiquitylates Miro1 at highly conserved lysine residues, 153, 230, 235, 330 and 572, upon phosphorylation by PINK1. We have further established an E2-ubiquitin discharge assay to assess Parkin activity and observe robust discharge of ubiquitin-loaded UbcH7 E2 ligase upon phosphorylation of Parkin at Ser65 by wild-type, but not kinase-inactive PINK1 or a Parkin Ser65Ala mutant, suggesting a possible mechanism of how Ser65 phosphorylation may activate Parkin E3 ligase activity. For the first time, to the best of our knowledge, we report the effect of Parkin disease-associated mutations in substrate-based assays using full-length untagged recombinant Parkin. Our mutation analysis indicates an essential role for the catalytic cysteine Cys431 and reveals fundamental new knowledge on how mutations may confer pathogenicity via disruption of Miro1 ubiquitylation, free ubiquitin chain formation or by impacting Parkin's ability to discharge ubiquitin from a loaded E2. This study provides further evidence that phosphorylation of Parkin at Ser65 is critical for its activation. It also provides evidence that Miro1 is a direct Parkin substrate. The assays and reagents developed in this study will be important to uncover new insights into Parkin biology as well as aid in the development of screens to identify small molecule Parkin activators for the treatment of Parkinson's disease. PMID:24647965

Critical assessment of enhancement factor measurements in surface-enhanced Raman scattering on different substrates.

PubMed

Rodrigues, Daniel C; de Souza, Michele L; Souza, Klester S; dos Santos, Diego P; Andrade, Gustavo F S; Temperini, Marcia L A

2015-09-07

The SERS enhancement factor (SERS-EF) is one of the most important parameters that characterizes the ability of a given substrate to enhance the Raman signal for SERS applications. The comparison of SERS intensities and SERS-EF values across different substrates is a common practice to unravel the performance of a given substrate. In this study, it is shown that such a comparison may lack significance if we compare substrates of very distinct nature and optical properties. It is specifically shown that the SERS-EF values for static substrates (e.g. immobilized metallic nanostructures) cannot be compared to those of dynamic ones (e.g. colloidal metal nanoparticle solutions), and that the optical properties for the latter show strong dependence on the metal-molecule interaction dynamics. The most representative experimental results concerning the dynamic substrates have been supported by generalized Mie theory simulations, which are tools used to describe the substrate complexity and the microscopic information not usually taken into account.

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.

Ag-NP@Ge-nanotaper/Si-micropillar ordered arrays as ultrasensitive and uniform surface enhanced Raman scattering substrates

NASA Astrophysics Data System (ADS)

Liu, Jing; Meng, Guowen; Li, Zhongbo; Huang, Zhulin; Li, Xiangdong

2015-10-01

Surface-enhanced Raman scattering (SERS) is considered to be an excellent candidate for analytical detection schemes, because of its molecular specificity, rapid response and high sensitivity. Here, SERS-substrates of Ag-nanoparticle (Ag-NP) decorated Ge-nanotapers grafted on hexagonally ordered Si-micropillar (denoted as Ag-NP@Ge-nanotaper/Si-micropillar) arrays are fabricated via a combinatorial process of two-step etching to achieve hexagonal Si-micropillar arrays, chemical vapor deposition of flocky Ge-nanotapers on each Si-micropillar and decoration of Ag-NPs onto the Ge-nanotapers through galvanic displacement. With high density three-dimensional (3D) ``hot spots'' created from the large quantities of the neighboring Ag-NPs and large-scale uniform morphology, the hierarchical Ag-NP@Ge-nanotaper/Si-micropillar arrays exhibit strong and reproducible SERS activity. Using our hierarchical 3D SERS-substrates, both methyl parathion (a commonly used pesticide) and PCB-2 (one congener of highly toxic polychlorinated biphenyls) with concentrations down to 10-7 M and 10-5 M have been detected respectively, showing great potential in SERS-based rapid trace-level detection of toxic organic pollutants in the environment.Surface-enhanced Raman scattering (SERS) is considered to be an excellent candidate for analytical detection schemes, because of its molecular specificity, rapid response and high sensitivity. Here, SERS-substrates of Ag-nanoparticle (Ag-NP) decorated Ge-nanotapers grafted on hexagonally ordered Si-micropillar (denoted as Ag-NP@Ge-nanotaper/Si-micropillar) arrays are fabricated via a combinatorial process of two-step etching to achieve hexagonal Si-micropillar arrays, chemical vapor deposition of flocky Ge-nanotapers on each Si-micropillar and decoration of Ag-NPs onto the Ge-nanotapers through galvanic displacement. With high density three-dimensional (3D) ``hot spots'' created from the large quantities of the neighboring Ag-NPs and large-scale uniform morphology, the hierarchical Ag-NP@Ge-nanotaper/Si-micropillar arrays exhibit strong and reproducible SERS activity. Using our hierarchical 3D SERS-substrates, both methyl parathion (a commonly used pesticide) and PCB-2 (one congener of highly toxic polychlorinated biphenyls) with concentrations down to 10-7 M and 10-5 M have been detected respectively, showing great potential in SERS-based rapid trace-level detection of toxic organic pollutants in the environment. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06001j

Multidimensional Co3O4 nano sponge for the highly sensitive SERS applications

NASA Astrophysics Data System (ADS)

Zhao, Miao-miao; Liu, Wen-yao; Du, Jian-gong; Guo, Xu-dong; Wang, Lei; Xia, Mei-jing; Tang, Jun

2017-01-01

In this work, surface enhanced Raman spectroscopy (SERS) substrates with Ag nanoparticles (NPs) decorated Co3O4 nanowires (NWs) grafted on the three-dimensional (3D) network architecture of Ni foam (denoted as Ag-NP@Co3O4-NW/Ni-foam) arrays are manufactured. In the experiment, the hierarchical Ag-NP@Co3O4-NW/Ni-foam arrays exhibit strong SERS activity due to the higher density of the "hot spots" created from the large quantities of neighboring Ag NPs. Using this hierarchical 3D SERS substrates, the crystal violet (a banned drug of aquaculture) with concentration down to 10-14 mol/L can be detected, which shows potential application in SERS-based rapid trace-level detection of harmful food additives.

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.

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..

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.

Synergistic effects of semiconductor substrate and noble metal nano-particles on SERS effect both theoretical and experimental aspects

NASA Astrophysics Data System (ADS)

Yang, Chen; Liang, Pei; Tang, Lisha; Zhou, Yongfeng; Cao, Yanting; Wu, Yanxiong; Zhang, De; Dong, Qianmin; Huang, Jie; He, Peng

2018-04-01

As a means of chemical identification and analysis, Surface enhanced Raman spectroscopy (SERS), with the advantages of high sensitivity and selectivity, non-destructive, high repeatability and in situ detection etc., has important significance in the field of composition detection, environmental science, biological medicine etc. Physical model of coupling effect between different semiconductor substrates and noble metal particles were investigated by using 3D-FDTD method. Mechanism and the effects of excitation wavelength, particle spacing and semiconductor substrate types on the SERS effect were discussed. The results showed that the optimal excitation wavelengths of three noble metals of Ag, Au, Cu, were located at 510, 600 and 630 nm, respectively; SERS effect of Ag, Au, Cu increases with the decreasing of the inter distance of particles, while the distance of the NPs reaches the critical value of 3 nm, the strength of SERS effect will be greatly enhanced. For the four different types of substrate of Ge, Si, SiO2 (glass) and Al2O3, the SERS effect of Ag on SiO2 > Ge > Al2O3 > Si. For Au and Cu nanoparticles, the SERS effect of them on oxide substrate is stronger than that on non-oxide substrate. In order to verify FDTD simulations, taking silver nanoparticles as an example, and silver nanoparticles prepared by chemical method were spinning coating on the four different substrates with R6G as probe molecules. The results show that the experimental results are consistent with FDTD theoretical simulations, and the SERS enhancement effect of Ag-SiO2 substrate is best. The results of this study have important theoretical significance to explain the variations of SERS enhancement on different noble metals, which is also an important guide for the preparation of SERS substrates, especially for the microfluidics. The better Raman effect can be realized by choosing proper substrate type, particle spacing and excitation wavelength, result in expanding the depth and width of SERS application.

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.

Ag/SiO2 surface-enhanced Raman scattering substrate for plasticizer detection

NASA Astrophysics Data System (ADS)

Wu, Ming-Chung; Lin, Ming-Pin; Lin, Ting-Han; Su, Wei-Fang

2018-04-01

In this study, we demonstrated a simple method of fabricating a high-performance surface-enhanced Raman scattering (SERS) substrate. Monodispersive SiO2 colloidal spheres were self-assembled on a silicon wafer, and then a silver layer was coated on it to obtain a Ag/SiO2 SERS substrate. The Ag/SiO2 SERS substrates were used to detect three kinds of plasticizer with different concentrations, namely, including bis(2-ethylhexyl)phthalate (DEHP), benzyl butyl phthalate (BBP), and dibutyl phthalate (DBP). The enhancement of Raman scattering intensity caused by surface plasmon resonance can be observed using the Ag/SiO2 SERS substrates. The Ag/SiO2 SERS substrate with a 150-nm-thick silver layer can detect plasticizers, and it satisfies the detection limit of plasticizers at 100 ppm. The developed highly sensitive Ag/SiO2 SERS substrates show a potential for the design and fabrication of functional sensors to identify the harmful plasticizers that plastic products release in daily life.

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.

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.

Controlled fabrication of silver nanoneedles array for SERS and their application in rapid detection of narcotics

NASA Astrophysics Data System (ADS)

Yang, Yong; Li, Zhi-Yuan; Yamaguchi, Kohei; Tanemura, Masaki; Huang, Zhengren; Jiang, Dongliang; Chen, Yuhui; Zhou, Fei; Nogami, Masayuki

2012-03-01

Novel surface-enhanced Raman scattering (SERS) substrates with high SERS-activity are ideal for novel SERS sensors, detectors to detect illicitly sold narcotics and explosives. The key to the wider application of SERS technique is to develop plasmon resonant structure with novel geometries to enhance Raman signals and to control the periodic ordering of these structures over a large area to obtain reproducible Raman enhancement. In this work, a simple Ar+-ion sputtering route has been developed to fabricate silver nanoneedles arrays on silicon substrates for SERS-active substrates to detect trace-level illicitly sold narcotics. These silver nanoneedles possess a very sharp apex with an apex diameter of 15 nm and an apex angle of 20°. The SERS enhancement factor of greater than 1010 was reproducibly achieved by the well-aligned nanoneedles arrays. Furthermore, ketamine hydrochloride molecules, one kind of illicitly sold narcotics, can be detected down to 27 ppb by using our SERS substrate within 3 s, indicating the sensitivity of our SERS substrates for trace amounts of narcotics and that SERS technology can become an important analytical technique in forensic laboratories because it can provide a rapid and nondestructive method for trace detection.

Fabrication of novel plasmonics-active substrates

NASA Astrophysics Data System (ADS)

Dhawan, Anuj; Gerhold, Michael; Du, Yan; Misra, Veena; Vo-Dinh, Tuan

2009-02-01

This paper describes methodologies for fabricating of highly efficient plasmonics-active SERS substrates - having metallic nanowire structures with pointed geometries and sub-5 nm gap between the metallic nanowires enabling concentration of high EM fields in these regions - on a wafer-scale by a reproducible process that is compatible with large-scale development of these substrates. Excitation of surface plasmons in these nanowire structures leads to substantial enhancement in the Raman scattering signal obtained from molecules lying in the vicinity of the nanostructure surface. The methodologies employed included metallic coating of silicon nanowires fabricated by employing deep UV lithography as well as controlled growth of silicon germanium on silicon nanostructures to form diamond-shaped nanowire structures followed by metallic coating. These SERS substrates were employed for detecting chemical and biological molecules of interest. In order to characterize the SERS substrates developed in this work, we obtained SERS signals from molecules such as p-mercaptobenzoic acid (pMBA) and cresyl fast violet (CFV) attached to or adsorbed on the metal-coated SERS substrates. It was observed that both gold-coated triangular shaped nanowire substrates as well as gold-coated diamond shaped nanowire substrates provided very high SERS signals for the nanowires having sub-15 nm gaps and that the SERS signal depends on the closest spacing between the metal-coated silicon and silicon germanium nanowires. SERS substrates developed by the different processes were also employed for detection of biological molecules such as DPA (Dipicolinic Acid), an excellent marker for spores of bacteria such as Anthrax.

SERS substrates fabricated using ceramic filters for the detection of bacteria

NASA Astrophysics Data System (ADS)

Mosier-Boss, P. A.; Sorensen, K. C.; George, R. D.; Obraztsova, A.

2016-01-01

SERS substrates were fabricated by filtering either Ag or Au colloidal particles onto rigid, ceramic filters - onto which suspensions of bacteria were then filtered. SERS spectra of the bacteria were obtained using a Raman spectrometer that has an 'orbital raster scan' capability. It was shown that bacteria samples prepared in this manner were uniformly distributed onto the surface of the SERS substrate. The effect of common buffer systems on the SERS spectra was investigated and the utility of using the SERS technique for speciation of bacteria was explored.

Review of SERS Substrates for Chemical Sensing

PubMed Central

Mosier-Boss, Pamela A.

2017-01-01

The SERS effect was initially discovered in the 1970s. Early research focused on understanding the phenomenon and increasing enhancement to achieve single molecule detection. From the mid-1980s to early 1990s, research started to move away from obtaining a fundamental understanding of the phenomenon to the exploration of analytical applications. At the same time, significant developments occurred in the field of photonics that led to the advent of inexpensive, robust, compact, field-deployable Raman systems. The 1990s also saw rapid development in nanoscience. This convergence of technologies (photonics and nanoscience) has led to accelerated development of SERS substrates to detect a wide range of chemical and biological analytes. It would be a monumental task to discuss all the different kinds of SERS substrates that have been explored. Likewise, it would be impossible to discuss the use of SERS for both chemical and biological detection. Instead, a review of the most common metallic (Ag, Cu, and Au) SERS substrates for chemical detection only is discussed, as well as SERS substrates that are commercially available. Other issues with SERS for chemical detection have been selectivity, reversibility, and reusability of the substrates. How these issues have been addressed is also discussed in this review. PMID:28594385

A versatile SERS-based immunoassay for immunoglobulin detection using antigen-coated gold nanoparticles and malachite green-conjugated protein A/G

USDA-ARS?s Scientific Manuscript database

A surface enhanced Raman scattering (SERS) immunoassay for antibody detection in serum is described in the present work. The developed assay is conducted in solution and utilizes Au nanoparticles coated with the envelope (E) protein of West Nile Virus (WNV) as the SERS-active substrate and malachite...

Copper nanowire coated carbon fibers as efficient substrates for detecting designer drugs using SERS.

PubMed

Halouzka, Vladimir; Halouzkova, Barbora; Jirovsky, David; Hemzal, Dusan; Ondra, Peter; Siranidi, Eirini; Kontos, Athanassios G; Falaras, Polycarpos; Hrbac, Jan

2017-04-01

Miniature Surface Enhanced Raman Scattering (SERS) sensors were fabricated by coating the carbon fiber microelectrodes with copper nanowires. The coating procedure, based on anodizing the copper wire in ultrapure water followed by cathodic deposition of the anode-derived material onto carbon fiber electrodes, provides a "clean" copper nanowire network. The developed miniature (10µm in diameter and 2mm in length) and nanoscopically rough SERS substrates are applicable in drug sensing, as shown by the detection and resolving of a range of seized designer drugs in trace amounts (microliter volumes of 10 -10 -10 -12 M solutions). The copper nanowire modified carbon microfiber substrates could also find further applications in biomedical and environmental sensing. Copyright © 2016 Elsevier B.V. All rights reserved.

Substrate specificity of mitochondrial intermediate peptidase analysed by a support-bound peptide library

PubMed Central

Marcondes, M.F.M.; Alves, F.M.; Assis, D.M.; Hirata, I.Y.; Juliano, L.; Oliveira, V.; Juliano, M.A.

2015-01-01

The substrate specificity of recombinant human mitochondrial intermediate peptidase (hMIP) using a synthetic support-bound FRET peptide library is presented. The collected fluorescent beads, which contained the hydrolysed peptides generated by hMIP, were sequenced by Edman degradation. The results showed that this peptidase presents a remarkable preference for polar uncharged residues at P1 and P1′ substrate positions: Ser = Gln > Thr at P1 and Ser > Thr at P1′. Non-polar residues were frequent at the substrate P3, P2, P2′ and P3′ positions. Analysis of the predicted MIP processing sites in imported mitochondrial matrix proteins shows these cleavages indeed occur between polar uncharged residues. Previous analysis of these processing sites indicated the importance of positions far from the MIP cleavage site, namely the presence of a hydrophobic residue (Phe or Leu) at P8 and a polar uncharged residue (Ser or Thr) at P5. To evaluate this, additional kinetic analyses were carried out, using fluorogenic substrates synthesized based on the processing sites attributed to MIP. The results described here underscore the importance of the P1 and P1′ substrate positions for the hydrolytic activity of hMIP. The information presented in this work will help in the design of new substrate-based inhibitors for this peptidase. PMID:26082885

Elevated gold ellipse nanoantenna dimers as sensitive and tunable surface enhanced Raman spectroscopy substrates

DOE PAGES

Jubb, A. M.; Jiao, Y.; Eres, Gyula; ...

2016-02-15

Here we demonstrate large area arrays of elevated gold ellipse dimers with precisely controlled gaps for use as sensitive and highly controllable surface enhanced Raman scattering (SERS) substrates. The significantly enhanced Raman signal observed with SERS arises from both localized and long range plasmonic effects. By controlling the geometry of a SERS substrate, in this case the size and aspect ratio of individual ellipses, the plasmon resonance can be tuned in a broad wavelength range, providing a method for designing the response of SERS substrates at different excitation wavelengths. Plasmon effects exhibited by the elevated gold ellipse dimer substrates aremore » also demonstrated and confirmed through finite difference time domain (FDTD) simulations. A plasmon resonance red shift with an increase of the ellipse aspect ratio is observed, allowing systematic control of the resulting SERS signal intensity. Optimized elevated ellipse dimer substrates with 10±2 nm gaps exhibit uniform SERS enhancement factors on the order of 10 9 for adsorbed p-mercaptoaniline molecules.« less

Toward practical SERS sensing

NASA Astrophysics Data System (ADS)

Zhao, Yiping

2012-06-01

Since its discovery more than 30 years ago, surface-enhanced Raman scattering (SERS) has been recognized as a highly sensitive detection technique for chemical and biological sensing and medical diagnostics. However, the practical application of this remarkably sensitive technique has not been widely accepted as a viable diagnostic method due to the difficulty in preparing robust and reproducible substrates that provide maximum SERS enhancement. Here, we demonstrate that the aligned silver nanorod (AgNR) array substrates engineered by the oblique angle deposition method are capable of providing extremely high SERS enhancement factors (>108). The substrates are large area, uniform, reproducible, and compatible with general microfabrication process. The enhancement factor depends strongly on the length and shape of the Ag nanorods and the underlying substrate coating. By optimizing AgNR SERS substrates, we show that SERS is able to detect trace amount of toxins, virus, bacteria, or other chemical and biological molecules, and distinguish different viruses/bacteria and virus/bacteria strains. The substrate can be tailored into a multi-well chip for high throughput screening, integrated into fiber tip for portable sensing, incorporated into fluid/microfluidic devices for in situ real-time monitoring, fabricated onto a flexible substrate for tracking and identification, or used as on-chip separation device for ultra-thin layer chromatography and diagnostics. By combining the unique SERS substrates with a handheld Raman system, it can become a practical and portable sensor system for field applications. All these developments have demonstrated that AgNR SERS substrates could play an important role in the future for practical clinical, industrial, defense, and security sensing applications.

SERS substrates fabricated using ceramic filters for the detection of bacteria.

PubMed

Mosier-Boss, P A; Sorensen, K C; George, R D; Obraztsova, A

2016-01-15

SERS substrates were fabricated by filtering either Ag or Au colloidal particles onto rigid, ceramic filters - onto which suspensions of bacteria were then filtered. SERS spectra of the bacteria were obtained using a Raman spectrometer that has an 'orbital raster scan' capability. It was shown that bacteria samples prepared in this manner were uniformly distributed onto the surface of the SERS substrate. The effect of common buffer systems on the SERS spectra was investigated and the utility of using the SERS technique for speciation of bacteria was explored. Published by Elsevier B.V.

Plasmonic Paper as a Novel Chem/Bio Detection Platform

NASA Astrophysics Data System (ADS)

Tian, Limei

The time varying electric field of electromagnetic (EM) radiation causes oscillation of conduction electrons of metal nanoparticles. The resonance of such oscillation, termed localized surface plasmon resonance (LSPR), falls into the visible spectral region for noble metals such as gold, silver and copper. LSPR of metal nanostructures is sensitive to numerous factors such as composition, size, shape, dielectric properties of surrounding medium, and proximity to other nanostructures (plasmon coupling). The sensitivity of LSPR to the refractive index of surrounding medium renders it an attractive platform for chemical and biological sensing. When the excitation light is in resonance with the plasmon frequency of the metal nanoparticle, it radiates a characteristic dipolar radiation causing a characteristic spatial distribution in which certain areas show higher EM field intensity, which is manifested as electromagnetic field enhancement. Surface enhanced Raman scattering (SERS) involves dramatic enhancement of the intensity of the Raman scattering from the analyte adsorbed on or in proximity to a nanostructured metal surface exhibiting such strong EM field enhancement. Both LSPR and SERS have been widely investigated for highly sensitive and label-free chemical & biological sensors. Most of the SERS/LSPR sensors demonstrated so far rely on rigid planar substrates (e.g., glass, silicon) owing to the well-established lithographic approaches, which are routinely employed for either fabrication or assembly of plasmonic nanotransducers. In many cases, their rigid nature results in low conformal contact with the sample and hence poor sample collection efficiency. We hypothesized that paper substrates are an excellent alternative to conventional rigid substrates to significantly improve the (multi-)functionality of LSPR/SERS substrates, dramatically simplify the fabrication procedures and lower the cost. The choice of paper substrates for the implementation of SERS/LSPR sensors is rationalized by numerous advantages such as (i) high specific surface area resulting in large dynamic range (ii) excellent wicking properties for rapid uptake and transport of analytes to test domains (iii) compatibility with conventional printing approaches, enabling multi-analyte plasmonic sensors (iv) significant reduction in cost (v) smaller sample volume requirement (vi) easy disposability. In this work, we have introduced novel SERS and LSPR substrates based on conventional filter paper decorated with plasmonic nanostructures, called plasmonic paper. A flexible SERS substrate based on common filter paper adsorbed with gold nanostructures allows conformal contact with real-world surfaces, enabling rapid trace detection. To realize multifunctional SERS substrates, paper substrates were cut into star-shaped structures and the fingers were differentially functionalized with polyelectrolytes that allows separation and pre-concentration of different components of a complex sample in a small surface area by taking advantage of the properties of cellulose paper and shape-enhanced capillary effect. Plasmonic paper can also serve as a novel LSPR biosensing platform by decorating the paper substrate with biofunctionalized nanostructures. Furthermore, calligraphy approach was employed to create well-isolated test domains on paper substrates using functionalized plasmonic nanostructures as ink for multiplexed chemical sensing and label-free biosensing. These plasmonic paper substrates exhibit excellent sample collection efficiency and do not require complex fabrication processes. This class of substrates is expected to have applications not only to first responders and military personal but also to several areas of medical, food analysis, and environmental research.

Towards field detection of polycyclic aromatic hydrocarbons (PAHs) in environment water using a self-assembled SERS sensor

NASA Astrophysics Data System (ADS)

Yan, Xia; Shi, Xiaofeng; Yang, Jie; Zhang, Xu; Jia, Wenjie; Ma, Jun

2017-10-01

A self-assembled surface enhanced Raman scattering (SERS) sensor is reported in this paper. To achieve high sensitivity, a high sensitive SERS substrate and a high efficient self-constructed light path were made. The SERS substrate was composed by gold nanoparticles (AuNPs, pH=13), glycidyl methacrylate-ethylene dimethacrylate (GMA-EDMA) porous material and syringe filter. The substrate had a good repeatability, and the relative standard deviation (RSD) of the same substrate was less than 5%. The efficiency of the self-constructed light path is about two times better than RPB Y type reflection fiber when the energy density was roughly equal on samples. The size of the SERS sensor is 350×300×180 mm and the weight is 15 kg. Its miniaturization and portable can comply with the requirements of field detection. Besides, it has good sensitivity, stability and selectivity. For lab experiments, strong enhancements of Raman scattering from organic pollutant polycyclic aromatic hydrocarbons (PAHs) molecules were exhibited. The dependences of SERS intensities on concentrations of PAHs were investigated, and the results indicated that they revealed a satisfactory linear relationship in low concentrations. The limits of detection (LODs) of PAHs phenanthrene and fluorene are 8.3×10-10 mol/L and 7.1×10-10 mol/L respectively [signal to noise ratio (S/N) =3]. Based on this SERS sensor, signals of benzo (a) pyrene and pyrene were found in environmental water and the sensor would be an ideal candidate for field detection of PAHs.

Multi-branched gold nanostars with fractal structure for SERS detection of the pesticide thiram

NASA Astrophysics Data System (ADS)

Zhu, Jian; Liu, Mei-Jin; Li, Jian-Jun; Li, Xin; Zhao, Jun-Wu

2018-01-01

The surface-enhanced Raman scattering (SERS) activity of multi-branched gold nanostars with fractal structure has been investigated for trace detection of pesticide thiram. Raman spectrum results show that the gold nanostars substrate can produce about 102 fold stronger signal than the thiram alone with the thiram concentration increase of 103 times and 1.4 fold stronger signal than the gold nanostars without fractal feature. In the detection procedure, the most prominent SERS peak at 1376 cm- 1 has been chosen to characterize and quantify the concentration of thiram. Experimental results indicate this Raman substrate based on fractal gold nanostars exhibits excellent selective probing performance for thiram with a detection limit as low as 10- 10 M in solution and 0.24 ng/cm2 in apple peels. Interference experiment results show that the effects from the interfering pesticides could be neglected in the detection procedure. Therefore, the gold nanostars as a SERS substrate have excellent sensitivity and selectivity.

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.

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.

Colorimetry and SERS dual-mode detection of telomerase activity: combining rapid screening with high sensitivity

NASA Astrophysics Data System (ADS)

Zong, Shenfei; Wang, Zhuyuan; Chen, Hui; Hu, Guohua; Liu, Min; Chen, Peng; Cui, Yiping

2014-01-01

As an important biomarker and therapeutic target, telomerase has attracted considerable attention concerning its detection and monitoring. Here, we present a colorimetry and surface enhanced Raman scattering (SERS) dual-mode telomerase activity detection method, which has several distinctive advantages. First, colorimetric functionality allows rapid preliminary discrimination of telomerase activity by the naked eye. Second, the employment of SERS technique results in greatly improved detection sensitivity. Third, the combination of colorimetry and SERS into one detection system can ensure highly efficacious and sensitive screening of numerous samples. Besides, the avoidance of polymerase chain reaction (PCR) procedures further guarantees fine reliability and simplicity. Generally, the presented method is realized by an ``elongate and capture'' procedure. To be specific, gold nanoparticles modified with Raman molecules and telomeric repeat complementary oligonucleotide are employed as the colorimetric-SERS bifunctional reporting nanotag, while magnetic nanoparticles functionalized with telomerase substrate oligonucleotide are used as the capturing substrate. Telomerase can synthesize and elongate telomeric repeats onto the capturing substrate. The elongated telomeric repeats subsequently facilitate capturing of the reporting nanotag via hybridization between telomeric repeat and its complementary strand. The captured nanotags can cause a significant difference in the color and SERS intensity of the magnetically separated sediments. Thus both the color and SERS can be used as indicators of the telomerase activity. With fast screening ability and outstanding sensitivity, we anticipate that this method would greatly promote practical application of telomerase-based early-stage cancer diagnosis.As an important biomarker and therapeutic target, telomerase has attracted considerable attention concerning its detection and monitoring. Here, we present a colorimetry and surface enhanced Raman scattering (SERS) dual-mode telomerase activity detection method, which has several distinctive advantages. First, colorimetric functionality allows rapid preliminary discrimination of telomerase activity by the naked eye. Second, the employment of SERS technique results in greatly improved detection sensitivity. Third, the combination of colorimetry and SERS into one detection system can ensure highly efficacious and sensitive screening of numerous samples. Besides, the avoidance of polymerase chain reaction (PCR) procedures further guarantees fine reliability and simplicity. Generally, the presented method is realized by an ``elongate and capture'' procedure. To be specific, gold nanoparticles modified with Raman molecules and telomeric repeat complementary oligonucleotide are employed as the colorimetric-SERS bifunctional reporting nanotag, while magnetic nanoparticles functionalized with telomerase substrate oligonucleotide are used as the capturing substrate. Telomerase can synthesize and elongate telomeric repeats onto the capturing substrate. The elongated telomeric repeats subsequently facilitate capturing of the reporting nanotag via hybridization between telomeric repeat and its complementary strand. The captured nanotags can cause a significant difference in the color and SERS intensity of the magnetically separated sediments. Thus both the color and SERS can be used as indicators of the telomerase activity. With fast screening ability and outstanding sensitivity, we anticipate that this method would greatly promote practical application of telomerase-based early-stage cancer diagnosis. Electronic supplementary information (ESI) available: TEM images of individual MB@Au NPs, results of dynamic light scattering analysis and extinction spectrum obtained using colorimetry detection. See DOI: 10.1039/c3nr04942f

SERS-based viral fingerprinting: current capabilities and challenges

NASA Astrophysics Data System (ADS)

Driskell, J. D.; Abell, J. L.; Dluhy, R. A.; Zhao, Y.-P.; Tripp, R. A.

2010-04-01

Silver nanorod array substrates are fabricated by oblique angle deposition and characterized for optimal SERS performance. Using UV-visible-NIR spectrophotometry we show that the nanorods have a transverse surface plasmon resonance mode at ~357 nm and a broad absorbance spanning 600-800 nm when excited along the longitudinal direction. We demonstrate that SERS enhancement is optimized using an excitation wavelength of 633 or 785 nm. The large area uniformity in SERS signal (<10% variation) and reproducibility among preparations (<15% variation) provides a unique opportunity for SERS-based whole-organism fingerprinting. Egg prepared avian influenza virus and clinical sputum samples of human influenza virus were investigated to demonstrate SERS-based detection of a virus in a complex sample matrix and to assess the effect of different background matrices on the detection of similar viruses.

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).

Fabrication of chitosan-silver nanoparticle hybrid 3D porous structure as a SERS substrate for biomedical applications

NASA Astrophysics Data System (ADS)

Jung, Gyeong-Bok; Kim, Ji-Hye; Burm, Jin Sik; Park, Hun-Kuk

2013-05-01

We propose a simple, low-cost, large-area, and functional surface enhanced Raman scattering (SERS) substrate for biomedical applications. The SERS substrate with chitosan-silver nanoparticles (chitosan-Ag NPs) hybrid 3D porous structure was fabricated simply by a one-step method. The chitosan was used as a template for the Ag NPs deposition. SERS enhancement by the chitosan-Ag NPs substrate was experimentally verified using rhodamine B as an analyte. Thiolated single stranded DNA was also measured for atopic dermatitis genetic markers (chemokines CCL17) at a low concentration of 5 pM. We successfully designed a novel SERS substrate with silver nanoparticle hybridized 3D porous chitosan that has the potential to become a highly sensitive and selective tool for biomedical applications.

Disulphide linkage: To get cleaved or not? Bulk and nano copper based SERS of cystine

NASA Astrophysics Data System (ADS)

P. J., Arathi; Seemesh, Bhaskar; Rajendra Kumar Reddy, G.; Suresh Kumar, P.; Ramanathan, V.

2018-05-01

Different nano-structures of noble metals have been the conventional substrates for carrying out Surface Enhanced Raman Spectroscopy (SERS). In this paper we examine electrodeposited copper (Cu) nano-structures on pencil graphite as novel substrate to carry out SERS measurements by considering L-cystine (Cys-Cys) (dimer of the amino acid cysteine) as the probe. The formation of monolayer of the probe molecule on the substrates was confirmed using cyclic voltammetric measurements. Mode of adsorption of Cys-Cys was observed to be different on bulk Cu (taken in the wire form) and nano-structured Cu on pencil graphite. Whereas in the former the disulphide bond of Cys-Cys remained intact, it got cleaved when Cys-Cys was adsorbed on electrodeposited copper indicating the activated nature of the nano-structure compared to bulk copper. Csbnd S stretching mode of vibration underwent blue shift in Cys-Cys adsorbed on Cu on pencil graphite vis-à-vis Cys-Cys adsorbed on Cu wire. Further evidence on the cleavage of the Csbnd S bond on an activated substrate was obtained by considering a bimetallic substrate comprising of silver on copper which was electrodeposited on pencil graphite. Our studies have demonstrated that nano-copper surface is an excellent substrate for SERS giving 200 μM as lower detection limit for Cys-Cys.

Peptide microarray analysis of substrate specificity of the transmembrane Ser/Thr kinase KPI-2 reveals reactivity with cystic fibrosis transmembrane conductance regulator and phosphorylase.

PubMed

Wang, Hong; Brautigan, David L

2006-11-01

Human lemur (Lmr) kinases are predicted to be Tyr kinases based on sequences and are related to neurotrophin receptor Trk kinases. This study used homogeneous recombinant KPI-2 (Lmr2, LMTK2, Cprk, brain-enriched protein kinase) kinase domain and a library of 1,154 peptides on a microarray to analyze substrate specificity. We found that KPI-2 is strictly a Ser/Thr kinase that reacts with Ser either preceded by or followed by Pro residues but unlike other Pro-directed kinases does not strictly require an adjacent Pro residue. The most reactive peptide in the library corresponds to Ser-737 of cystic fibrosis transmembrane conductance regulator, and the recombinant R domain of cystic fibrosis transmembrane conductance regulator was a preferred substrate. Furthermore the KPI-2 kinase phosphorylated peptides corresponding to the single site in phosphorylase and purified phosphorylase b, making this only the second known phosphorylase b kinase. Phosphorylase was used as a specific substrate to show that KPI-2 is inhibited in living cells by addition of nerve growth factor or serum. The results demonstrate the utility of the peptide library to probe specificity and discover kinase substrates and offer a specific assay that reveals hormonal regulation of the activity of this unusual transmembrane kinase.

Large-area, uniform and low-cost dual-mode plasmonic naked-eye colorimetry and SERS sensor with handheld Raman spectrometer.

PubMed

Xu, Zhida; Jiang, Jing; Wang, Xinhao; Han, Kevin; Ameen, Abid; Khan, Ibrahim; Chang, Te-Wei; Liu, Gang Logan

2016-03-21

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 10(8) 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 × 10(8), 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.

Parameter optimization for Ag-coated TiO2 nanotube arrays as recyclable SERS substrates

NASA Astrophysics Data System (ADS)

Sun, Yuyang; Yang, Lulu; Liao, Fan; Dang, Qian; Shao, Mingwang

2018-06-01

The Ag-coated titanium dioxide nanotube arrays (Ag-coated TNTs) are obtained via the deposition of Ag nanoparticles on the two-step anodized TNTs. The wall thickness of TNTs is modulated via finite difference time domain simulation to get the favorable electromagnetic field for surface enhanced Raman scattering (SERS). Ag-coated TNTs with optimal wall thickness of 20 nm were employed as the SERS substrates to detect 2-mercaptobenzoxazole, which show superior detection sensitivity and uniformity. In addition, due to the photocatalysis of TNTs, the SERS substrates could clean themselves and be repeatedly used by photo-degradation of target molecules under the ultra-violet irradiation. The Ag-coated TNTs are a kind of bifunctional SERS substrates which can produce high-quality SERS signals and reuse to reduce the cost.

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.

High performance and reusable SERS substrates using Ag/ZnO heterostructure on periodic silicon nanotube substrate

NASA Astrophysics Data System (ADS)

Lai, Yi-Chen; Ho, Hsin-Chia; Shih, Bo-Wei; Tsai, Feng-Yu; Hsueh, Chun-Hway

2018-05-01

Surface-enhanced Raman scattering (SERS) substrate with a higher surface area, enhanced light harvesting, multiple hot spots and strong electromagnetic field enhancements would exhibit enhanced Raman signals. Herein, the Ag nanoparticle/ZnO nanowire heterostructure decorated periodic silicon nanotube (Ag@ZnO@SiNT) substrate was proposed and fabricated. The proposed structure employed as SERS-active substrate was examined, and the results showed both the high performance in terms of high sensitivity and good reproducibility. Furthermore, the Ag@ZnO@SiNT substrate demonstrated the self-cleaning performance through the photocatalytic degradation of probed molecules upon UV-irradiation. The results showed that the proposed nanostructure had high performance, good reproducibility and reusability, and it is a promising SERS-active substrate for molecular sensing and cleaning.

A Selective Surface-Enhanced Raman Scattering Sensor for Mercury(II) Based on a Porous Polymer Material and the Target-Mediated Displacement of a T-Rich Strand

NASA Astrophysics Data System (ADS)

Kang, Y.; Zhang, L.; Zhang, H.; Wu, T.; Du, Y.

2017-05-01

A sensitive and selective surface-enhanced Raman scattering (SERS) sensor for mercury(II) was fabricated based on the target-mediated displacement of a T-rich oligonucleotide strand. A DNA/aptamer duplex was prepared by the hybridization between a tetramethylrhodamine(TMR)-labeled thymine(T)-rich Hg2+-specific aptamer (denoted as TMR-aptamer) and a thiolated adenine-rich capturing DNA. The duplex can be immobilized onto the SERS substrate of the Ag-moiety modified glycidyl methacrylate-ethylene dimethacrylate (denoted as Ag-GMA-EDMA) via self-assembly by the thiol anchor, in which the TMR-aptamer exists in a double-stranded chain. In this case, the label of the TMR moiety approaches the substrate surface and produces a strong SERS signal. Upon the addition of the target, a pair of TMR-aptamers could cooperatively coordinate with Hg2+ to form a stable duplex-like structure mediated by the T-Hg2+-T complex between two adjacent strands, which triggers the release of the TMR-aptamer from the SERS substrate surface, thus drawing the TMR tags away from the substrate with a significant decrease in the SERS signal. This optical sensor shows a sensitive response to Hg2+ in a concentration from 5 nM to 2.0 μM with a detection limit of 2.5 nM. The prepared sensor is negligibly responsive to other metal ions, can be easily regenerated, and shows good performance in real sample analysis.

The use of a handheld Raman system for virus detection

NASA Astrophysics Data System (ADS)

Song, Chunyuan; Driskell, Jeremy D.; Tripp, Ralph A.; Cui, Yiping; Zhao, Yiping

2012-06-01

The combination of surface enhanced Raman spectroscopy (SERS) with a handheld Raman system would lead to a powerful portable device for defense and security applications. The Thermo Scientific FirstDefender RM instrument is a 785-nm handheld Raman spectrometer intended for rapid field identification of unknown solid and liquid samples. Its sensitivity and effectiveness for SERS-based detection was initially confirmed by evaluating detection of 1,2-di(4- pyridyl)ethylene as a reporter molecule on a silver nanorod (AgNR) substrate, and the results are comparable to those from a confocal Bruker Raman system. As avian influenza A viruses (AIV) are recognized as an important emerging threat to public health, this portable handheld Raman spectrometer is used, for the first time, to detect and identify avian influenza A viruses using a multi-well AgNR SERS chip. The SERS spectra obtained had rich peaks which demonstrated that the instrument can be effectively used for SERS-based influenza virus detection. According to the SERS spectra, these different influenza viruses were distinguished from the negative control via the principal component analysis and by partial least squares-discriminate analysis. Together, these results show that the combination effective SERS substrates when combined with a portable Raman spectrometer provides a powerful field device for chemical and biological sensing.

DNA origami based Au-Ag-core-shell nanoparticle dimers with single-molecule SERS sensitivity

NASA Astrophysics Data System (ADS)

Prinz, J.; Heck, C.; Ellerik, L.; Merk, V.; Bald, I.

2016-03-01

DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled. Electronic supplementary information (ESI) available: Additional information about materials and methods, designs of DNA origami templates, height profiles, additional SERS spectra, assignment of DNA bands, SEM images, additional AFM images, FDTD simulations, additional reference spectra for Cy3 and detailed description of EF estimation, simulated absorption and scattering spectra. See DOI: 10.1039/c5nr08674d

In Situ Fabrication of 3D Ag@ZnO Nanostructures for Microfluidic Surface-Enhanced Raman Scattering Systems

PubMed Central

2015-01-01

In this work, we develop an in situ method to grow highly controllable, sensitive, three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrates via an optothermal effect within microfluidic devices. Implementing this approach, we fabricate SERS substrates composed of Ag@ZnO structures at prescribed locations inside microfluidic channels, sites within which current fabrication of SERS structures has been arduous. Conveniently, properties of the 3D Ag@ZnO nanostructures such as length, packing density, and coverage can also be adjusted by tuning laser irradiation parameters. After exploring the fabrication of the 3D nanostructures, we demonstrate a SERS enhancement factor of up to ∼2 × 106 and investigate the optical properties of the 3D Ag@ZnO structures through finite-difference time-domain simulations. To illustrate the potential value of our technique, low concentrations of biomolecules in the liquid state are detected. Moreover, an integrated cell-trapping function of the 3D Ag@ZnO structures records the surface chemical fingerprint of a living cell. Overall, our optothermal-effect-based fabrication technique offers an effective combination of microfluidics with SERS, resolving problems associated with the fabrication of SERS substrates in microfluidic channels. With its advantages in functionality, simplicity, and sensitivity, the microfluidic-SERS platform presented should be valuable in many biological, biochemical, and biomedical applications. PMID:25402207

Improving surface-enhanced Raman scattering effect using gold-coated hierarchical polystyrene bead substrates modified with postgrowth microwave treatment.

PubMed

Yuen, Clement; Zheng, Wei; Huang, Zhiwei

2008-01-01

We report a novel postgrowth microwave heating implementation by selectively modifying hierarchical polystyrene (PS) bead substrates coated with gold (Au) films to effectively improve the surface-enhanced Raman scattering (SERS) effect on the analytes. The SERS signal of probe molecule rhodamine 6G (Rh 6G) on the microwave-treated Au-PS substrates can be improved by 10-fold, while the detection limit of Rh 6G in concentration can be enhanced by two orders of magnitude compared to the as-growth substrates. The high-quality SERS spectrum of saliva can also be acquired using the modified substrates, demonstrating the potential for the realization of the high-performance SERS substrates for biomedical applications.

Cicada wing decorated by silver nanoparticles as low-cost and active/sensitive substrates for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Guo, Lei; Zhang, Chang Xing; Deng, Li; Zhang, Guo Xin; Xu, Hai Jun; Sun, Xiao Ming

2014-06-01

A green, low-cost and highly efficient surface-enhanced Raman scattering (SERS) substrate was achieved by a chemical deposition of silver nanoparticles on a cicada wing, which has the large-scale nanosized protrusions on its surface. Employing the already-formed Ag/cicada wing as substrate for SERS detection, the detection limit for rhodamine 6G could reach 10-7M, the Raman enhancement factor of the substrate was as large as 106 and the relative standard deviation remains lower than 7%. The three-dimensional finite-difference time-domain simulation results showed that two types of inter-Ag-nanoparticle nanogaps in the formed geometry created a huge number of SERS "hot spots" where the electromagnetic field is substantially amplified and contributes to the higher SERS sensitivity. Meanwhile, the water contact angle of the SERS substrate is roughly 150°, which indicates the super-hydrophobic surface of the substrate. This feature may be conducive to the gathering of target molecules during the SERS detection, which in turn further improves the detection limit of target molecules. In order to improve the application of the substrate, thiram was used as the probe molecule, and the detection limit also reached 10-7 M. Meanwhile, the calibration of the Raman peak intensities of Rhodamine 6G and thiram allowed their quantitative detection. Therefore, the green and low-cost SERS substrates could be used for fast and quantitative detection of trace organic molecules. Our findings may contribute to the development of the green and low-cost SERS substrates and will allow the fast and quantitative detection of trace organic molecules.

Simultaneous detection of multiple biomarkers by means of SERS on polymer nanopillar gold arrays

NASA Astrophysics Data System (ADS)

Morasso, Carlo; Picciolini, Silvia; Mehn, Dora; Pellacani, Paola; Frangolho, Ana; Marchesini, Gerardo; Vanna, Renzo; Gualerzi, Alice; Bedoni, Marzia; Marabelli, Franco; Gramatica, Furio

2016-03-01

The detection of biomarkers by means of Surface Enhanced Raman Spectroscopy (SERS) is foreseen to became a very important tool in the clinical practice because of its excellent sensitivity and potential for the simultaneous detection of multiple biomarkers. In the present paper we describe how it was possible to build a sensor for the detection of genetic biomarkers involved in acute myeloid leukemia. The assay is based on the use of a specifically designed SERS substrate made of a 2D crystal structure of polymeric pillars embedded in a gold layer. This substrate is characterized by good enhancing properties coupled with an excellent homogeneity. The SERS substrate was conjugated with DNA probes complementary to a target sequence and used in a sandwich assay with gold nanoparticles labeled with a second DNA probe and a Raman reporter. The so developed assay allowed the detection of a leukemia biomarker (WT1 gene) and an housekeeping gene with low picomolar sensitivity. At last, we optimized the assay in order to tackle one of the main limitations of SERS based assay: the loss of signal that is observed when the Raman spectra are collected in liquid. Combining a preferential functionalization on the polymeric pillars with a different height of the polymer pillars from the gold layer the assay demonstrated its effectiveness even when measured in buffer.

SERS as analytical tool for detection of bacteria

NASA Astrophysics Data System (ADS)

Cialla, Dana; Rösch, Petra; Möller, Robert; Popp, Jürgen

2007-07-01

The detection of single bacteria should be improved by lowering the acquisition time via the application of SERS (surface enhanced Raman spectroscopy). Nano structured colloids or surfaces consisting of gold or silver can be used as SERS active substrates. However, for biological applications mostly gold is used as SERS active substrate since silver is toxic for bacterial cells. Furthermore, the application of gold as a SERS-active substrate allows the usage of Raman excitation wavelengths in the red part of the electromagnetic spectrum. For the SERS investigations on bacteria different colloids (purchased and self prepared, preaggregated and non-aggregated) are chosen as SERS active substrates. The application of different gold colloids under gently mixing conditions to prevent the bacterial damage allowed the recording of reproducible SERS spectra of bacteria. The SERS spectra of B. pumilus are dominated by contributions of ingredients of the outer cell wall, e.g. the peptidoglycan layer. SEM images of the coated bacteria demonstrate the incomplete adsorption most probably due to variations within the binding affinities between different outer cell components and the gold colloids.

Ag-NP@Ge-nanotaper/Si-micropillar ordered arrays as ultrasensitive and uniform surface enhanced Raman scattering substrates.

PubMed

Liu, Jing; Meng, Guowen; Li, Zhongbo; Huang, Zhulin; Li, Xiangdong

2015-11-21

Surface-enhanced Raman scattering (SERS) is considered to be an excellent candidate for analytical detection schemes, because of its molecular specificity, rapid response and high sensitivity. Here, SERS-substrates of Ag-nanoparticle (Ag-NP) decorated Ge-nanotapers grafted on hexagonally ordered Si-micropillar (denoted as Ag-NP@Ge-nanotaper/Si-micropillar) arrays are fabricated via a combinatorial process of two-step etching to achieve hexagonal Si-micropillar arrays, chemical vapor deposition of flocky Ge-nanotapers on each Si-micropillar and decoration of Ag-NPs onto the Ge-nanotapers through galvanic displacement. With high density three-dimensional (3D) "hot spots" created from the large quantities of the neighboring Ag-NPs and large-scale uniform morphology, the hierarchical Ag-NP@Ge-nanotaper/Si-micropillar arrays exhibit strong and reproducible SERS activity. Using our hierarchical 3D SERS-substrates, both methyl parathion (a commonly used pesticide) and PCB-2 (one congener of highly toxic polychlorinated biphenyls) with concentrations down to 10(-7) M and 10(-5) M have been detected respectively, showing great potential in SERS-based rapid trace-level detection of toxic organic pollutants in the environment.

Wafer-Scale Hierarchical Nanopillar Arrays Based on Au Masks and Reactive Ion Etching for Effective 3D SERS Substrate.

PubMed

Men, Dandan; Wu, Yingyi; Wang, Chu; Xiang, Junhuai; Yang, Ganlan; Wan, Changjun; Zhang, Honghua

2018-02-04

Two-dimensional (2D) periodic micro/nanostructured arrays as SERS substrates have attracted intense attention due to their excellent uniformity and good stability. In this work, periodic hierarchical SiO₂ nanopillar arrays decorated with Ag nanoparticles (NPs) with clean surface were prepared on a wafer-scale using monolayer Au NP arrays as masks, followed by reactive ion etching (RIE), depositing Ag layer and annealing. For the prepared SiO₂ nanopillar arrays decorated with Ag NPs, the size of Ag NPs was tuned from ca. 24 to 126 nanometers by controlling the deposition thickness of Ag film. Importantly, the SiO₂ nanopillar arrays decorated with Ag NPs could be used as highly sensitive SERS substrate for the detection of 4-aminothiophenol (4-ATP) and rhodamine 6G (R6G) due to the high loading of Ag NPs and a very uniform morphology. With a deposition thickness of Ag layer of 30 nm, the SiO₂ nanopillar arrays decorated with Ag NPs exhibited the best sensitive SERS activity. The excellent SERS performance of this substrate is mainly attributed to high-density "hotspots" derived from nanogaps between Ag NPs. Furthermore, this strategy might be extended to synthesize other nanostructured arrays with a large area, which are difficult to be prepared only via conventional wet-chemical or physical methods.

Low-Cost, Disposable, Flexible and Highly Reproducible Screen Printed SERS Substrates for the Detection of Various Chemicals

PubMed Central

Wu, Wei; Liu, Li; Dai, Zhigao; Liu, Juhua; Yang, Shuanglei; Zhou, Li; Xiao, Xiangheng; Jiang, Changzhong; Roy, Vellaisamy A.L.

2015-01-01

Ideal SERS substrates for sensing applications should exhibit strong signal enhancement, generate a reproducible and uniform response, and should be able to fabricate in large-scale and low-cost. Herein, we demonstrate low-cost, highly sensitive, disposable and reproducible SERS substrates by means of screen printing Ag nanoparticles (NPs) on a plastic PET (Polyethylene terephthalate) substrates. While there are many complex methods for the fabrication of SERS substrates, screen printing is suitable for large-area fabrication and overcomes the uneven radial distribution. Using as-printed Ag substrates as the SERS platform, detection of various commonly known chemicals have been done. The SERS detection limit of Rhodamine 6G (R6G) is higher than the concentration of 1 × 10−10 M. The relative standard deviation (RSD) value for 784 points on the detection of R6G and Malachite green (MG) is less than 20% revealing a homogeneous SERS distribution and high reproducibility. Moreover, melamine (MA) is detected in fresh liquid-milk without additional pretreatment, which may accelerate the application of rapid on-line detection of MA in liquid milk. Our screen printing method highlights the use of large-scale printing strategies for the fabrication of well-defined functional nanostructures with applications well beyond the field of SERS sensing. PMID:25974125

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

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.

High performance SERS on nanoporous gold substrates synthesized by chemical de-alloying a Au-based metallic glass

NASA Astrophysics Data System (ADS)

Xue, Yanpeng; Scaglione, Federico; Rizzi, Paola; Battezzati, Livio

2017-12-01

A Au20Cu48Ag7Pd5Si20 metallic glass precursor has been used to synthesize nanoporous gold by chemical de-alloying in a mixture of HNO3 and HF. Gold ligaments of size ranging from 45 to 100 nm were obtained as a function of HNO3 concentration, electrolyte temperature and de-alloying time. The as-prepared nanoporous gold exhibited strong surface enhanced Raman scattering (SERS) effect using 4,4‧-bi-pyridine as probe molecule. For application in melamine sensing, the detection limit of 10-6 M was achieved, which indicated that this biocompatible material has great potential as SERS active substrate.

Surface enhanced Raman scattering substrates prepared by thermal evaporation on liquid surfaces.

PubMed

Ye, Ziran; Sun, Guofang; Sui, Chenghua; Yan, Bo; Gao, Fan; Cai, Pinggen; Lv, Bin; Li, Yun; Chen, Naibo; Xu, Fengyun; Wang, Ke; Ye, Gaoxiang; Yang, Shikuan

2018-06-25

We present an effective surface-enhancement Raman scattering(SERS) substrate enabled by depositing metallic film on a liquid surface at room temperature. Thermal evaporation is used to deposit Au atoms on silicone oil surface and then form quasi-continuous films. Due to the isotropic characteristics of the liquid surface, this film consists of substantial nanoparticles with uniform diameter, which is different from films fabricated on solid substrates and can be served as an applicable substrate for SERS detection. With the assistance of this substrate, SERS signals of Rhodamine 6G(R6G) were significantly enhanced, the dependence between SERS spectra and film thickness was investigated. Analytical simulation results confirm the experimental observations and the superiorities of our proposed method for preparation of SERS substrate. This work provides a potential application of metallic film deposition on free-sustained surface and holds promise as an efficient sensor in rapid trace detection of small molecule analytes. © 2018 IOP Publishing Ltd.

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.

Laser writing of single-crystalline gold substrates for surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Singh, Astha; Sharma, Geeta; Ranjan, Neeraj; Mittholiya, Kshitij; Bhatnagar, Anuj; Singh, B. P.; Mathur, Deepak; Vasa, Parinda

2017-07-01

Surface enhanced Raman scattering (SERS) spectroscopy, a powerful contemporary tool for studying low-concentration analytes via surface plasmon induced enhancement of local electric field, is of utility in biochemistry, material science, threat detection, and environmental studies. We have developed a simple, fast, scalable, and relatively low-cost optical method of fabricating and characterizing large-area, reusable and broadband SERS substrates with long storage lifetime. We use tightly focused, intense infra-red laser pulses to write gratings on single-crystalline, Au (1 1 1) gold films on mica which act as SERS substrates. Our single-crystalline SERS substrates compare favourably, in terms of surface quality and roughness, to those fabricated in poly-crystalline Au films. Tests show that our SERS substrates have the potential of detecting urea and 1,10-phenantroline adulterants in milk and water, respectively, at 0.01 ppm (or lower) concentrations.

[Monolithic column-gold composite substrate preparation and application to SERS detection of pigment].

PubMed

Xie, Yun-Fei; Li, Yan; Yu, Hui; Qian, He; Yao, Wei-Rong

2014-03-01

In the present study, we developed a novel SERS substrate with the porous monolith material combined with classic gold nanoparticles, and erythrosine as the research object, by adjusting the different experimental conditions for optimal SERS enhancements, including system pH and mixing time, and ultimately selected the optimum pH value 5.06 and mixing time 25 min. Compared with the traditional gold plastic substrate enhancement effect, the experimental conditions were applied to the monolith substrate SERS detection of dye erythrosine, different concentrations of samples were used for erythrosine SERS detection, and the detection limit reached 0.1 g x mL(-1). The method uses the payload of gold nanoparticles in mesoporous materials to effectively enhance the SERS signal. And this method has the advantages of simpleness and good stability, which provides a favorable theoretical basis for the rapid prohibited colorings screening.

Effects of surface topography on SERS response: Correlating nanoscopy with spectroscopy

NASA Astrophysics Data System (ADS)

Das, Sumit Kumar; Ghosh, Manash; Chowdhury, Joydeep

2018-05-01

This paper reports for the first time the hidden correlation between the topographical features of the bilayer Langmuir-Blodgett (LB) film substrates of stearic acid (SA) incubated in Au@Ag nanocolloids over various dipping times (DTs) with their corresponding SERS responses. The topographies of the as prepared substrates are investigated from the statistical considerations in terms of lateral correlation length, interface width, Hurst and Lyapnov exponents. The real space of the substrates are mapped directly from the FESEM and AFM images of the bilayer LB film of SA immersed in Au@Ag nanocolloids over various DTs ranging between 6 and 72 h. The SERS spectra of the Rhodamine 6G molecules adsorbed on the as prepared substrates have been reported. The statistical parameters of the substrates that exhibit maximum SERS efficacy have been suggested. The far field distributions in presence and in absence of Raman dipole together with spatial distribution of the near field from the hottest spot of the as prepared substrate have also been reported. To our knowledge, this is the first report that links nanoscopy with SERS spectroscopy from statistical considerations and is expected to open a new window towards the fabrication of more efficient and reproducible SERS active substrates in future endeavours.

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.

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).

Enabling Technologies for Point and Remote Sensing of Chemical and Biological Agents Using Surface Enhanced Raman Scattering (SERS) Techniques

DTIC Science & Technology

2009-09-01

silver colloid. .........................15 Figure 10. SEM images of various Bacillus spores on (a) fabricated substrate, (b) Klarite substrate...Figure 12. Comparison of SERS spectra from several Bacillus spore samples collected on Klarite substrates collected on Renishaw system...19 Figure 13. Comparison of SERS spectra from several Bacillus spore samples on FON

Highly Sensitive, Uniform, and Reproducible Surface-Enhanced Raman Spectroscopy Substrate with Nanometer-Scale Quasi-periodic Nanostructures.

PubMed

Jin, Yuanhao; Wang, Yingcheng; Chen, Mo; Xiao, Xiaoyang; Zhang, Tianfu; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Li, Qunqing

2017-09-20

We introduce a simple and cost-effective approach for fabrication of effective surface-enhanced Raman spectroscopy (SERS) substrates. It is shown that the as-fabricated substrates show excellent SERS effects in various probe molecules with high sensitivity, that is, picomolar level detection, and also good reliability. With a SERS enhancement factor beyond 10 8 and excellent reproducibility (deviation less than 5%) of signal intensity, the fabrication of the SERS substrate is realized on a four-inch wafer and proven to be effective in pesticide residue detection. The SERS substrate is realized first through the fabrication of quasi-periodic nanostructured silicon with dimension features in tens of nanometers using superaligned carbon nanotubes networks as an etching mask, after which a large amount of hot spots with nanometer gaps are formed through deposition of a gold film. With rigorous nanostructure design, the enhanced performance of electromagnetic field distribution for nanostructures is optimized. With the advantage of cost-effective large-area preparation, it is believed that the as-fabricated SERS substrate could be used in a wide variety of actual applications where detection of trace amounts is necessary.

Colorimetry and SERS dual-mode detection of telomerase activity: combining rapid screening with high sensitivity.

PubMed

Zong, Shenfei; Wang, Zhuyuan; Chen, Hui; Hu, Guohua; Liu, Min; Chen, Peng; Cui, Yiping

2014-01-01

As an important biomarker and therapeutic target, telomerase has attracted considerable attention concerning its detection and monitoring. Here, we present a colorimetry and surface enhanced Raman scattering (SERS) dual-mode telomerase activity detection method, which has several distinctive advantages. First, colorimetric functionality allows rapid preliminary discrimination of telomerase activity by the naked eye. Second, the employment of SERS technique results in greatly improved detection sensitivity. Third, the combination of colorimetry and SERS into one detection system can ensure highly efficacious and sensitive screening of numerous samples. Besides, the avoidance of polymerase chain reaction (PCR) procedures further guarantees fine reliability and simplicity. Generally, the presented method is realized by an "elongate and capture" procedure. To be specific, gold nanoparticles modified with Raman molecules and telomeric repeat complementary oligonucleotide are employed as the colorimetric-SERS bifunctional reporting nanotag, while magnetic nanoparticles functionalized with telomerase substrate oligonucleotide are used as the capturing substrate. Telomerase can synthesize and elongate telomeric repeats onto the capturing substrate. The elongated telomeric repeats subsequently facilitate capturing of the reporting nanotag via hybridization between telomeric repeat and its complementary strand. The captured nanotags can cause a significant difference in the color and SERS intensity of the magnetically separated sediments. Thus both the color and SERS can be used as indicators of the telomerase activity. With fast screening ability and outstanding sensitivity, we anticipate that this method would greatly promote practical application of telomerase-based early-stage cancer diagnosis.

Millimeter-Sized Suspended Plasmonic Nanohole Arrays for Surface-Tension-Driven Flow-Through SERS

PubMed Central

2015-01-01

We present metallic nanohole arrays fabricated on suspended membranes as an optofluidic substrate. Millimeter-sized suspended nanohole arrays were fabricated using nanoimprint lithography. We demonstrate refractive-index-based tuning of the optical spectra using a sucrose solution for the optimization of SERS signal intensity, leading to a Raman enhancement factor of 107. Furthermore, compared to dead-ended nanohole arrays, suspended nanohole arrays capable of flow-through detection increased the measured SERS signal intensity by 50 times. For directed transport of analytes, we present a novel methodology utilizing surface tension to generate spontaneous flow through the nanoholes with flow rates of 1 μL/min, obviating the need for external pumps or microfluidic interconnects. Using this method for SERS, we obtained a 50 times higher signal as compared to diffusion-limited transport and could detect 100 pM 4-mercaptopyridine. The suspended nanohole substrates presented herein possess a uniform and reproducible geometry and show the potential for improved analyte transport and SERS detection. PMID:25678744

Enhanced Self-Organized Dewetting of Ultrathin Polymer Blend Film for Large-Area Fabrication of SERS Substrate.

PubMed

Zhang, Huanhuan; Xu, Lin; Xu, Yabo; Huang, Gang; Zhao, Xueyu; Lai, Yuqing; Shi, Tongfei

2016-12-06

We study the enhanced dewetting of ultrathin Polystyrene (PS)/Poly (methyl methacrylate) (PMMA) blend films in a mixed solution, and reveal the dewetting can act as a simple and effective method to fabricate large-area surface-enhanced Raman scattering (SERS) substrate. A bilayer structure consisting of under PMMA layer and upper PS layer forms due to vertical phase separation of immiscible PS/PMMA during the spin-coating process. The thicker layer of the bilayer structure dominates the dewetting structures of PS/PMMA blend films. The diameter and diameter distribution of droplets, and the average separation spacing between the droplets can be precisely controlled via the change of blend ratio and film thickness. The dewetting structure of 8 nm PS/PMMA (1:1 wt%) blend film is proved to successfully fabricate large-area (3.5 cm × 3.5 cm) universal SERS substrate via deposited a silver layer on the dewetting structure. The SERS substrate shows good SERS-signal reproducibility (RSD < 7.2%) and high enhancement factor (2.5 × 10 7 ). The enhanced dewetting of polymer blend films broadens the application of dewetting of polymer films, especially in the nanotechnology, and may open a new approach for the fabrication of large-area SERS substrate to promote the application of SERS substrate in the rapid sensitive detection of trace molecules.

Enhanced Self-Organized Dewetting of Ultrathin Polymer Blend Film for Large-Area Fabrication of SERS Substrate

PubMed Central

Zhang, Huanhuan; Xu, Lin; Xu, Yabo; Huang, Gang; Zhao, Xueyu; Lai, Yuqing; Shi, Tongfei

2016-01-01

We study the enhanced dewetting of ultrathin Polystyrene (PS)/Poly (methyl methacrylate) (PMMA) blend films in a mixed solution, and reveal the dewetting can act as a simple and effective method to fabricate large-area surface-enhanced Raman scattering (SERS) substrate. A bilayer structure consisting of under PMMA layer and upper PS layer forms due to vertical phase separation of immiscible PS/PMMA during the spin-coating process. The thicker layer of the bilayer structure dominates the dewetting structures of PS/PMMA blend films. The diameter and diameter distribution of droplets, and the average separation spacing between the droplets can be precisely controlled via the change of blend ratio and film thickness. The dewetting structure of 8 nm PS/PMMA (1:1 wt%) blend film is proved to successfully fabricate large-area (3.5 cm × 3.5 cm) universal SERS substrate via deposited a silver layer on the dewetting structure. The SERS substrate shows good SERS-signal reproducibility (RSD < 7.2%) and high enhancement factor (2.5 × 107). The enhanced dewetting of polymer blend films broadens the application of dewetting of polymer films, especially in the nanotechnology, and may open a new approach for the fabrication of large-area SERS substrate to promote the application of SERS substrate in the rapid sensitive detection of trace molecules. PMID:27922062

A separable surface-enhanced Raman scattering substrate modified with MIL-101 for detection of overlapping and invisible compounds after thin-layer chromatography development.

PubMed

Zhang, Bin Bin; Shi, Yi; Chen, Hui; Zhu, Qing Xia; Lu, Feng; Li, Ying Wei

2018-01-02

By coupling surface-enhanced Raman spectroscopy (SERS) with thin-layer chromatography (TLC), a powerful method for detecting complex samples was successfully developed. However, in the TLC-SERS method, metal nanoparticles serving as the SERS-active substrate are likely to disturb the detection of target compounds, particularly in overlapping compounds after TLC development. In addition, the SERS detection of compounds that are invisible under both visible light and UV 254/365 after TLC development is still a significant challenge. In this study, we demonstrated a facile strategy to fabricate a TLC plate with metal-organic framework-modified gold nanoparticles as a separable SERS substrate, on which all separated components, including overlapping and invisible compounds, could be detected by a point-by-point SERS scan along the developing direction. Rhodamine 6G (R6G) was used as a probe to evaluate the performance of the substrate. The results indicated that the substrate provided good sensitivity and reproducibility, and optimal SERS signals could be collected in 5 s. Furthermore, this new substrate exhibited a long shelf life. Thus, our method has great potential for the sensitive and rapid detection of overlapping and invisible compounds in complex samples after TLC development. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Optimization of a multi-well array SERS chip

NASA Astrophysics Data System (ADS)

Abell, J. L.; Driskell, J. D.; Dluhy, R. A.; Tripp, R. A.; Zhao, Y.-P.

2009-05-01

SERS-active substrates are fabricated by oblique angle deposition and patterned by a polymer-molding technique to provide a uniform array for high throughput biosensing and multiplexing. Using a conventional SERS-active molecule, 1,2-Bis(4-pyridyl)ethylene (BPE), we show that this device provides a uniform Raman signal enhancement from well to well. The patterning technique employed in this study demonstrates a flexibility allowing for patterning control and customization, and performance optimization of the substrate. Avian influenza is analyzed to demonstrate the ability of this multi-well patterned SERS substrate for biosensing.

Geometrical and morphological optimizations of plasmonic nanoarrays for high-performance SERS detection

NASA Astrophysics Data System (ADS)

Li, W. Q.; Wang, G.; Zhang, X. N.; Geng, H. P.; Shen, J. L.; Wang, L. S.; Zhao, J.; Xu, L. F.; Zhang, L. J.; Wu, Y. Q.; Tai, R. Z.; Chen, G.

2015-09-01

Here we present an in-depth and comprehensive study of the effect of the geometry and morphology of nanoarray (NA) substrates on their surface-enhanced Raman scattering (SERS) performance. The high-quality SERS-active NA substrates of various unit shapes and pitches are assembled through electron beam lithography and fabricated by electron beam physical vapor deposition. Good agreement is found on comparing the Raman scattering results with the integrals of the fourth power of local electric fields from the three-dimensional numerical simulations. A novel type of hybrid NA substrate composed of disordered nanoparticles and a periodic NA is fabricated and characterized. The morphology of NAs has little influence on the SERS performance of hybrid NA substrates and they perform better than both their counterparts pure NA and disordered nanoparticle substrates.

Geometrical and morphological optimizations of plasmonic nanoarrays for high-performance SERS detection.

PubMed

Li, W Q; Wang, G; Zhang, X N; Geng, H P; Shen, J L; Wang, L S; Zhao, J; Xu, L F; Zhang, L J; Wu, Y Q; Tai, R Z; Chen, G

2015-10-07

Here we present an in-depth and comprehensive study of the effect of the geometry and morphology of nanoarray (NA) substrates on their surface-enhanced Raman scattering (SERS) performance. The high-quality SERS-active NA substrates of various unit shapes and pitches are assembled through electron beam lithography and fabricated by electron beam physical vapor deposition. Good agreement is found on comparing the Raman scattering results with the integrals of the fourth power of local electric fields from the three-dimensional numerical simulations. A novel type of hybrid NA substrate composed of disordered nanoparticles and a periodic NA is fabricated and characterized. The morphology of NAs has little influence on the SERS performance of hybrid NA substrates and they perform better than both their counterparts pure NA and disordered nanoparticle substrates.

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.

Use of Standing Gold Nanorods for Detection of Malachite Green and Crystal Violet in Fish by SERS.

PubMed

Chen, Xiaowei; Nguyen, Trang H D; Gu, Liqun; Lin, Mengshi

2017-07-01

With growing consumption of aquaculture products, there is increasing demand on rapid and sensitive techniques that can detect prohibited substances in the seafood products. This study aimed to develop a novel surface-enhanced Raman spectroscopy (SERS) method coupled with simplified extraction protocol and novel gold nanorod (AuNR) substrates to detect banned aquaculture substances (malachite green [MG] and crystal violet [CV]) and their mixture (1:1) in aqueous solution and fish samples. Multivariate statistical tools such as principal component analysis (PCA) and partial least squares regression (PLSR) were used in data analysis. PCA results demonstrate that SERS can distinguish MG, CV and their mixture (1:1) in aqueous solution and in fish samples. The detection limit of SERS coupled with standing AuNR substrates is 1 ppb for both MG and CV in fish samples. A good linear relationship between the actual concentration and predicted concentration of analytes based on PLSR models with R 2 values from 0.87 to 0.99 were obtained, indicating satisfactory quantification results of this method. These results demonstrate that the SERS method coupled with AuNR substrates can be used for rapid and accurate detection of MG and CV in fish samples. © 2017 Institute of Food Technologists®.

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

A Ag synchronously deposited and doped TiO2 hybrid as an ultrasensitive SERS substrate: a multifunctional platform for SERS detection and photocatalytic degradation.

PubMed

Yang, Libin; Sang, Qinqin; Du, Juan; Yang, Ming; Li, Xiuling; Shen, Yu; Han, Xiaoxia; Jiang, Xin; Zhao, Bing

2018-06-06

Ag simultaneously deposited and doped TiO2 (Ag-TiO2) hybrid nanoparticles (NPs) were prepared via a sol-hydrothermal method, as both a sensitive surface-enhanced Raman scattering (SERS) substrate and a superior photocatalyst for the first time. Ag-TiO2 hybrid NPs exhibit excellent SERS performance for several probe molecules and the enhancement factor is calculated to be 1.86 × 105. The detection limit of the 4-mercaptobenzoic acid (4-MBA) probe on the Ag-TiO2 substrate is 1 × 10-9 mol L-1, which is four orders of magnitude lower than that on pure TiO2 as a consequence of the synergistic effects of TiO2 and Ag. This is the highest SERS sensitivity among the reported semiconductor substrates and even comparable to noble metal substrates, and a SERS enhancement mechanism from the synergistic contribution of the semiconductor and noble metal was proposed. And importantly, the Ag-TiO2 hybrid shows excellent photocatalytic degradation activity for the detected species under UV light irradiation at lower concentration conditions, even for the hard to degrade 4-MBA molecule. This makes the Ag-TiO2 hybrid promising as a dual-function platform for both highly sensitive SERS detection and photocatalytic degradation of a pollutant system. Moreover, it also proves that the Ag-TiO2 hybrid can serve as a promising recyclable SERS-active substrate by virtue of its photocatalytic self-cleaning properties for some specific applications, for instance comparative studies of different species on the same SERS platform, in addition to the economic benefit.

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.

Facile fabrication of Ag dendrite-integrated anodic aluminum oxide membrane as effective three-dimensional SERS substrate

NASA Astrophysics Data System (ADS)

Zhang, Cong-yun; Lu, Ya; Zhao, Bin; Hao, Yao-wu; Liu, Ya-qing

2016-07-01

A novel surface enhanced Raman scattering (SERS)-active substrate has been successfully developed, where Ag-dendrites are assembled on the surface and embedded in the channels of anodic aluminum oxide (AAO) membrane, via electrodeposition in AgNO3/PVP aqueous system. Reaction conditions were systematically investigated to attain the best Raman enhancement. The growth mechanism of Ag dendritic nanostructures has been proposed. The Ag dendrite-integrated AAO membrane with unique hierarchical structures exhibits high SERS activity for detecting rhodamine 6G with a detection limit as low as 1 × 10-11 M. Furthermore, the three-dimensional (3D) substrates display a good reproducibility with the average intensity variations at the major Raman peak less than 12%. Most importantly, the 3D SERS substrates without any surface modification show an outstanding SERS response for the molecules with weak affinity for noble metal surfaces. The potential application for the detection of polycyclic aromatic hydrocarbons (PAHs) was evaluated with fluoranthene as Raman target molecule and a sensitive SERS detection with a limit down to 10-8 M was reached. The 3D SERS-active substrate shows promising potential for rapid detection of trace organic pollutants even weak affinity molecules in the environment.

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

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.

Raman-based system for DNA sequencing-mapping and other separations

DOEpatents

Vo-Dinh, Tuan

1994-01-01

DNA sequencing and mapping are performed by using a Raman spectrometer with a surface enhanced Raman scattering (SERS) substrate to enhance the Raman signal. A SERS label is attached to a DNA fragment and then analyzed with the Raman spectrometer to identify the DNA fragment according to characteristics of the Raman spectrum generated.

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.

Systematic investigation of the SERS efficiency and SERS hotspots in gas-phase deposited Ag nanoparticle assemblies.

PubMed

He, L B; Wang, Y L; Xie, X; Han, M; Song, F Q; Wang, B J; Cheng, W L; Xu, H X; Sun, L T

2017-02-15

Gas-phase deposited Ag nanoparticle assemblies are one of the most commonly used plasmonic substrates benefiting from their remarkable advantages such as clean particle surface, tunable particle density, available inter-particle gaps, low-cost and scalable fabrication, and excellent industry compatibility. However, their performance efficiencies are difficult to optimize due to the lack of knowledge of the hotspots inside their structures. We here report a design of delicate rainbow-like Ag nanoparticle assemblies, based on which the hotspots can be revealed through a combinatorial approach. The findings show that the hotspots in gas-phase deposited Ag nanoparticle assemblies are uniquely entangled by the excitation energy and specific inter-particle gaps, differing from the matching conditions in periodic arrays. For Ag nanoparticle assemblies deposited on Formvar-filmed substrates, the mean particle size is maintained around 10 nm, while the particle density can be widely tuned. The one possessing the highest SERS efficiency (under 473 nm excitation) have a particle number density of around 7100 μm -2 . Gaps with an inter-particle spacing of around 3 nm are found to serve as SERS hotspots, and these hotspots contribute to 68% of the overall SERS intensity. For Ag nanoparticle assemblies fabricated on carbon-filmed substrates, the mean particle size can be feasibly tuned. The one possessing the highest SERS efficiency under 473 nm excitation has a particle number density of around 460 μm -2 and a mean particle size of around 42.1 nm. The construction of Ag-analyte-Ag sandwich-like nanoparticle assemblies by a two-step-deposition method slightly improves the SERS efficiency when the particle number density is low, but suppresses the SERS efficiency when the particle number density is high.

Microfluidic setup for on-line SERS monitoring using laser induced nanoparticle spots as SERS active substrate.

PubMed

Buja, Oana-M; Gordan, Ovidiu D; Leopold, Nicolae; Morschhauser, Andreas; Nestler, Jörg; Zahn, Dietrich R T

2017-01-01

A microfluidic setup which enables on-line monitoring of residues of malachite green (MG) using surface-enhanced Raman scattering (SERS) is reported. The SERS active substrate was prepared via laser induced synthesis of silver or gold nanoparticles spot on the bottom of a 200 μm inner dimension glass capillary, by focusing the laser beam during a continuous flow of a mixture of silver nitrate or gold chloride and sodium citrate. The described microfluidic setup enables within a few minutes the monitoring of several processes: the synthesis of the SERS active spot, MG adsorption to the metal surface, detection of the analyte when saturation of the SERS signal is reached, and finally, the desorption of MG from the spot. Moreover, after MG complete desorption, the regeneration of the SERS active spot was achieved. The detection of MG was possible down to 10 -7 M concentration with a good reproducibility when using silver or gold spots as SERS substrate.

Analysis of the electrodeposition and surface chemistry of CdTe, CdSe, and CdS thin films through substrate-overlayer surface-enhanced Raman spectroscopy.

PubMed

Gu, Junsi; Fahrenkrug, Eli; Maldonado, Stephen

2014-09-02

The substrate-overlayer approach has been used to acquire surface enhanced Raman spectra (SERS) during and after electrochemical atomic layer deposition (ECALD) of CdSe, CdTe, and CdS thin films. The collected data suggest that SERS measurements performed with off-resonance (i.e. far from the surface plasmonic wavelength of the underlying SERS substrate) laser excitation do not introduce perturbations to the ECALD processes. Spectra acquired in this way afford rapid insight on the quality of the semiconductor film during the course of an ECALD process. For example, SERS data are used to highlight ECALD conditions that yield crystalline CdSe and CdS films. In contrast, SERS measurements with short wavelength laser excitation show evidence of photoelectrochemical effects that were not germane to the intended ECALD process. Using the semiconductor films prepared by ECALD, the substrate-overlayer SERS approach also affords analysis of semiconductor surface adsorbates. Specifically, Raman spectra of benzenethiol adsorbed onto CdSe, CdTe, and CdS films are detailed. Spectral shifts in the vibronic features of adsorbate bonding suggest subtle differences in substrate-adsorbate interactions, highlighting the sensitivity of this methodology.

Fast self-assembly of silver nanoparticle monolayer in hydrophobic environment and its application as SERS substrate

NASA Astrophysics Data System (ADS)

Leiterer, Christian; Zopf, David; Seise, Barbara; Jahn, Franka; Weber, Karina; Popp, Jürgen; Cialla-May, Dana; Fritzsche, Wolfgang

2014-09-01

We present a method which allows the straightforward wet-chemical synthesis of silver nanoparticles (AgNPs), hydrophobic coating assembling into monolayer, and their utilization as substrates for surface-enhanced Raman spectroscopy (SERS). In order to fabricate the SERS-active substrates, AgNPs were synthesized in water by chemical reduction of Ag+, coated with a hydrophobic shell (dodecanethiol), transferred to a non-polar solvent, and finally assembled through precipitation into a SERS-active self-assembled monolayer (SAM). Simple approaches for concentration and purification of the coated AgNPs are shown. The synthesized particles and SAMs were characterized by transmission electron microscopy, optical imaging, and spectroscopic measurements. This manuscript can be used as a do-it-yourself (DIY) tutorial which allows making SAMs from coated AgNPs (<15 nm) in every laboratory within less than 1 h and their utilization as potential low-cost SERS substrates (movie 1-4).

[Preparation of a kind of SERS-active substrates for spot fast analysis].

PubMed

Ji, Nan; Li, Zhi-Shi; Zhao, Bing; Zou, Bo

2013-02-01

A kind of SERS-active substrates was prepared using chemical self-assembly method, aiming at spot fast analysis using portable Raman spectrometer. PDDA was first absorbed on the inner wall of vials, and then Ag colloids were assembled on the inner wall. UV-Vis spectra and Raman spectra of two kinds of blank vials were investigated and the transparent vials were thought to be better for SERS-vials. UV-Vis spectra were used to monitor the assembly process of Ag colloids. SERS activity of our substrates was characterized using p-ATP as probing molecules.

Recognition of Artificial Nucleobases by E. coli Purine Nucleoside Phosphorylase versus its Ser90Ala Mutant in the Synthesis of Base-Modified Nucleosides.

PubMed

Fateev, Ilja V; Kharitonova, Maria I; Antonov, Konstantin V; Konstantinova, Irina D; Stepanenko, Vasily N; Esipov, Roman S; Seela, Frank; Temburnikar, Kartik W; Seley-Radtke, Katherine L; Stepchenko, Vladimir A; Sokolov, Yuri A; Miroshnikov, Anatoly I; Mikhailopulo, Igor A

2015-09-14

A wide range of natural purine analogues was used as probe to assess the mechanism of recognition by the wild-type (WT) E. coli purine nucleoside phosphorylase (PNP) versus its Ser90Ala mutant. The results were analyzed from viewpoint of the role of the Ser90 residue and the structural features of the bases. It was found that the Ser90 residue of the PNP 1) plays an important role in the binding and activation of 8-aza-7-deazapurines in the synthesis of their nucleosides, 2) participates in the binding of α-D-pentofuranose-1-phosphates at the catalytic site of the PNP, and 3) catalyzes the dephosphorylation of intermediary formed 2-deoxy-α-D-ribofuranose-1-phosphate in the trans-2-deoxyribosylation reaction. 5-Aza-7-deazaguanine manifested excellent substrate activity for both enzymes, 8-amino-7-thiaguanine and 2-aminobenzothiazole showed no substrate activity for both enzymes. On the contrary, the 2-amino derivatives of benzimidazole and benzoxazole are substrates and are converted into the N1- and unusual N2-glycosides, respectively. 9-Deaza-5-iodoxanthine showed moderate inhibitory activity of the WT E. coli PNP, whereas 9-deazaxanthine and its 2'-deoxyriboside are weak inhibitors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatic Assemblies of Well-Dispersed AgNPs on the Surface of Electrospun Nanofibers as Highly Active SERS Substrates for Wide-Range pH Sensing.

PubMed

Yang, Tong; Ma, Jun; Zhen, Shu Jun; Huang, Cheng Zhi

2016-06-15

Surface-enhanced Raman scattering (SERS) has shown high promise in analysis and bioanalysis, wherein noble metal nanoparticles (NMNPs) such as silver nanoparticles were employed as substrates because of their strong localized surface plasmon resonance (LSPR) properties. However, SERS-based pH sensing was restricted because of the aggregation of NMNPs in acidic medium or biosamples with high ionic strength. Herein, by using the electrostatic interaction as a driving force, AgNPs are assembled on the surface of ethylene imine polymer (PEI)/poly(vinyl alcohol) (PVA) electrospun nanofibers, which are then applied as highly sensitive and reproducible SERS substrate with an enhancement factor (EF) of 10(7)-10(8). When p-aminothiophenol (p-ATP) is used as an indicator with its b2 mode, a good and wide linear response to pH ranging from 2.56 to 11.20 could be available, and the as-prepared nanocomposite fibers then could be fabricated as excellent pH sensors in complicated biological samples such as urine, considering that the pH of urine could reflect the acid-base status of a person. This work not only emerges a cost-effective, direct, and convenient approach to homogeneously decorate AgNPs on the surface of polymer nanofibers but also supplies a route for preparing other noble metal nanofibrous sensing membranes.

Graphene oxide-Ag nanoparticles-pyramidal silicon hybrid system for homogeneous, long-term stable and sensitive SERS activity

NASA Astrophysics Data System (ADS)

Guo, Jia; Xu, Shicai; Liu, Xiaoyun; Li, Zhe; Hu, Litao; Li, Zhen; Chen, Peixi; Ma, Yong; Jiang, Shouzhen; Ning, Tingyin

2017-02-01

In our work, few layers graphene oxide (GO) were directly synthesized on Ag nanoparticles (AgNPs) by spin-coating method to fabricate a GO-AgNPs hybrid structure on a pyramidal silicon (PSi) substrate for surface-enhanced Raman scattering (SERS). The GO-AgNPs-PSi substrate showed excellent Raman enhancement effect, the minimum detected concentration for Rhodamine 6G (R6G) can reach 10-12 M, which is one order of magnitude lower than the AgNPs-PSi substrate and two order of magnitude lower than the GO-AgNPs-flat-Si substrate. The linear fit calibration curve with error bars is presented and the value of R2 of 612 and 773 cm-1 can reach 0.986 and 0.980, respectively. The excellent linear response between the Raman intensity and R6G concentrations prove that the prepared GO-AgNPs-PSi substrates can serve as good SERS substrate for molecule detection. The maximum deviations of SERS intensities from 20 positions of the GO-AgNPs-PSi substrate are less than 8%, revealing the high homogeneity of the SERS substrate. The excellent homogeneity of the enhanced Raman signals can be attributed to well-separated pyramid arrays of PSi, the uniform morphology of AgNPs and multi-functions of GO layer. Besides, the uniform GO film can effectively protect AgNPs from oxidation and endow the hybrid system a good stability and long lifetime. This GO-AgNPs-PSi substrate may provide a new way toward practical applications for the ultrasensitive and label-free SERS detection in areas of medicine, food safety and biotechnology.

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.

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.

Stamping SERS for creatinine sensing

NASA Astrophysics Data System (ADS)

Li, Ming; Du, Yong; Zhao, Fusheng; Zeng, Jianbo; Santos, Greggy M.; Mohan, Chandra; Shih, Wei-Chuan

2015-03-01

Urine can be obtained easily, readily and non-invasively. The analysis of urine can provide metabolic information of the body and the condition of renal function. Creatinine is one of the major components of human urine associated with muscle metabolism. Since the content of creatinine excreted into urine is relatively constant, it is used as an internal standard to normalize water variations. Moreover, the detection of creatinine concentration in urine is important for the renal clearance test, which can monitor the filtration function of kidney and health status. In more details, kidney failure can be imminent when the creatinine concentration in urine is high. A simple device and protocol for creatinine sensing in urine samples can be valuable for point-of-care applications. We reported quantitative analysis of creatinine in urine samples by using stamping surface enhanced Raman scattering (S-SERS) technique with nanoporous gold disk (NPGD) based SERS substrate. S-SERS technique enables label-free and multiplexed molecular sensing under dry condition, while NPGD provides a robust, controllable, and high-sensitivity SERS substrate. The performance of S-SERS with NGPDs is evaluated by the detection and quantification of pure creatinine and creatinine in artificial urine within physiologically relevant concentration ranges.

The development of "fab-chips" as low-cost, sensitive surface-enhanced Raman spectroscopy (SERS) substrates for analytical applications.

PubMed

Robinson, Ashley M; Zhao, Lili; Shah Alam, Marwa Y; Bhandari, Paridhi; Harroun, Scott G; Dendukuri, Dhananjaya; Blackburn, Jonathan; Brosseau, Christa L

2015-02-07

The demand for methods and technologies capable of rapid, inexpensive and continuous monitoring of health status or exposure to environmental pollutants persists. In this work, the development of novel surface-enhanced Raman spectroscopy (SERS) substrates from metal-coated silk fabric, known as zari, presents the potential for SERS substrates to be incorporated into clothing and other textiles for the routine monitoring of important analytes, such as disease biomarkers or environmental pollutants. Characterization of the zari fabric was completed using scanning electron microscopy, energy dispersive X-ray analysis and Raman spectroscopy. Silver nanoparticles (AgNPs) were prepared, characterized by transmission electron microscopy and UV-vis spectroscopy, and used to treat fabric samples by incubation, drop-coating and in situ synthesis. The quality of the treated fabric was evaluated by collecting the SERS signal of 4,4'-bipyridine on these substrates. When AgNPs were drop-coated on the fabric, sensitive and reproducible substrates were obtained. Adenine was selected as a second probe molecule, because it dominates the SERS signal of DNA, which is an important class of disease biomarker, particularly for pathogens such as Plasmodium spp. and Mycobacterium tuberculosis. Excellent signal enhancement could be achieved on these affordable substrates, suggesting that the developed fabric chips have the potential for expanding the use of SERS as a diagnostic and environmental monitoring tool for application in wearable sensor technologies.

Conductive scanning probe microscopy of the semicontinuous gold film and its SERS enhancement toward two-step photo-induced charge transfer and effect of the supportive layer

NASA Astrophysics Data System (ADS)

Sinthiptharakoon, K.; Sapcharoenkun, C.; Nuntawong, N.; Duong, B.; Wutikhun, T.; Treetong, A.; Meemuk, B.; Kasamechonchung, P.; Klamchuen, A.

2018-05-01

The semicontinuous gold film, enabling various electronic applications including development of surface-enhanced Raman scattering (SERS) substrate, is investigated using conductive atomic force microscopy (CAFM) and Kelvin probe force microscopy (KPFM) to reveal and investigate local electronic characteristics potentially associated with SERS generation of the film material. Although the gold film fully covers the underlying silicon surface, CAFM results reveal that local conductivity of the film is not continuous with insulating nanoislands appearing throughout the surface due to incomplete film percolation. Our analysis also suggests the two-step photo-induced charge transfer (CT) play the dominant role in the enhancement of SERS intensity with strong contribution from free electrons of the silicon support. Silicon-to-gold charge transport is illustrated by KPFM results showing that Fermi level of the gold film is slightly inhomogeneous and far below the silicon conduction band. We propose that inhomogeneity of the film workfunction affecting chemical charge transfer between gold and Raman probe molecule is associated with the SERS intensity varying across the surface. These findings provide deeper understanding of charge transfer mechanism for SERS which can help in design and development of the semicontinuous gold film-based SERS substrate and other electronic applications.

DNA origami based Au–Ag-core–shell nanoparticle dimers with single-molecule SERS sensitivity† †Electronic supplementary information (ESI) available: Additional information about materials and methods, designs of DNA origami templates, height profiles, additional SERS spectra, assignment of DNA bands, SEM images, additional AFM images, FDTD simulations, additional reference spectra for Cy3 and detailed description of EF estimation, simulated absorption and scattering spectra. See DOI: 10.1039/c5nr08674d Click here for additional data file.

PubMed Central

Prinz, J.; Heck, C.; Ellerik, L.; Merk, V.

2016-01-01

DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled. PMID:26892770

Quantitative Analysis of Single and Mix Food Antiseptics Basing on SERS Spectra with PLSR Method

NASA Astrophysics Data System (ADS)

Hou, Mengjing; Huang, Yu; Ma, Lingwei; Zhang, Zhengjun

2016-06-01

Usage and dosage of food antiseptics are very concerned due to their decisive influence in food safety. Surface-enhanced Raman scattering (SERS) effect was employed in this research to realize trace potassium sorbate (PS) and sodium benzoate (SB) detection. HfO2 ultrathin film-coated Ag NR array was fabricated as SERS substrate. Protected by HfO2 film, the SERS substrate possesses good acid resistance, which enables it to be applicable in acidic environment where PS and SB work. Regression relationship between SERS spectra of 0.3~10 mg/L PS solution and their concentration was calibrated by partial least squares regression (PLSR) method, and the concentration prediction performance was quite satisfactory. Furthermore, mixture solution of PS and SB was also quantitatively analyzed by PLSR method. Spectrum data of characteristic peak sections corresponding to PS and SB was used to establish the regression models of these two solutes, respectively, and their concentrations were determined accurately despite their characteristic peak sections overlapping. It is possible that the unique modeling process of PLSR method prevented the overlapped Raman signal from reducing the model accuracy.

Rapid Surface Enhanced Raman Scattering (SERS) Detection of Sibutramine Hydrochloride in Pharmaceutical Capsules with a β-Cyclodextrin- Ag/Polyvivnyl Alcohol Hydrogel Substrate.

PubMed

Ouyang, Lei; Jiang, Zuyan; Wang, Nan; Zhu, Lihua; Tang, Heqing

2017-07-10

Sibutramine hydrochloride (SH) is a banned weight-loss drug, but its illegal addition to health products is still rampant. This suggests a very urgent need for a fast and precise detection method for SH. Surface Enhanced Raman Scattering (SERS) is a promising candidate for this purpose, but the weak affinity between SH and bare metal limits its direct SERS detection. In the present work, β-cyclodextrin was capped in situ onto the surface of Ag nanoparticles to function as a scaffold to capture SH. The obtained Ag nanoparticles were encapsulated into polyvinyl alcohol (PVA) to fabricate a SERS active hydrogel with excellent reproducibility. A facile SERS strategy based on such substrate was proposed for trace SH quantification with a linear range of 7.0-150.0 µg·mL -1 , and a detection limit low to 3.0 µg·mL -1 . It was applied to analyze seven types of commercial slimming capsules with satisfactory results, showing good prospect for real applications.

Rapid Surface Enhanced Raman Scattering (SERS) Detection of Sibutramine Hydrochloride in Pharmaceutical Capsules with a β-Cyclodextrin- Ag/Polyvivnyl Alcohol Hydrogel Substrate

PubMed Central

Ouyang, Lei; Jiang, Zuyan; Wang, Nan; Zhu, Lihua; Tang, Heqing

2017-01-01

Sibutramine hydrochloride (SH) is a banned weight-loss drug, but its illegal addition to health products is still rampant. This suggests a very urgent need for a fast and precise detection method for SH. Surface Enhanced Raman Scattering (SERS) is a promising candidate for this purpose, but the weak affinity between SH and bare metal limits its direct SERS detection. In the present work, β-cyclodextrin was capped in situ onto the surface of Ag nanoparticles to function as a scaffold to capture SH. The obtained Ag nanoparticles were encapsulated into polyvinyl alcohol (PVA) to fabricate a SERS active hydrogel with excellent reproducibility. A facile SERS strategy based on such substrate was proposed for trace SH quantification with a linear range of 7.0–150.0 µg·mL–1, and a detection limit low to 3.0 µg·mL−1. It was applied to analyze seven types of commercial slimming capsules with satisfactory results, showing good prospect for real applications. PMID:28698502

Raman-based system for DNA sequencing-mapping and other separations

DOEpatents

Vo-Dinh, T.

1994-04-26

DNA sequencing and mapping are performed by using a Raman spectrometer with a surface enhanced Raman scattering (SERS) substrate to enhance the Raman signal. A SERS label is attached to a DNA fragment and then analyzed with the Raman spectrometer to identify the DNA fragment according to characteristics of the Raman spectrum generated. 11 figures.

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.

Large-area high-performance SERS substrates with deep controllable sub-10-nm gap structure fabricated by depositing Au film on the cicada wing

NASA Astrophysics Data System (ADS)

Jiwei, Qi; Yudong, Li; Ming, Yang; Qiang, Wu; Zongqiang, Chen; Wudeng, Wang; Wenqiang, Lu; Xuanyi, Yu; Jingjun, Xu; Qian, Sun

2013-10-01

Noble metal nanogap structure supports strong surface-enhanced Raman scattering (SERS) which can be used to detect single molecules. However, the lack of reproducible fabrication techniques with nanometer-level control over the gap size has limited practical applications. In this letter, by depositing the Au film onto the cicada wing, we engineer the ordered array of nanopillar structures on the wing to form large-area high-performance SERS substrates. Through the control of the thickness of the Au film deposited onto the cicada wing, the gap sizes between neighboring nanopillars are fine defined. SERS substrates with sub-10-nm gap sizes are obtained, which have the highest average Raman enhancement factor (EF) larger than 2 × 108, about 40 times as large as that of commercial Klarite® substrates. The cicada wings used as templates are natural and environment-friendly. The depositing method is low cost and high throughput so that our large-area high-performance SERS substrates have great advantage for chemical/biological sensing applications.

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.

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.

Design, fabrication, and characterization of metallic nanostructures for surface-enhanced Raman spectroscopy and plasmonic applications

NASA Astrophysics Data System (ADS)

Hao, Qingzhen

Metal/dielectric nanostructures have the ability to sustain coherent electron oscillations known as surface plasmons. Due to their capability of localizing and guiding light in sub-wavelength metal nanostructures beyond diffraction limits, surface plasmon-based photonics, or “plasmonics” has opened new physical phenomena and lead to novel applications in metamaterials, optoelectronics, surface enhanced spectroscopy and biological sensing. This dissertation centers on design, fabrication, characterization of metallic nanostructures and their applications in surface-enhanced Raman spectroscopy (SERS) and actively tunable plasmonics. Metal-dielectric nanostructures are the building blocks for photonic metamaterials. One valuable design guideline for metamaterials is the Babinet’s principle, which governs the optical properties of complementary nanostructures. However, most complementary metamaterials are designed for the far infrared region or beyond, where the optical absorption of metal is small. We have developed a novel dual fabrication method, capable of simultaneously producing optically thin complementary structures. From experimental measurements and theoretical simulations, we showed that Babinet’s principle qualitatively holds in the visible region for the optically thin complements. The complementary structure is also a good platform to study subtle differences between nanoparticles and nanoholes in SERS (a surface sensitive technique, which can enhance the conventional Raman cross-section by 106˜108 fold, thus very useful for highly sensitive biochemical sensing). Through experimental measurement and theoretical analysis, we showed that the SERS enhancement spectrum (plot of SERS enhancement versus excitation wavelengths), dominated by local near-field, for nanoholes closely follows their far-field optical transmission spectrum. However, the enhancement spectrum for nanoparticles red-shifts significantly from their far-field optical extinction spectrum, due to nontrivial high orders of evanescent scattering modes. This study unveils the different near-field properties between nanoparticle and nanohole arrays and adds important details to the conventional wisdom for SERS substrate design. Besides SERS studies on gold substrates, I further extended my research to transition metals, i.e. platinum. I have carried out a comparative study of SERS performance for gold and platinum substrates. The commonly observed low enhancement from a platinum substrate is explained by the larger Fano interference between its free intra-band electrons and its bound inter-band electrons. A major challenge in applying SERS for biochemical sensing is to fabricate substrates with excellent sensitivity and uniform surface functionality. Graphene, a single sheet of carbon atoms with an ideal two-dimensional honeycomb crystal structure, offers excellent surface chemical properties. We synthesized high quality single-layer graphene sheets by chemical vapor deposition (CVD) on copper foils and transferred them to gold nanostructures, i.e., nanoparticle or nanohole arrays. Our experimental data show that graphene coated metallic substrates could achieve higher sensitivity of SERS detection than bare metallic substrates. The combined graphene-nanostructure substrates show about three-fold or nine-fold enhancement in the Raman signal of methylene blue (MB) compared with the bare nanohole or nanoparticle substrates, respectively. The difference in the enhancement factors between the nanohole and nanoparticle substrates is explained by the different coating morphologies of graphene on the two substrates. SERS enhancement of graphene is further investigated on mechanically exfoliated graphene. We found that SERS enhancement of graphene can be tuned by changing its Fermi level through doping. Both molecular doping and gate doping experiments show that hole-doped graphene yields a larger SERS enhancement in MB than electron-doped graphene, which indicates that the SERS enhancement of graphene involves the chemical mechanism. SERS enhancement from metallic nanostructures, on the other hand, is mainly an electromagnetic effect, relying on the plasmonic properties of the nanostructures. Full-wave electromagnetic simulations indicate that graphene does not alter the plasmonic properties of nanostructures significantly, and consequently there is little influence on the electromagnetic SERS enhancement. However, graphene offers additional chemical enhancement which could be combined with the conventional SERS enhancement of bare gold nanostructures to achieve higher detection sensitivity. Besides SERS, plasmonics offers an opportunity to merge photonics and electronics at the nanoscale, namely optoelectronics, to obtain even larger data capacity and speed of operation. As a necessary component for optoelectronic devices, various optical switches have been developed. First, a thin layer of frequency responsive liquid crystals (LCs) is integrated with a gold nanoparticle or nanohole array. The frequency of the applied voltage controls the configuration of LCs to align parallel or perpendicular to the nanoparticle. The transmission spectra of the system shift back and forth as a result of changing effective LCs dielectric function. We demonstrated that this hybrid system is highly reversible and repeatable. We further extend this concept to use photosensitive LCs to change the absorption bands of a plasmonic absorber. We construct a tunable plasmonic absorber by integrating a photosensitive nematic liquid crystal (PNLC) layer onto an asymmetric gold nanodisk array. A repeatable tuning range of ˜ 25 nm in the dual absorption bands of the plasmonic nanodisk array is demonstrated in the near infrared region.

Fabrication of Semiconductor ZnO Nanostructures for Versatile SERS Application

PubMed Central

Yang, Lili; Yang, Yong; Ma, Yunfeng; Li, Shuai; Wei, Yuquan; Huang, Zhengren; Long, Nguyen Viet

2017-01-01

Since the initial discovery of surface-enhanced Raman scattering (SERS) in the 1970s, it has exhibited a huge potential application in many fields due to its outstanding advantages. Since the ultra-sensitive noble metallic nanostructures have increasingly exposed themselves as having some problems during application, semiconductors have been gradually exploited as one of the critical SERS substrate materials due to their distinctive advantages when compared with noble metals. ZnO is one of the most representative metallic oxide semiconductors with an abundant reserve, various and cost-effective fabrication techniques, as well as special physical and chemical properties. Thanks to the varied morphologies, size-dependent exciton, good chemical stability, a tunable band gap, carrier concentration, and stoichiometry, ZnO nanostructures have the potential to be exploited as SERS substrates. Moreover, other distinctive properties possessed by ZnO such as biocompatibility, photocatcalysis and self-cleaning, and gas- and chemo-sensitivity can be synergistically integrated and exerted with SERS activity to realize the multifunctional potential of ZnO substrates. In this review, we discuss the inevitable development trend of exploiting the potential semiconductor ZnO as a SERS substrate. After clarifying the root cause of the great disparity between the enhancement factor (EF) of noble metals and that of ZnO nanostructures, two specific methods are put forward to improve the SERS activity of ZnO, namely: elemental doping and combination of ZnO with noble metals. Then, we introduce a distinctive advantage of ZnO as SERS substrate and illustrate the necessity of reporting a meaningful average EF. We also summarize some fabrication methods for ZnO nanostructures with varied dimensions (0–3 dimensions). Finally, we present an overview of ZnO nanostructures for the versatile SERS application. PMID:29156600

GaAs Monolithic Microwave Subsystem Technology Base

DTIC Science & Technology

1980-01-01

To provide a captive source of reliable, high-quality GaAs substrates, a new crystal growth and substrate preparation facility which utilizes a high...Symp. GaAs and Related Compounds, Inst. Phys. Conf. Ser. 24, 6. 20. Wood, Woodcock and Harris (1978) GaAs and Related Compounds, Inst. Phys. Conf

Therapeutic drug monitoring of flucytosine in serum using a SERS-active membrane system

NASA Astrophysics Data System (ADS)

Berger, Adam G.; White, Ian M.

2017-02-01

A need exists for near real-time therapeutic drug monitoring (TDM), in particular for antibiotics and antifungals in patient samples at the point-of-care. To truly fit the point-of-care need, techniques must be rapid and easy to use. Here we report a membrane system utilizing inkjet-fabricated surface enhanced Raman spectroscopy (SERS) sensors that allows sensitive and specific analysis despite the elimination of sophisticated chromatography equipment, expensive analytical instruments, and other systems relegated to the central lab. We utilize inkjet-fabricated paper SERS sensors as substrates for 5FC detection; the use of paper-based SERS substrates leverages the natural wicking ability and filtering properties of microporous membranes. We investigate the use of microporous membranes in the vertical flow assay to allow separation of the flucytosine from whole blood. The passive vertical flow assay serves as a valuable method for physical separation of target analytes from complex biological matrices. This work further establishes a platform for easy, sensitive, and specific TDM of 5FC from whole blood.

Fabrication of flexible gold nanorods polymer metafilm via phase transfer method as SERS substrate for detecting food contaminants.

PubMed

Yang, Nan; You, Ting-Ting; Gao, Yu-Kun; Zhang, Chen-Meng; Yin, Penggang

2018-06-08

Surface enhanced Raman scattering (SERS) has been widely used in detection of food safety due to the nondestructive examination property. Here, we reported a flexible SERS film based on polymer immobilized gold nanorods polymer metafilm. Polystyrene-polyisoprene-polystyrene (SIS), a transparent and flexible along with excellent elasticity polymer was chosen as main support of gold nanorods. A simple phase transfer progress was adopted to mix the gold nanorods with polymer which can further used in most water-insoluble polymers. The SERS film performed satisfactorily while tested in a series of standard Raman probes like crystal violet (CV) and malachite green (MG). Moreover, the excellent reproducibility and elastic properties make the film promising substrates in practical detection. Hence, the MG detection on fish surface and trace thiram detection on orange pericarp were inspected with the detection result of 1 × 10-10 M and 1 × 10-6 M which below the demand of National standard of China, exactly matching the realistic application requirements.

Surface-Enhanced Raman Spectroscopy: Substrates and Analyzers You Can Use

NASA Astrophysics Data System (ADS)

Inscore, Frank; Shende, Chetan; Sengupta, Atanu; Huang, Hermes; Farquharson, Stuart

2010-08-01

Following the recognition of the surface-enhanced Raman scattering effect in 1977, there was an explosion of research aimed at understanding this phenomenon of molecular interactions with nano-scale particles, and more than 1000 papers were published by 1982. Since the mid-1990's there has been a resurgence in SERS-based research with the detection of single-molecules and the acknowledgement of "hot-spots". These measurements provoked new examination of SERS theory with a focus on the structure of these hot spots: fractal clusters, edges, or inter-particle gaps. Meanwhile, Real-Time Analyzers has been developing SERS-active sample systems and analyzers to exploit this phenomenon for trace chemical analysis. This presentation reviews the analytical capabilities and limitations for many of the SERS-active substrates, as well as RTA's metal-doped sol-gels. The latter includes the use of the sol-gels in sample systems and analyzers, and their application to poisons in water supplies, food contamination, drug and explosives detection and proteomics.

Nanosphere Templating Through Controlled Evaporation: A High Throughput Method For Building SERS Substrates

NASA Astrophysics Data System (ADS)

Alexander, Kristen; Hampton, Meredith; Lopez, Rene; Desimone, Joseph

2009-03-01

When a pair of noble metal nanoparticles are brought close together, the plasmonic properties of the pair (known as a ``dimer'') give rise to intense electric field enhancements in the interstitial gap. These fields present a simple yet exquisitely sensitive system for performing single molecule surface-enhanced Raman spectroscopy (SM-SERS). Problems associated with current fabrication methods of SERS-active substrates include reproducibility issues, high cost of production and low throughput. In this study, we present a novel method for the high throughput fabrication of high quality SERS substrates. Using a polymer templating technique followed by the placement of thiolated nanoparticles through meniscus force deposition, we are able to fabricate large arrays of identical, uniformly spaced dimers in a quick, reproducible manner. Subsequent theoretical and experimental studies have confirmed the strong dependence of the SERS enhancement on both substrate geometry (e.g. dimer size, shape and gap size) and the polarization of the excitation source.

Nanosphere Templating Through Controlled Evaporation: A High Throughput Method For Building SERS Substrates

NASA Astrophysics Data System (ADS)

Alexander, Kristen; Lopez, Rene; Hampton, Meredith; Desimone, Joseph

2008-10-01

When a pair of noble metal nanoparticles are brought close together, the plasmonic properties of the pair (known as a ``dimer'') give rise to intense electric field enhancements in the interstitial gap. These fields present a simple yet exquisitely sensitive system for performing single molecule surface-enhanced Raman spectroscopy (SM-SERS). Problems associated with current fabrication methods of SERS-active substrates include reproducibility issues, high cost of production and low throughput. In this study, we present a novel method for the high throughput fabrication of high quality SERS substrates. Using a polymer templating technique followed by the placement of thiolated nanoparticles through meniscus force deposition, we are able to fabricate large arrays of identical, uniformly spaced dimers in a quick, reproducible manner. Subsequent theoretical and experimental studies have confirmed the strong dependence of the SERS enhancement on both substrate geometry (e.g. dimer size, shape and gap size) and the polarization of the excitation source.

Gold/silver coated nanoporous ceramic membranes: a new substrate for SERS studies

NASA Astrophysics Data System (ADS)

Kassu, A.; Robinson, P.; Sharma, A.; Ruffin, P. B.; Brantley, C.; Edwards, E.

2010-08-01

Surface Enhanced Raman Scattering (SERS) is a recently discovered powerful technique which has demonstrated sensitivity and selectivity for detecting single molecules of certain chemical species. This is due to an enhancement of Raman scattered light by factors as large as 1015. Gold and Silver-coated substrates fabricated by electron-beam lithography on Silicon are widely used in SERS technique. In this paper, we report the use of nanoporous ceramic membranes for SERS studies. Nanoporous membranes are widely used as a separation membrane in medical devices, fuel cells and other studies. Three different pore diameter sizes of commercially available nanoporous ceramic membranes: 35 nm, 55nm and 80nm are used in the study. To make the membranes SERS active, they are coated with gold/silver using sputtering techniques. We have seen that the membranes coated with gold layer remain unaffected even when immersed in water for several days. The results show that gold coated nanoporous membranes have sensitivity comparable to substrates fabricated by electron-beam lithography on Silicon substrates.

Sensitive SERS detection at the single-particle level based on nanometer-separated mushroom-shaped plasmonic dimers

NASA Astrophysics Data System (ADS)

Xiang, Quan; Li, Zhiqin; Zheng, Mengjie; Liu, Qing; Chen, Yiqin; Yang, Lan; Jiang, Tian; Duan, Huigao

2018-03-01

Elevated metallic nanostructures with nanogaps (<10 nm) possess advantages for surface enhanced Raman scattering (SERS) via the synergic effects of nanogaps and efficient decoupling from the substrate through an elevated three-dimensional (3D) design. In this work, we demonstrate a pattern-transfer-free process to reliably define elevated nanometer-separated mushroom-shaped dimers directly from 3D resist patterns based on the gap-narrowing effect during the metallic film deposition. By controlling the initial size of nanogaps in resist structures and the following deposited film thickness, metallic nanogaps could be tuned at the sub-10 nm scale with single-digit nanometer precision. Both experimental and simulated results revealed that gold dimer on mushroom-shaped pillars have the capability to achieve higher SERS enhancement factor comparing to those plasmonic dimers on cylindrical pillars or on a common SiO2/Si substrate, implying that the nanometer-gapped elevated dimer is an ideal platform to achieve the highest possible field enhancement for various plasmonic applications.

Sea-urchin-like Fe3O4@C@Ag particles: an efficient SERS substrate for detection of organic pollutants

NASA Astrophysics Data System (ADS)

Ye, Yingjie; Chen, Jin; Ding, Qianqian; Lin, Dongyue; Dong, Ronglu; Yang, Liangbao; Liu, Jinhuai

2013-06-01

Ag-coated sea-urchin-like Fe3O4@C core-shell particles can be synthesized by a facile one-step solvothermal method, followed by deposition of high-density Ag nanoparticles onto the carbon surface through an in situ growth process, respectively. The as-synthesized Ag-coated Fe3O4@C particles can be used as a surface-enhanced Raman scattering (SERS) substrate holding reproducible properties under an external magnetic force. The magnetic function of the particles allows concentrating the composite particles into small spatial regions, which can be exploited to decrease the amount of material per analysis while improving its SERS detection limit. In contrast to the traditional SERS substrates, the present Fe3O4@C@Ag particles hold the advantages of enrichment of organic pollutants for improving SERS detection limit and recycled utilization.Ag-coated sea-urchin-like Fe3O4@C core-shell particles can be synthesized by a facile one-step solvothermal method, followed by deposition of high-density Ag nanoparticles onto the carbon surface through an in situ growth process, respectively. The as-synthesized Ag-coated Fe3O4@C particles can be used as a surface-enhanced Raman scattering (SERS) substrate holding reproducible properties under an external magnetic force. The magnetic function of the particles allows concentrating the composite particles into small spatial regions, which can be exploited to decrease the amount of material per analysis while improving its SERS detection limit. In contrast to the traditional SERS substrates, the present Fe3O4@C@Ag particles hold the advantages of enrichment of organic pollutants for improving SERS detection limit and recycled utilization. Electronic supplementary information (ESI) available: Additional XRD patterns and SEM images of Fe3O4@C particles, SERS spectra of 4-ATP and 4-MPY using Fe3O4@C@Ag particles as the active substrates, magnetic behaviour of Fe3O4@C and Fe3O4@C@Ag particles. See DOI: 10.1039/c3nr01273e

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.

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.

Preparation and Raman enhancement properties of gold nanostars

NASA Astrophysics Data System (ADS)

Shan, Feng; Zhang, Tong

2018-03-01

Gold nanostars (GNSs) have a series of sharp tips structures, which will produce strong hot spots and have great application potential in Raman enhancement. In this paper, muti-tip GNSs have been prepared experimentally, and the control techniques of their tip and size have been mastered. For the first time, a fast and efficient self-assembly technique without additives has been developed, and a series of Surface Enhanced Raman Scattering (SERS) substrates have been successfully prepared by using this technique. The effect of different GNSs density of substrates on SERS signal is further studied experimentally. The results show that the SERS signal is closely related to the density of particles in the substrate. The higher density of GNSs in the substrate, the more hot spots covered by the incident light plate, and the greater contribution to the SERS signal.

In situ laser-induced photochemical silver substrate synthesis and sequential SERS detection in a flow cell.

PubMed

Herman, Krisztian; Szabó, László; Leopold, Loredana F; Chiş, Vasile; Leopold, Nicolae

2011-05-01

A new, simple, and effective approach for multianalyte sequential surface-enhanced Raman scattering (SERS) detection in a flow cell is reported. The silver substrate was prepared in situ by laser-induced photochemical synthesis. By focusing the laser on the 320 μm inner diameter glass capillary at 0.5 ml/min continuous flow of 1 mM silver nitrate and 10 mM sodium citrate mixture, a SERS active silver spot on the inner wall of the glass capillary was prepared in a few seconds. The test analytes, dacarbazine, 4-(2-pyridylazo)resorcinol (PAR) complex with Cu(II), and amoxicillin, were sequentially injected into the flow cell. Each analyte was adsorbed to the silver surface, enabling the recording of high intensity SERS spectra even at 2 s integration times, followed by desorption from the silver surface and being washed away from the capillary. Before and after each analyte passed the detection window, citrate background spectra were recorded, and thus, no "memory effects" perturbed the SERS detection. A good reproducibility of the SERS spectra obtained under flow conditions was observed. The laser-induced photochemically synthesized silver substrate enables high Raman enhancement, is characterized by fast preparation with a high success rate, and represents a valuable alternative for silver colloids as SERS substrate in flow approaches.

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.

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.

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.

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.

Gold coatings on polymer laser induced periodic surface structures: assessment as substrates for surface-enhanced Raman scattering.

PubMed

Rebollar, Esther; Sanz, Mikel; Pérez, Susana; Hernández, Margarita; Martín-Fabiani, Ignacio; Rueda, Daniel R; Ezquerra, Tiberio A; Domingo, Concepción; Castillejo, Marta

2012-12-05

We report on the fabrication of gold coated nanostructured polymer thin films and on their characterization as substrates for surface enhanced Raman spectroscopy (SERS). Laser induced periodic surface structures (LIPSS) were obtained on thin polymer films of poly(trimethylene terephthalate) (PTT) upon laser irradiation with the fourth harmonic of a Nd:YAG laser (266 nm, pulse duration 6 ns) resulting in a period close to the incident wavelength. The nanostructured polymer substrates were coated with a nanoparticle assembled gold layer by pulsed laser deposition using the fifth harmonic of a Nd:YAG laser (213 nm, pulse duration 15 ns). Different deposition times resulted in thicknesses from a few nanometres up to several tens of nanometres. Analysis by atomic force microscopy and grazing incident small angle X-ray scattering showed that gold coating preserved the LIPSS relief. The capabilities of the produced nanostructures as substrates for SERS have been investigated using benzenethiol as a test molecule. The SERS signal is substantially larger than that observed for a gold-coated flat substrate. Advantages of this new type of SERS substrates are discussed.

Multifunctional Fe3O4@SiO2-Au Satellite Structured SERS Probe for Charge Selective Detection of Food Dyes.

PubMed

Sun, Zhenli; Du, Jingjing; Yan, Li; Chen, Shu; Yang, Zhilin; Jing, Chuanyong

2016-02-10

Nanofabrication of multifunctional surface-enhanced Raman scattering (SERS) substrates is strongly desirable but currently remains a challenge. The motivation of this study was to design such a substrate, a versatile core-satellite Fe3O4@SiO2-Au (FA) hetero-nanostructure, and demonstrate its use for charge-selective detection of food dye molecules as an exemplary application. Our experimental results and three-dimensional finite difference time domain (FDTD) simulation suggest that tuning the Au nanoparticle (NP) gap to sub-10 nm, which could be readily accomplished, substantially enhanced the Raman signals. Further layer-by-layer deposition of a charged polyelectrolyte on this magnetic SERS substrate induced active adsorption and selective detection of food dye molecules of opposite charge on the substrates. Molecular dynamics (MD) simulations suggest that the selective SERS enhancement could be attributed to the high affinity and close contact (within a 20 Å range) between the substrate and molecules. Density function theory (DFT) calculations confirm the charge transfer from food dye molecules to Au NPs via the polyelectrolytes. This multifunctional SERS platform provides easy separation and selective detection of charged molecules from complex chemical mixtures.

Silver nanoparticle deposition on inverse opal SiO2 films embedded in protective polypropylene micropits for SERS applications

NASA Astrophysics Data System (ADS)

Ammosova, Lena; Ankudze, Bright; Philip, Anish; Jiang, Yu; Pakkanen, Tuula T.; Pakkanen, Tapani A.

2018-01-01

Common methods to fabricate surface enhanced Raman scattering (SERS) substrates with controlled micro-nanohierarchy are often complex and expensive. In this study, we demonstrate a simple and cost effective method to fabricate SERS substrates with complex geometries. Microworking robot structuration is used to pattern a polypropylene (PP) substrate with micropits, facilitating protective microenvironment for brittle SiO2 inverse opal (IO) structure. Hierarchical SiO2 IO patterns were obtained using polystyrene (PS) spheres as a sacrificial template, and were selectively embedded into the hydrophilized PP micropits. The same microworking robot technique was subsequently used to deposit silver nanoparticle ink into the SiO2 IO cavities. The fabricated multi-level micro-nanohierarchy surface was studied to enhance Raman scattering of the 4-aminothiophenol (4-ATP) analyte molecule. The results show that the SERS performance of the micro-nanohierarchical substrate increases significantly the Raman scattering intensity compared to substrates with structured 2D surface geometries.

Facile fabrication of microfluidic surface-enhanced Raman scattering devices via lift-up lithography

NASA Astrophysics Data System (ADS)

Wu, Yuanzi; Jiang, Ye; Zheng, Xiaoshan; Jia, Shasha; Zhu, Zhi; Ren, Bin; Ma, Hongwei

2018-04-01

We describe a facile and low-cost approach for a flexibly integrated surface-enhanced Raman scattering (SERS) substrate in microfluidic chips. Briefly, a SERS substrate was fabricated by the electrostatic assembling of gold nanoparticles, and shaped into designed patterns by subsequent lift-up soft lithography. The SERS micro-pattern could be further integrated within microfluidic channels conveniently. The resulting microfluidic SERS chip allowed ultrasensitive in situ SERS monitoring from the transparent glass window. With its advantages in simplicity, functionality and cost-effectiveness, this method could be readily expanded into optical microfluidic fabrication for biochemical applications.

Surface-Enhanced Raman Scattering (SERS) for Detection in Immunoassays. Applications, fundamentals, and optimization

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

Driskell, Jeremy Daniel

2006-08-09

Immunoassays have been utilized for the detection of biological analytes for several decades. Many formats and detection strategies have been explored, each having unique advantages and disadvantages. More recently, surface-enhanced Raman scattering (SERS) has been introduced as a readout method for immunoassays, and has shown great potential to meet many key analytical figures of merit. This technology is in its infancy and this dissertation explores the diversity of this method as well as the mechanism responsible for surface enhancement. Approaches to reduce assay times are also investigated. Implementing the knowledge gained from these studies will lead to a more sensitivemore » immunoassay requiring less time than its predecessors. This dissertation is organized into six sections. The first section includes a literature review of the previous work that led to this dissertation. A general overview of the different approaches to immunoassays is given, outlining the strengths and weaknesses of each. Included is a detailed review of binding kinetics, which is central for decreasing assay times. Next, the theoretical underpinnings of SERS is reviewed at its current level of understanding. Past work has argued that surface plasmon resonance (SPR) of the enhancing substrate influences the SERS signal; therefore, the SPR of the extrinsic Raman labels (ERLs) utilized in our SERS-based immunoassay is discussed. Four original research chapters follow the Introduction, each presented as separate manuscripts. Chapter 2 modifies a SERS-based immunoassay previously developed in our group, extending it to the low-level detection of viral pathogens and demonstrating its versatility in terms of analyte type, Chapter 3 investigates the influence of ERL size, material composition, and separation distance between the ERLs and capture substrate on the SERS signal. This chapter links SPR with SERS enhancement factors and is consistent with many of the results from theoretical treatments of SPR and SERS. Chapter 4 introduces a novel method of reducing sample incubation time via capture substrate rotation. Moreover, this work led to a method of virus quantification without the use of standards. Chapter 5 extends the methodology developed in Chapter 4 to both the antigen and ERL labeling step to perform assays with improved analytical performance in less time than can be accomplished in diffusion controlled assays. This dissertation concludes with a general summary and speculates on the future of this exciting approach to carrying out immunoassays.« less

A novel bifunctional Ni-doped TiO2 inverse opal with enhanced SERS performance and excellent photocatalytic activity

NASA Astrophysics Data System (ADS)

Li, Xuehong; Wu, Yun; Shen, Yuhua; Sun, Yan; Yang, Ying; Xie, Anjian

2018-01-01

Three-dimensional inverse opal photonic microarray (IOPM) structure exhibits good qualities in structural regularity and interconnectivity, such as high specific surface area, large pore volume, uniform pore size, and ordered periodic construction. Here, a novel nickel-doped titanium dioxide IOPM (Ni-TiO2 IOPM) was fabricated for the first time as a bifunctional material for the applications of surface-enhanced Raman scattering (SERS) substrate and photocatalyst. The Ni doping could change the defect concentration of the substrate to enhance the SERS effect, and could increase the light absorption of the substrate in visible region. The synergistic effect of Ni doping and the periodically ordered porous structure enhanced both SERS sensitivity and photocatalytic activity. As a SERS substrate, the Ni-TiO2 IOPM exhibited highly sensitive detection capability for 4-mercaptobenzoic acid (4-MBA) at a concentration as low as 1 × 10-11 M. Under simulated sunlight, about 95% of the methylene blue (MB) was degraded within 90 min when Ni-TiO2 IOPM was used as the photocatalytst. The Ni-TiO2 IOPM prepared in this work may be a promising bifunctional SERS substrate candidate for organic sewage detection and environment protection. In addition, the fabrication strategy can be extended to synthesize other nanomaterials with orderly and porous structure.

Incorporation of multilayered silver nanoparticles into polymer brushes as 3-dimensional SERS substrates and their application for bacteria detection

NASA Astrophysics Data System (ADS)

Zhang, Qian; Wang, Xiang-Dong; Tian, Ting; Chu, Li-Qiang

2017-06-01

Surface-enhanced Raman scattering (SERS) sensors have been extensively studied for ultrasensitive detection of diverse chemical or biological analytes. Facile fabrication of highly sensitive SERS substrates is believed to be of crucial importance in these analytical applications. In this regard, the preparation of 3-dimensional (3D) SERS substrates are explored via the incorporation of multilayered silver nanoparticles (AgNPs) into poly (oligo(ethylene glycol) methacrylate) (POEGMA) brushes by repeating the immersion-rinsing-drying steps for different lengths of time (i.e., the so-called in-stacking method). The POEGMA brushes of different chain lengths are synthesized by surface-initiated atom transfer radical polymerization (ATRP) with various reaction time. The resulting POEGMA/AgNP nanocomposites are characterized by FE-SEM, UV-vis and Raman spectroscopy. FE-SEM and UV-vis results indicate that the AgNPs are successfully incorporated into the POEGMA brushes with a 3D configuration. The nanocomposite films are employed as SERS substrates for the detection of a Raman reporter molecule (i.e., 4-aminothiophenol), giving rise to an enhancement factor of up to 1.29 × 107 and also having relatively good uniformity and reproducibility. The obtained 3D SERS substrates are also used for the detection of a typical gram-positive bacterium, Staphylococcus aureus. The limit of detection is found to be as low as ca. 8 CFU/mL.

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.

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.

Preparation of surface enhanced Raman substrate and its characterization

NASA Astrophysics Data System (ADS)

Liu, Y.; Wang, J. Y.; Wang, J. Q.

2017-10-01

Surface enhanced Raman spectroscopy (SERS) is a fast, convenient and highly sensitive detection technique, and preparing the good effect and repeatable substrate is the key to realize the trace amount and quantitative detection in the field of food safety detection. In this paper, a surface enhanced Raman substrate based on submicrometer silver particles structure was prepared by chemical deposition method, and characterized its structure and optical properties.

Nanofabrication of densely packed metal-polymer arrays for surface-enhanced Raman spectrometry.

PubMed

De Jesús, M A; Giesfeldt, K S; Oran, J M; Abu-Hatab, N A; Lavrik, N V; Sepaniak, M J

2005-12-01

A key element to improve the analytical capabilities of surface-enhanced Raman spectroscopy (SERS) resides in the performance characteristics of the SERS-active substrate. Variables such as shape, size, and homogeneous distribution of the metal nanoparticles throughout the substrate surface are important in the design of more analytically sensitive and reliable substrates. Electron-beam lithography (EBL) has emerged as a powerful tool for the systematic fabrication of substrates with periodic nanoscale features. EBL also allows the rational design of nanoscale features that are optimized to the frequency of the Raman laser source. In this work, the efficiency of EBL fabricated substrates are studied by measuring the relative SERS signals of Rhodamine 6G and 1,10-phenanthro-line adsorbed on a series of cubic, elliptical, and hexagonal nanopatterned pillars of ma-N 2403 directly coated by physical vapor deposition with 25 nm films of Ag or Au. The raw analyte SERS signals, and signals normalized to metal nanoparticle surface area or numbers of loci, are used to study the effects of nanoparticle morphology on the performance of a rapidly created, diverse collection of substrates. For the excitation wavelength used, the nanoparticle size, geometry, and orientation of the particle primary axis relative to the excitation polarization vector, and particularly the density of nanoparticles, are shown to strongly influence substrate performance. A correlation between the inverse of the magnitude of the laser backscatter passed by the spectrometer and SERS activities of the various substrate patterns is also noted and provides a simple means to evaluate possible efficient coupling of the excitation radiation to localized surface plasmons for Raman enhancement.

Nanotextured thin films for detection of chemicals by surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Korivi, Naga; Jiang, Li; Ahmed, Syed; Nujhat, Nabila; Idrees, Mohanad; Rangari, Vijaya

2017-11-01

We report on the development of large area, nanostructured films that function as substrates for surface enhanced Raman scattering (SERS) detection of chemicals. The films are made of polyethylene terephthalate layers partially embedded with multi-walled carbon nanotubes and coated with a thin layer of gold. The films are fabricated by a facile method involving spin-coating, acid dip, and magnetron sputtering. The films perform effectively as SERS substrates when used in the detection of dye pollutants such as Congo red dye, with an enhancement factor of 1.1  ×  106 and a detection limit of 10-7 M which is the lowest reported for CR detection by freestanding SERS film substrates. The films have a long shelf life, and cost US0.20 per cm2 of active area, far less than commercially available SERS substrates. This is the first such work on the use of a polymer layer modified with carbon nanotubes to create a nano-scale texture and arbitrary ‘hot-spots’, contributing to the SERS effect.

SERS activity of Ag decorated nanodiamond and nano-β-SiC, diamond-like-carbon and thermally annealed diamond thin film surfaces.

PubMed

Kuntumalla, Mohan Kumar; Srikanth, Vadali Venkata Satya Siva; Ravulapalli, Satyavathi; Gangadharini, Upender; Ojha, Harish; Desai, Narayana Rao; Bansal, Chandrahas

2015-09-07

In the recent past surface enhanced Raman scattering (SERS) based bio-sensing has gained prominence owing to the simplicity and efficiency of the SERS technique. Dedicated and continuous research efforts have been made to develop SERS substrates that are not only stable, durable and reproducible but also facilitate real-time bio-sensing. In this context diamond, β-SiC and diamond-like-carbon (DLC) and other related thin films have been promoted as excellent candidates for bio-technological applications including real time bio-sensing. In this work, SERS activities of nanodiamond, nano-β-SiC, DLC, thermally annealed diamond thin film surfaces were examined. DLC and thermally annealed diamond thin films were found to show SERS activity without any metal nanostructures on their surfaces. The observed SERS activities of the considered surfaces are explained in terms of the electromagnetic enhancement mechanism and charge transfer resonance process.

Surface-Enhanced Raman Spectroscopy for Staphylococcus aureus DNA Detection by Using Surface-Enhanced Raman Scattering Tag on Au Film Over Nanosphere Substrate.

PubMed

Chen, Jian; Wang, Jun-Feng; Wu, Xue-Zhong; Rong, Zhen; Dong, Pei-Tao; Xiao, Rui

2018-06-01

We developed a high-performance surface-enhanced Raman scattering (SERS) sensing platform that can be used for specific and sensitive DNA detection. The SERS platform combines the advantages of Au film over nanosphere (AuFON) substrate and Ag@PATP@SiO2 SERS tag. SERS tag-on-AuFON is a sensing system that operates by the self-assembly of SERS tag onto an AuFON substrate in the presence of target DNAs. The SERS signals can be dramatically enhanced by the formation of "hot spots" in the interstices between the assembled nanostructures, as confirmed by finite-difference time-domain (FDTD) simulation. As a new sensing platform, SERS tag-on-AuFON was utilized to detect Staphylococcus aureus (S. aureus) DNA with a limit of detection at 1 nM. A linear relationship was also observed between the SERS intensity at Raman peak 1439 cm-1 and the logarithm of target DNA concentrations ranging from 1 μM to 1 nM. Besides, the sensing platform showed good homogeneity, with a relative standard deviation of about 1%. The sensitive SERS platform created in this study is a promising tool for detecting trace biochemical molecules because of its relatively simple and effective fabrication procedure, high sensitivity, and high reproducibility of the SERS effect.

A New Smart Surface-Enhanced Raman Scattering Sensor Based on pH-Responsive Polyacryloyl Hydrazine Capped Ag Nanoparticles.

PubMed

Yuan, Shuai; Ge, Fengyan; Zhou, Man; Cai, Zaisheng; Guang, Shanyi

2017-08-14

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.

Microfluidic chip based micro RNA detection through the combination of fluorescence and surface enhanced Raman scattering techniques

NASA Astrophysics Data System (ADS)

Wang, Zhile; Zong, Shenfei; Wang, Zhuyuan; Wu, Lei; Chen, Peng; Yun, Binfeng; Cui, Yiping

2017-03-01

We present a novel microfluidic chip based method for the detection of micro RNA (miRNA) via the combination of fluorescence and surface enhanced Raman scattering (SERS) spectroscopies. First, silver nanoparticles (Ag NPs) are immobilized onto a glass slide, forming a SERS enhancing substrate. Then a specificially designed molecular beacon (MB) is attached to the SERS substrate. The 3‧ end of the MB is decorated with a thiol group to facilitate the attachment of the MB, while the 5‧ end of the MB is labeled with an organic dye 6-FAM, which is used both as the fluorophore and SERS reporter. In the absence of target miRNA, the MB will form a hairpin structure, making 6-FAM close to the Ag NPs. Hence, the fluorescence of 6-FAM will be quenched and the Raman signal of 6-FAM will be enhanced. On the contrary, with target miRNA present, hybridization between the miRNA and MB will unfold the MB and increase the distance between 6-FAM and the Ag NPs. Thus the fluorescence of 6-FAM will recover and the SERS signal of 6-FAM will decrease. So the target miRNA will simultaneously introduce opposite changing trends in the intensities of the fluorescence and SERS signals. By combining the opposite changes in the two optical spectra, an improved sensitivity and linearity toward the target miRNA is achieved as compared with using solely fluorescence or SERS. Moreover, introducing the microfluidic chip can reduce the reaction time, reagent dosage and complexity of detection. With the improved sensitivity and simplicity, we anticipate that the presented method can have great potential in the investigation of miRNA related diseases.

Ultrasensitive SERS Flow Detector Using Hydrodynamic Focusing

PubMed Central

Negri, Pierre; Jacobs, Kevin T.; Dada, Oluwatosin O.; Schultz, Zachary D.

2013-01-01

Label-free, chemical specific detection in flow is important for high throughput characterization of analytes in applications such as flow injection analysis, electrophoresis, and chromatography. We have developed a surface-enhanced Raman scattering (SERS) flow detector capable of ultrasensitive optical detection on the millisecond time scale. The device employs hydrodynamic focusing to improve SERS detection in a flow channel where a sheath flow confines analyte molecules eluted from a fused silica capillary over a planar SERS-active substrate. Increased analyte interactions with the SERS substrate significantly improve detection sensitivity. The performance of this flow detector was investigated using a combination of finite element simulations, fluorescence imaging, and Raman experiments. Computational fluid dynamics based on finite element analysis was used to optimize the flow conditions. The modeling indicates that a number of factors, such as the capillary dimensions and the ratio of the sheath flow to analyte flow rates, are critical for obtaining optimal results. Sample confinement resulting from the flow dynamics was confirmed using wide-field fluorescence imaging of rhodamine 6G (R6G). Raman experiments at different sheath flow rates showed increased sensitivity compared with the modeling predictions, suggesting increased adsorption. Using a 50-millisecond acquisitions, a sheath flow rate of 180 μL/min, and a sample flow rate of 5 μL/min, a linear dynamic range from nanomolar to micromolar concentrations of R6G with a LOD of 1 nM is observed. At low analyte concentrations, rapid analyte desorption is observed, enabling repeated and high-throughput SERS detection. The flow detector offers substantial advantages over conventional SERS-based assays such as minimal sample volumes and high detection efficiency. PMID:24074461

M13 Bacteriophage/Silver Nanowire Surface-Enhanced Raman Scattering Sensor for Sensitive and Selective Pesticide Detection.

PubMed

Koh, Eun Hye; Mun, ChaeWon; Kim, ChunTae; Park, Sung-Gyu; Choi, Eun Jung; Kim, Sun Ho; Dang, Jaejeung; Choo, Jaebum; Oh, Jin-Woo; Kim, Dong-Ho; Jung, Ho Sang

2018-03-28

A surface-enhanced Raman scattering (SERS) sensor comprising silver nanowires (AgNWs) and genetically engineered M13 bacteriophages expressing a tryptophan-histidine-tryptophan (WHW) peptide sequence (BPWHW) was fabricated by simple mixing of BPWHW and AgNW solutions, followed by vacuum filtration onto a glass-fiber filter paper (GFFP) membrane. The AgNWs stacked on the GFFP formed a high density of SERS-active hot spots at the points of nanowire intersections, and the surface-coated BPWHW functioned as a bioreceptor for selective pesticide detection. The BPWHW-functionalized AgNW (BPWHW/AgNW) sensor was characterized by scanning electron microscopy, confocal scanning fluorescence microscopy, atomic force microscopy, and Fourier transform infrared spectroscopy. The Raman signal enhancement and the selective pesticide SERS detection properties of the BPWHW/AgNW sensor were investigated in the presence of control substrates such as wild-type M13 bacteriophage-decorated AgNWs (BPWT/AgNW) and undecorated AgNWs (AgNW). The BPWHW/AgNW sensor exhibited a significantly higher capture capability for pesticides, especially paraquat (PQ), than the control SERS substrates, and it also showed a relatively higher selectivity for PQ than for other bipyridylium pesticides such as diquat and difenzoquat. Furthermore, as a field application test, PQ was detected on the surface of PQ-pretreated apple peels, and the results demonstrated the feasibility of using a paper-based SERS substrate for on-site residual pesticide detection. The developed M13 bacteriophage-functionalized AgNW SERS sensor might be applicable for the detection of various pesticides and chemicals through modification of the M13 bacteriophage surface peptide sequence.

Sensitive SERS detection of DNA methyltransferase by target triggering primer generation-based multiple signal amplification strategy.

PubMed

Li, Ying; Yu, Chuanfeng; Han, Huixia; Zhao, Caisheng; Zhang, Xiaoru

2016-07-15

A novel and sensitive surface-enhanced Raman scattering (SERS) method is proposed for the assay of DNA methyltransferase (MTase) activity and evaluation of inhibitors by developing a target triggering primer generation-based multiple signal amplification strategy. By using of a duplex substrate for Dam MTase, two hairpin templates and a Raman probe, multiple signal amplification mode is achieved. Once recognized by Dam MTase, the duplex substrate can be cleaved by Dpn I endonuclease and two primers are released for triggering the multiple signal amplification reaction. Consequently, a wide dynamic range and remarkably high sensitivity are obtained under isothermal conditions. The detection limit is 2.57×10(-4)UmL(-1). This assay exhibits an excellent selectivity and is successfully applied in the screening of inhibitors for Dam MTase. In addition, this novel sensing system is potentially universal as the recognition element can be conveniently designed for other target analytes by changing the substrate of DNA MTase. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface enhanced Raman spectroscopy analysis of HeLa cells using a multilayer substrate

NASA Astrophysics Data System (ADS)

Aguilar-Hernández, I. A.; Pichardo-Molina, J. L.; Lopez-Luke, T.; Ornelas-Soto, N.

2017-08-01

Single cell analysis can provide important information regarding cell composition, and can be used for biomedical applications. In this work, a SERS active substrate formed by 3 layers of gold nanospheres and a final layer of gold nanocubes was used for the label-free SERS analysis of HeLa cells. Nanocubes were selected due to the high electromagnetic enhancement expected in nanoparticles with sharp corners. Significant improvement in the reproducibility and quality of SERS spectra was found when compared to the spectra obtained using a nanosphere-only substrate and normal Raman spectroscopy.

Sub-100 nm gold nanohole-enhanced Raman scattering on flexible PDMS sheets.

PubMed

Lee, Seunghyun; Ongko, Andry; Kim, Ho Young; Yim, Sang-Gu; Jeon, Geumhye; Jeong, Hee Jin; Lee, Seungwoo; Kwak, Minseok; Yang, Seung Yun

2016-08-05

Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive vibrational spectroscopy technique enabling detection of multiple analytes at the molecular level in a nondestructive and rapid manner. In this work, we introduce a new approach to fabricate deep subwavelength-scaled (sub-100 nm) metallic nanohole arrays (quasi-3D metallic nanoholes) on flexible and highly efficient SERS substrates. Target structures have been fabricated using a two-step process consisting of (i) direct pattern transfer of spin-coated polymer films onto polydimethylsiloxane (PDMS) substrates by plasma etching with transferred anodic aluminum oxide masks, and (ii) producing SERS-active substrates by functionalization of the etched polymeric films followed by Au deposition. Such an all-dry, top-down lithographic approach enables on-demand patterning of SERS-active metallic nanoholes with high structural fidelity even onto flexible and stretchable substrates, thus making possible multiple sensing modes in a versatile fashion. For example, metallic nanoholes on flexible PDMS substrates are highly amenable to their integration with curved glass sticks, which can be used in optical fiber-integrated SERS systems. Au surfaces immobilized by probe DNA molecules show a selective enhancement of Raman scattering with Cy5-labeled complementary DNA (as compared to flat Au surfaces), demonstrating the potential of using the quasi-3D Au nanohole arrays for bio-sensing applications.

Sub-100 nm gold nanohole-enhanced Raman scattering on flexible PDMS sheets

NASA Astrophysics Data System (ADS)

Lee, Seunghyun; Ongko, Andry; Kim, Ho Young; Yim, Sang-Gu; Jeon, Geumhye; Jeong, Hee Jin; Lee, Seungwoo; Kwak, Minseok; Yang, Seung Yun

2016-08-01

Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive vibrational spectroscopy technique enabling detection of multiple analytes at the molecular level in a nondestructive and rapid manner. In this work, we introduce a new approach to fabricate deep subwavelength-scaled (sub-100 nm) metallic nanohole arrays (quasi-3D metallic nanoholes) on flexible and highly efficient SERS substrates. Target structures have been fabricated using a two-step process consisting of (i) direct pattern transfer of spin-coated polymer films onto polydimethylsiloxane (PDMS) substrates by plasma etching with transferred anodic aluminum oxide masks, and (ii) producing SERS-active substrates by functionalization of the etched polymeric films followed by Au deposition. Such an all-dry, top-down lithographic approach enables on-demand patterning of SERS-active metallic nanoholes with high structural fidelity even onto flexible and stretchable substrates, thus making possible multiple sensing modes in a versatile fashion. For example, metallic nanoholes on flexible PDMS substrates are highly amenable to their integration with curved glass sticks, which can be used in optical fiber-integrated SERS systems. Au surfaces immobilized by probe DNA molecules show a selective enhancement of Raman scattering with Cy5-labeled complementary DNA (as compared to flat Au surfaces), demonstrating the potential of using the quasi-3D Au nanohole arrays for bio-sensing applications.

Efficient surface enhanced Raman scattering on confeito-like gold nanoparticle-adsorbed self-assembled monolayers.

PubMed

Chang, Chia-Chi; Imae, Toyoko; Chen, Liang-Yih; Ujihara, Masaki

2015-12-28

Confeito-like gold nanoparticles (AuNPs; average diameter = 80 nm) exhibiting a plasmon absorption band at 590 nm were adsorbed through immersion-adsorption on two self-assembled monolayers (SAMs) of 3-aminopropyltriethoxysilane (APTES-SAM) and polystyrene spheres coated with amine-terminated poly(amido amine) dendrimers (DEN/PS-SAM). The surface enhanced Raman scattering (SERS) effect on the SAM substrates was examined using the molecules of a probe dye, rhodamine 6G (R6G). The Raman scattering was strongly intensified on both substrates, but the enhancement factor (>10,000) of the AuNP/DEN/PS-SAM hierarchy substrate was 5-10 times higher than that of the AuNP/APTES-SAM substrate. This strong enhancement is attributed to the large surface area of the substrate and the presence of hot spots. Furthermore, analyzing the R6G concentration dependence of SERS suggested that the enhancement mechanism effectively excited the R6G molecules in the first layer on the hot spots and invoked the strong SERS effect. These results indicate that the SERS activity of confeito-like AuNPs on SAM substrates has high potential in molecular electronic devices and ultrasensitive analyses.

Rapid, controllable growth of silver nanostructured surface-enhanced Raman scattering substrates for red blood cell detection

NASA Astrophysics Data System (ADS)

Zhang, Shu; Tian, Xueli; Yin, Jun; Liu, Yu; Dong, Zhanmin; Sun, Jia-Lin; Ma, Wanyun

2016-04-01

Silver nanostructured films suitable for use as surface-enhanced Raman scattering (SERS) substrates are prepared in just 2 hours by the solid-state ionics method. By changing the intensity of the external direct current, we can readily control the surface morphology and growth rate of the silver nanostructured films. A detailed investigation of the surface enhancement of the silver nanostructured films using Rhodamine 6G (R6G) as a molecular probe revealed that the enhancement factor of the films was up to 1011. We used the silver nanostructured films as substrates in SERS detection of human red blood cells (RBCs). The SERS spectra of RBCs on the silver nanostructured film could be clearly detected at a laser power of just 0.05 mW. Comparison of the SERS spectra of RBCs obtained from younger and older donors showed that the SERS spectra depended on donor age. A greater proportion of the haemoglobin in the RBCs of older donors was in the deoxygenated state than that of the younger donors. This implies that haemoglobin of older people has lower oxygen-carrying capacity than that of younger people. Overall, the fabricated silver substrates show promise in biomedical SERS spectral detection.

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.

Sensitive SERS-pH sensing in biological media using metal carbonyl functionalized planar substrates.

PubMed

Kong, Kien Voon; Dinish, U S; Lau, Weber Kam On; Olivo, Malini

2014-04-15

Conventional nanoparticle based Surface enhanced Raman scattering (SERS) technique for pH sensing often fails due to the aggregation of particles when detecting in acidic medium or biosamples having high ionic strength. Here, We develop SERS based pH sensing using a novel Raman reporter, arene chromium tricarbonyl linked aminothiophenol (Cr(CO)3-ATP), functionalized onto a nano-roughened planar substrates coated with gold. Unlike the SERS spectrum of the ATP molecule that dominates in the 400-1700 cm(-1) region, which is highly interfered by bio-molecules signals, metal carbonyl-ATP (Cr(CO)3)-ATP) offers the advantage of monitoring the pH dependent strong CO stretching vibrations in the mid-IR (1800-2200 cm(-1)) range. Raman signal of the CO stretching vibrations at ~1820 cm(-1) has strong dependency on the pH value of the environment, where its peak undergo noticeable shift as the pH of the medium is varied from 3.0 to 9.0. The sensor showed better sensitivity in the acidic range of the pH. We also demonstrate the pH sensing in a urine sample, which has high ionic strength and our data closely correlate to the value obtained from conventional sensor. In future, this study may lead to a sensitive chip based pH sensing platform in bio-fluids for the early diagnosis of diseases. © 2013 Published by Elsevier B.V.

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.

Magnetically optimized SERS assay for rapid detection of trace drug-related biomarkers in saliva and fingerprints.

PubMed

Yang, Tianxi; Guo, Xiaoyu; Wang, Hui; Fu, Shuyue; Wen, Ying; Yang, Haifeng

2015-06-15

New developments in the fields of human healthcare and social security call for the exploration of an easy and on-field method to detect drug-related biomarkers. In this paper, Au nanoparticles dotted magnetic nanocomposites (AMN) modified with inositol hexakisphosphate (IP6) were used as surface-enhanced Raman scattering (SERS) substrate to quickly monitor trace drug-related biomarkers in saliva and to on-site screen a trace drug biomarker in fingerprints. Due to inducing with an external magnet, such substrate presented a huge SERS activity, which has met the sensitivity requirement for assay to detect the drug biomarkers in saliva from the U.S. Substance Abuse and Mental Health Services Administration, and also the limit of detection for drug biomarker in fingerprint reached 100 nM. In addition, this AMN-based SERS assay was successfully conducted using a portable Raman spectrometer, which could be used to on-site and accurately differentiate between the smokers and drug addicts in near future. Copyright © 2015 Elsevier B.V. All rights reserved.

Extended domains of organized nanorings of silver grains as surface-enhanced Raman scattering sensors for molecular detection

NASA Astrophysics Data System (ADS)

Bechelany, M.; Brodard, P.; Philippe, L.; Michler, J.

2009-11-01

The possibility to synthesize large areas of silver grains organized in nanorings using a simple technique based on nanosphere lithography and electroless plating as a metal deposition method is described for the first time. In addition, we present a systematic SERS study of the obtained long-range ordered silver nanodots and nanorings. The possibility to precisely control the size, the interdistance and the morphology of these nanostructures allows us to systematically investigate the influence of these parameters on SERS. We show that the best possible SERS substrates should not only present optimal sizes, interdistances and shapes, but also a grain-like structure composed of sub-100 nm grains in order to maximize the number of hot-spots. In addition, we show that grains arranged in nanorings present higher enhancement factors (EF = 5.5 × 105) as compared to similar arrays made of nanodots. A wide range of applications, including real-time monitoring of catalytic surface reactions, environmental and security monitoring as well as clinical and pharmaceutical screening, can be envisaged for these SERS substrates.

Extended domains of organized nanorings of silver grains as surface-enhanced Raman scattering sensors for molecular detection.

PubMed

Bechelany, M; Brodard, P; Philippe, L; Michler, J

2009-11-11

The possibility to synthesize large areas of silver grains organized in nanorings using a simple technique based on nanosphere lithography and electroless plating as a metal deposition method is described for the first time. In addition, we present a systematic SERS study of the obtained long-range ordered silver nanodots and nanorings. The possibility to precisely control the size, the interdistance and the morphology of these nanostructures allows us to systematically investigate the influence of these parameters on SERS. We show that the best possible SERS substrates should not only present optimal sizes, interdistances and shapes, but also a grain-like structure composed of sub-100 nm grains in order to maximize the number of hot-spots. In addition, we show that grains arranged in nanorings present higher enhancement factors (E(F) = 5.5 x 10(5)) as compared to similar arrays made of nanodots. A wide range of applications, including real-time monitoring of catalytic surface reactions, environmental and security monitoring as well as clinical and pharmaceutical screening, can be envisaged for these SERS substrates.

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.

Electrochemical Fabrication of Nanostructures on Porous Silicon for Biochemical Sensing Platforms.

PubMed

Ko, Euna; Hwang, Joonki; Kim, Ji Hye; Lee, Joo Heon; Lee, Sung Hwan; Tran, Van-Khue; Chung, Woo Sung; Park, Chan Ho; Choo, Jaebum; Seong, Gi Hun

2016-01-01

We present a method for the electrochemical patterning of gold nanoparticles (AuNPs) or silver nanoparticles (AgNPs) on porous silicon, and explore their applications in: (1) the quantitative analysis of hydroxylamine as a chemical sensing electrode and (2) as a highly sensitive surface-enhanced Raman spectroscopy (SERS) substrate for Rhodamine 6G. For hydroxylamine detection, AuNPs-porous silicon can enhance the electrochemical oxidation of hydroxylamine. The current changed linearly for concentrations ranging from 100 μM to 1.32 mM (R(2) = 0.995), and the detection limit was determined to be as low as 55 μM. When used as SERS substrates, these materials also showed that nanoparticles decorated on porous silicon substrates have more SERS hot spots than those decorated on crystalline silicon substrates, resulting in a larger SERS signal. Moreover, AgNPs-porous silicon provided five-times higher signal compared to AuNPs-porous silicon. From these results, we expect that nanoparticles decorated on porous silicon substrates can be used in various types of biochemical sensing platforms.

Gold sputtered Blu-Ray disks as novel and cost effective sensors for surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Nieuwoudt, Michél. K.; Martin, Jacob W.; Oosterbeek, Reece N.; Novikova, Nina I.; Wang, Xindi; Malmström, Jenny; Williams, David E.; Simpson, M. C.

2015-03-01

Surface Enhanced Raman spectroscopy (SERS) offers sensitive and non-invasive detection of a variety of compounds as well as unparalleled information for establishing the molecular identity of both inorganic and organic compounds, not only in biological fluids but in all other aqueous and non-aqueous media. The localized hotspots produced through SERS at the solution/nanostructure interface of clustered gold or silver nano-particles enables detection levels of parts per trillion. Recent developments in advanced fabrication methods have enabled the manufacture of SERS substrates with repeatable surface nanostructures which provide reproducible quantitative analysis, historically a weakness of the SERS technique. In this paper we describe the novel use of gold sputtered Blu-Ray surfaces as SERS substrates. Blu-Ray disks provide ideal surfaces of SERS substrates with their repeatable and regular nano-gratings. We show that the unique surface features and composition of the recording surface enables the formation of gold nano-islands with nanogaps, simply through gold sputtering, and relate this to a 600 fold signal increase of the melamine Raman signal in aqueous solutions and detection to 68 ppb. Melamine is a triazine compound and appears not only as environmental contaminant in environmental groundwater but also as an adulterant in foods due to its high nitrogen content. We have shown significant SERS signal enhancements for spectra of melamine using gold-sputtered Blu-Ray disk surfaces, with reproducibility of 12%. Blu-Ray disks have a unique combination of design, surface features and composition of the recording surface which makes them ideal for preparation of SERS substrates by gold sputter-coating.

On-chip ultra-thin layer chromatography and surface enhanced Raman spectroscopy.

PubMed

Chen, Jing; Abell, Justin; Huang, Yao-wen; Zhao, Yiping

2012-09-07

We demonstrate that silver nanorod (AgNR) array substrates can be used for on-chip separation and detection of chemical mixtures by combining ultra-thin layer chromatography (UTLC) and surface enhanced Raman spectroscopy (SERS). The UTLC-SERS plate consists of an AgNR array fabricated by oblique angle deposition. The capability of the AgNR substrates to separate the different compounds in a mixture was explored using a mixture of four dyes and a mixture of melamine and Rhodamine 6G at varied concentrations with different mobile phase solvents. After UTLC separation, spatially-resolved SERS spectra were collected along the mobile phase development direction and the intensities of specific SERS peaks from each component were used to generate chromatograms. The AgNR substrates demonstrate the potential for separating the test dyes with plate heights as low as 9.6 μm. The limits of detection are between 10(-5)-10(-6) M. Furthermore, we show that the coupling of UTLC with SERS improves the SERS detection specificity, as small amounts of target analytes can be separated from the interfering background components.

Potential application of SERS for arsenic speciation in biological matrices.

PubMed

Yang, Mingwei; Matulis, Shannon; Boise, Lawrence H; McGoron, Anthony J; Cai, Yong

2017-08-01

Speciation of arsenic is usually carried out using chromatography-based methods coupled with spectroscopic determination; however, the inevitable procedures involving sample preparation and separation could potentially alter the integrity of the arsenic metabolites present in biological samples. Surface-enhanced Raman spectroscopy (SERS) could be a promising alternative for providing a reliable arsenic analysis under the influence of a cellular matrix. A method for arsenic speciation using SERS in cellular matrix was developed in this study and four arsenicals were selected, including arsenite (As III ), arsenate (As V ), monomethylarsonic acid (MMA V ) and dimethylarsinic acid (DMA V ). Silver nanoparticles in the form of colliodal suspension with different surface charges, i.e., coated with citrate (AgNPs-Citrate) and spermine (AgNPs-Spermine) were employed as SERS substrates. Adsorption of arsenicals on nanoparticles in colloidal suspensions and the cellular matrix and the pH, size, and zeta potential of the colloidal suspensions were investigated for a better understanding of the SERS signal response of arsenicals in the colloidal suspensions or under the influence of cellular matrix. Arsenicals showed substantially different SERS responses in the two colloidal suspensions, mainly because of the distinct difference in the interaction between the arsenicals and the nanoparticles. Arsenic speciation in cell lysate could be successfully carried out in AgNPs-Spermine suspension, while AgNPs-Citrate could not yield significant SERS signals under the experimental conditions. This study proved that AgNPs-Spermine colloidal suspension could be a promising SERS substrate for studying arsenic metabolism in a biological matrix, reducing the bias caused by traditional techniques that involve sample extraction and pretreatment.

Improved galvanic replacement growth of Ag microstructures on Cu micro-grid for enhanced SERS detection of organic molecules.

PubMed

Guo, Tian-Long; Li, Ji-Guang; Sun, Xudong; Sakka, Yoshio

2016-04-01

Galvanic growth of Ag nano/micro-structures on Cu micro-grid was systematically studied for surface-enhanced Raman scattering (SERS) applications. Detailed characterizations via FE-SEM and HR-TEM showed that processing parameters, (reaction time, Ag(+) concentration, and PVP addition) all substantially affect thermodynamics/kinetics of the replacement reaction to yield substrates of significantly different microstructures/homogeneities and thus varied SERS performances (sensitivity, enhancement factor, and reproducibility) of the Ag substrates in the detection of R6G analyte. PVP as an additive was shown to notably alter nucleation/growth behaviors of the Ag crystals and promote the deposition of dense and uniform Ag films of nearly monodisperse polyhedrons/nanoplates through suppressing dendrites crystallization. Under optimized synthesis (50mM of Ag(+), 30s of reaction, and 700 wt.% of PVP), Ag substrates exhibiting a high Raman signal enhancement factor of ~1.1 × 10(6) and a low relative standard deviation of ~0.13 in the repeated detection of 10 μM R6G were obtained. The facile deposition and excellent performance reported in this work may allow the Ag microstructures to find wider SERS applications. Moreover, growth mechanisms of the different Ag nano/micro-structures were discussed based on extensive FE-SEM and HR-TEM analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

Plasmonic nanostructures for bioanalytical applications of SERS

NASA Astrophysics Data System (ADS)

Kahraman, Mehmet; Wachsmann-Hogiu, Sebastian

2016-03-01

Surface-enhanced Raman scattering (SERS) is a potential analytical technique for the detection and identification of chemicals and biological molecules and structures in the close vicinity of metallic nanostructures. We present a novel method to fabricate tunable plasmonic nanostructures and perform a comprehensive structural and optical characterization of the structures. Spherical latex particles are uniformly deposited on glass slides and used as templates to obtain nanovoid structures on polydimethylsiloxane surfaces. The diameter and depth of the nanovoids are controlled by the size of the latex particles. The nanovoids are coated with a thin Ag layer for fabrication of uniform plasmonic nanostructures. Structural characterization of the surfaces is performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Optical properties of these plasmonic nanostructures are evaluated via UV/Vis spectroscopy, and SERS. The sample preparation step is the key point to obtain strong and reproducible SERS spectra from the biological structures. When the colloidal suspension is used as a SERS substrate for the protein detection, the electrostatic interaction of the proteins with the nanoparticles is described by the nature of their charge status, which influences the aggregation properties such as the size and shape of the aggregates, which is critical for the SERS experiment. However, when the solid SERS substrates are fabricated, SERS signal of the proteins that are background free and independent of the protein charge. Pros and cons of using plasmonic nano colloids and nanostructures as SERS substrate will be discussed for label-free detection of proteins using SERS.

Surface enhanced Raman spectroscopy detection of biomolecules using EBL fabricated nanostructured substrates.

PubMed

Peters, Robert F; Gutierrez-Rivera, Luis; Dew, Steven K; Stepanova, Maria

2015-03-20

Fabrication and characterization of conjugate nano-biological systems interfacing metallic nanostructures on solid supports with immobilized biomolecules is reported. The entire sequence of relevant experimental steps is described, involving the fabrication of nanostructured substrates using electron beam lithography, immobilization of biomolecules on the substrates, and their characterization utilizing surface-enhanced Raman spectroscopy (SERS). Three different designs of nano-biological systems are employed, including protein A, glucose binding protein, and a dopamine binding DNA aptamer. In the latter two cases, the binding of respective ligands, D-glucose and dopamine, is also included. The three kinds of biomolecules are immobilized on nanostructured substrates by different methods, and the results of SERS imaging are reported. The capabilities of SERS to detect vibrational modes from surface-immobilized proteins, as well as to capture the protein-ligand and aptamer-ligand binding are demonstrated. The results also illustrate the influence of the surface nanostructure geometry, biomolecules immobilization strategy, Raman activity of the molecules and presence or absence of the ligand binding on the SERS spectra acquired.

Ultra-thin layer chromatography and surface enhanced Raman spectroscopy on silver nanorod array substrates prepared by oblique angle deposition

NASA Astrophysics Data System (ADS)

Chen, Jing; Abell, Justin; Huang, Yao-wen; Zhao, Yiping

2012-06-01

We demonstrate the potential use of silver nanorod (AgNR) array substrates for on-chip separation and detection of chemical mixtures by ultra-thin layer chromatography (UTLC) and surface enhanced Raman spectroscopy (SERS). The capability of the AgNR substrates to separate different compounds in a mixture was explored using a mixture of the food colorant Brilliant Blue FCF and lactic acid, and the mixtures of Methylene Violet and BSA at various concentrations. After the UTLC process, spatially-resolved SERS spectra were collected along the mobile phase development direction and the intensities of specific SERS peaks from each component were used to generate chromatograms. The AgNR substrates demonstrate the capability of separating Brilliant Blue from lactic acid, as well as revealing the SERS signal of Methylene Violet from the massive BSA background after a simple UTLC step. This technique may have significant practical implications in actual detection of small molecules from complex food or clinical backgrounds.

SERS analysis of Ag nanostructures produced by ion-beam deposition

NASA Astrophysics Data System (ADS)

Atanasov, P. A.; Nedyalkov, N. N.; Nikov, Ru G.; Grüner, Ch; Rauschenbach, B.; Fukata, N.

2018-03-01

This study deals with the development of a novel technique for formation of advanced Ag nanostructures (NSs) to be applied to high-resolution analyses based on surface enhanced Raman scattering (SERS). It has direct bearing on human health and food quality, e.g., monitoring small amount or traces of pollutants or undesirable additives. Three types of nanostructured Ag samples were produced using ion-beam deposition at glancing angle (GLAD) on quartz. All fabricated structures were covered with BI-58 pesticide (dimethoate) or Rhodamine 6G (R6G) for testing their potential for use as substrates for (SERS).

Facile fabrication of superhydrophobic hybrid nanotip and nanopore arrays as surface-enhanced Raman spectroscopy substrates

NASA Astrophysics Data System (ADS)

Li, Yuxin; Li, Juan; Wang, Tiankun; Zhang, Zhongyue; Bai, Yu; Hao, Changchun; Feng, Chenchen; Ma, Yingjun; Sun, Runguang

2018-06-01

We demonstrate the fabrication of superhydrophobic hybrid nanotip and nanopore arrays (NTNPAs) that can act as sensitive surface-enhanced Raman spectroscopy (SERS) substrates. The large-area substrates were fabricated by following a facile, low-cost process consisting of the one-step voltage-variation anodization of Al foil, followed by Ag nanoparticle deposition and fluorosilane (FS) modification. Uniformly distributed, large-area (5 × 5 cm2) NTNPAs can be obtained rapidly by anodizing Al foil for 1560 s followed by Ag deposition for 400 s, which showed good SERS reproducibility as using1 μM Rhodamine 6G (R6G) as analyte. SERS performances of superhydrophobic NTNPAs with different FS modification and Ag nanoparticle deposition orders were also studied. The nanosamples with FS modification followed by Ag nanoparticle deposition (FS-Ag) showed better SERS sensitivity than the nanosamples with Ag nanoparticle deposition followed by FS modification (Ag-FS). The detection limit of a directly dried R6G droplet can reach 10-8 M on the FS-Ag nanosamples. The results can help create practical high sensitive SERS substrates, which can be used in developing advanced bio- and chemical sensors.

Ag electrode modified with polyhexamethylene biguanide stabilized silver nanoparticles: a new type of SERS substrates for detection of enzymatically generated thiocholine

NASA Astrophysics Data System (ADS)

Tepanov, A. A.; Nechaeva, N. L.; Prokopkina, T. A.; Kudrinskiy, A. A.; Kurochkin, I. N.; Lisichkin, G. V.

2015-11-01

The detection of thiocholine is one of the most widespread techniques for estimation of the cholinesterase activity - acetylcholinesterase and butyrylcholinesterase. Both cholinesterases can be inhibited by organophosphates and carbamates and accordingly can be considered for estimation of these pollutants in the environment. In the current work, SERS spectroscopy was applied for the thiocholine detection. The Ag electrodes modified with silver nanoparticles stabilized by polyhexamethylene biguanide were for the first time suggested as SERS-substrates for that purpose. Such electrodes can be applicable for SERS detection of submicromolar concentrations of thiocholine.

A green, reusable SERS film with high sensitivity for in-situ detection of thiram in apple juice

NASA Astrophysics Data System (ADS)

Sun, Hongbao; Liu, Hai; Wu, Yiyong

2017-09-01

We report a green and reusable surface-enhanced Raman scattering (SERS) film based on PMMA/Ag NPs/graphene. By using this Raman substrate, the SERS signals of R6G were significantly enhanced reaching a minimum detectable concentration of 5 × 10-8 M, due to having lots of hot spots adhered backside to the exposed graphene. The SERS film can be used for in-situ monitoring of trace thiram in apple juice with a detection limit of 1 × 10-6 M (0.24 ppm), which is below the maximal residue limit (MRL) of 7 ppm in fruit prescribed by the U.S. Environmental Protection Agency (EPA). Furthermore, reusability studies show that the SERS film can be used repeatedly. In addition, the graphene-enhanced SERS technique shows great potential applications for the in-situ detection and identification of pesticide residues in environmental water, fruits and vegetables.

Cancer Osaka thyroid (Cot) phosphorylates Polo-like kinase (PLK1) at Ser137 but not at Thr210.

PubMed

Wu, Binhui; Jiang, Ping; Mu, Yuguang; Wilmouth, Rupert C

2009-12-01

Cancer Osaka thyroid (Cot) is a proto-oncogenic kinase which belongs to the MAP3K family. A peptide-based substrate screening assay revealed that Cot has the ability to phosphorylate Polo-like kinase 1 (Plk1) at Ser137. Kinase assays with intact Plk1 and peptides surrounding Ser137 and Thr210 indicated further that Cot phosphorylates Ser137 but not Thr210. Additional support came from 3D peptide structure prediction and Cot-Plk1 interaction modeling. In vivo experiments demonstrated that wild type Cot, but not a kinase-dead mutant, has the ability to phosphorylate Ser137. Knockdown of Cot in Hela showed a reduction in the level of phosphorylation of Ser137. These results imply for the first time that Cot might be an upstream kinase of Plk1 and suggest a new mechanism for the regulation of the cellular function of Plk1.

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.

Programmable SERS active substrates for chemical and biosensing applications using amorphous/crystalline hybrid silicon nanomaterial

PubMed Central

Powell, Jeffery Alexander; Venkatakrishnan, Krishnan; Tan, Bo

2016-01-01

We present the creation of a unique nanostructured amorphous/crystalline hybrid silicon material that exhibits surface enhanced Raman scattering (SERS) activity. This nanomaterial is an interconnected network of amorphous/crystalline nanospheroids which form a nanoweb structure; to our knowledge this material has not been previously observed nor has it been applied for use as a SERS sensing material. This material is formed using a femtosecond synthesis technique which facilitates a laser plume ion condensation formation mechanism. By fine-tuning the laser plume temperature and ion interaction mechanisms within the plume, we are able to precisely program the relative proportion of crystalline Si to amorphous Si content in the nanospheroids as well as the size distribution of individual nanospheroids and the size of Raman hotspot nanogaps. With the use of Rhodamine 6G (R6G) and Crystal Violet (CV) chemical dyes, we have been able to observe a maximum enhancement factor of 5.38 × 106 and 3.72 × 106 respectively, for the hybrid nanomaterial compared to a bulk Si wafer substrate. With the creation of a silicon-based nanomaterial capable of SERS detection of analytes, this work demonstrates a redefinition of the role of nanostructured Si from an inactive to SERS active role in nano-Raman sensing applications. PMID:26785682

Programmable SERS active substrates for chemical and biosensing applications using amorphous/crystalline hybrid silicon nanomaterial.

PubMed

Powell, Jeffery Alexander; Venkatakrishnan, Krishnan; Tan, Bo

2016-01-20

We present the creation of a unique nanostructured amorphous/crystalline hybrid silicon material that exhibits surface enhanced Raman scattering (SERS) activity. This nanomaterial is an interconnected network of amorphous/crystalline nanospheroids which form a nanoweb structure; to our knowledge this material has not been previously observed nor has it been applied for use as a SERS sensing material. This material is formed using a femtosecond synthesis technique which facilitates a laser plume ion condensation formation mechanism. By fine-tuning the laser plume temperature and ion interaction mechanisms within the plume, we are able to precisely program the relative proportion of crystalline Si to amorphous Si content in the nanospheroids as well as the size distribution of individual nanospheroids and the size of Raman hotspot nanogaps. With the use of Rhodamine 6G (R6G) and Crystal Violet (CV) chemical dyes, we have been able to observe a maximum enhancement factor of 5.38 × 10(6) and 3.72 × 10(6) respectively, for the hybrid nanomaterial compared to a bulk Si wafer substrate. With the creation of a silicon-based nanomaterial capable of SERS detection of analytes, this work demonstrates a redefinition of the role of nanostructured Si from an inactive to SERS active role in nano-Raman sensing applications.

Programmable SERS active substrates for chemical and biosensing applications using amorphous/crystalline hybrid silicon nanomaterial

NASA Astrophysics Data System (ADS)

Powell, Jeffery Alexander; Venkatakrishnan, Krishnan; Tan, Bo

2016-01-01

We present the creation of a unique nanostructured amorphous/crystalline hybrid silicon material that exhibits surface enhanced Raman scattering (SERS) activity. This nanomaterial is an interconnected network of amorphous/crystalline nanospheroids which form a nanoweb structure; to our knowledge this material has not been previously observed nor has it been applied for use as a SERS sensing material. This material is formed using a femtosecond synthesis technique which facilitates a laser plume ion condensation formation mechanism. By fine-tuning the laser plume temperature and ion interaction mechanisms within the plume, we are able to precisely program the relative proportion of crystalline Si to amorphous Si content in the nanospheroids as well as the size distribution of individual nanospheroids and the size of Raman hotspot nanogaps. With the use of Rhodamine 6G (R6G) and Crystal Violet (CV) chemical dyes, we have been able to observe a maximum enhancement factor of 5.38 × 106 and 3.72 × 106 respectively, for the hybrid nanomaterial compared to a bulk Si wafer substrate. With the creation of a silicon-based nanomaterial capable of SERS detection of analytes, this work demonstrates a redefinition of the role of nanostructured Si from an inactive to SERS active role in nano-Raman sensing applications.

Alkylamine capped metal nanoparticle "inks" for printable SERS substrates, electronics and broadband photodetectors.

PubMed

Polavarapu, Lakshminarayana; Manga, Kiran Kumar; Yu, Kuai; Ang, Priscilla Kailian; Cao, Hanh Duyen; Balapanuru, Janardhan; Loh, Kian Ping; Xu, Qing-Hua

2011-05-01

We report a facile and general method for the preparation of alkylamine capped metal (Au and Ag) nanoparticle "ink" with high solubility. Using these metal nanoparticle "inks", we have demonstrated their applications for large scale fabrication of highly efficient surface enhanced Raman scattering (SERS) substrates by a facile solution processing method. These SERS substrates can detect analytes down to a few nM. The flexible plastic SERS substrates have also been demonstrated. The annealing temperature dependent conductivity of the nanoparticle films indicated a transition temperature above which high conductivity was achieved. The transition temperature could be tailored to the plastic compatible temperatures by using proper alkylamine as the capping agent. The ultrafast electron relaxation studies of the nanoparticle films demonstrated that faster electron relaxation was observed at higher annealing temperatures due to stronger electronic coupling between the nanoparticles. The applications of these highly concentrated alkylamine capped metal nanoparticle inks for the printable electronics were demonstrated by printing the oleylamine capped gold nanoparticles ink as source and drain for the graphene field effect transistor. Furthermore, the broadband photoresponse properties of the Au and Ag nanoparticle films have been demonstrated by using visible and near-infrared lasers. These investigations demonstrate that these nanoparticle "inks" are promising for applications in printable SERS substrates, electronics, and broadband photoresponse devices. © The Royal Society of Chemistry 2011

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

Controllable optical activity of non-spherical Ag and Co SERS substrate with different magnetic field

NASA Astrophysics Data System (ADS)

Fan, Chun-Zhen; Zhu, Shuang-Mei; Xin, Hao-Yi

2017-02-01

We experimentally fabricate a non-spherical Ag and Co surface-enhanced Raman scattering (SERS) substrate, which not only retains the metallic plasmon resonant effect, but also possesses the magnetic field controllable characteristics. Raman detections are carried out with the test crystal violet (CV) and rhodamine 6G (R6G) molecules with the initiation of different magnitudes of external magnetic field. Experimental results indicate that our prepared substrate shows a higher SERS activity and magnetic controllability, where non-spherical Ag nanoparticles are driven to aggregate effectively by the magnetized Co and plenty of hot-spots are built around the metallic Ag nanoparticles, thereby leading to the enhancement of local electromagnetic field. Moreover, when the external magnetic field is increased, our prepared substrate demonstrates excellent SERS enhancement. With the 2500 Gs and 3500 Gs (1 Gs = 10-4 T) magnetic fields, SERS signal can also be obtained with the detection limit lowering down to 10-9 M. These results indicate that our proposed magnetic field controlled substrate enables us to freely achieve the enhanced and controllable SERS effect, which can be widely used in the optical sensing, single molecule detection and bio-medical applications. Project supported by the Key Science and Technology Research Project of Henan Province, China (Grant No. 162102210164), the Natural Science Foundation of Henan Educational Committee, China (Grant No. 17A140002), the National Natural Science Foundations of China (Grant Nos. 11574276, 11404291, and 11604079), and the Program for Science & Technology Innovation Talents in Universities of Henan Province, China (Grant No. 17HASTIT0).

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

NASA Astrophysics Data System (ADS)

Alexander, Troy A.; Gillespie, James B.; Pellegrino, Paul M.; Fell, Nicholas F., Jr.; Wood, Gary L.; Salamo, Gregory J.

2003-03-01

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 several Bacillus species. This technique may be useful in many applications; most notably, development of novel detection schemes toward potentially harmful biological agents. 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 several 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 785-nm laser diode was used to capture/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 species identification of bacterial spores.

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.

A new technique to transfer metallic nanoscale patterns to small and non-planar surfaces: Application to a fiber optic device for surface enhanced Raman scattering detection

NASA Astrophysics Data System (ADS)

Smythe, Elizabeth Jennings

This thesis focuses on the development of a bidirectional fiber optic probe for the detection of surface enhanced Raman scattering (SERS). One facet of this fiber-based probe featured an array of coupled optical antennas, which we designed to enhance the Raman signal of nearby analytes. When this array interacted with an analyte, it generated SERS signals specific to the chemical composition of the sample; some of these SERS signals coupled back into the fiber. We used the other facet of the probe to input light into the fiber and collect the SERS signals that coupled into the probe. In this dissertation, the development of the probe is broken into three sections: (i) characterization of antenna arrays, (ii) fabrication of the probe, and (iii) device measurements. In the first section we present a comprehensive study of metallic antenna arrays. We carried out this study to determine the effects of antenna geometry, spacing, and composition on the surface plasmon resonance (SPR) of a coupled antenna array; the wavelength range and strength of the SPR are functions of the shape and interactions of the antennas. The SPR of the array ultimately amplified the Raman signal of analytes and produced a measurable SERS signal, thus determination of the optimal array geometries for SERS generation was an important first step in the development of the SERS fiber probe. We then introduce a new technique developed to fabricate the SERS fiber probes. This technique involves transferring antenna arrays (created by standard lithographic methods) from a large silicon substrate to a fiber facet. We developed this fabrication technique to bypass many of the limitations presented by previously developed methods for patterning unconventional substrates (i.e. small and/or non-planar substrates), such as focused ion-beam milling and soft lithography. In the third section of this thesis, we present SERS measurements taken with the fiber probe. We constructed a measurement system to couple light into the probe and filter out background noise; this allowed simultaneous detection of multiple chemicals. Antenna array enhancement factor (EF) calculations are shown; these allowed us to determine that the probe efficiently collected SERS signals.

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.

The biochemical origins of the surface-enhanced Raman spectra of bacteria: a metabolomics profiling by SERS.

PubMed

Premasiri, W Ranjith; Lee, Jean C; Sauer-Budge, Alexis; Théberge, Roger; Costello, Catherine E; Ziegler, Lawrence D

2016-07-01

The dominant molecular species contributing to the surface-enhanced Raman spectroscopy (SERS) spectra of bacteria excited at 785 nm are the metabolites of purine degradation: adenine, hypoxanthine, xanthine, guanine, uric acid, and adenosine monophosphate. These molecules result from the starvation response of the bacterial cells in pure water washes following enrichment from nutrient-rich environments. Vibrational shifts due to isotopic labeling, bacterial SERS spectral fitting, SERS and mass spectrometry analysis of bacterial supernatant, SERS spectra of defined bacterial mutants, and the enzymatic substrate dependence of SERS spectra are used to identify these molecular components. The absence or presence of different degradation/salvage enzymes in the known purine metabolism pathways of these organisms plays a central role in determining the bacterial specificity of these purine-base SERS signatures. These results provide the biochemical basis for the development of SERS as a rapid bacterial diagnostic and illustrate how SERS can be applied more generally for metabolic profiling as a probe of cellular activity. Graphical Abstract Bacterial typing by metabolites released under stress.

Substrate Oxide Layer Thickness Optimization for a Dual-Width Plasmonic Grating for Surface-Enhanced Raman Spectroscopy (SERS) Biosensor Applications

PubMed Central

Bauman, Stephen J.; Brawley, Zachary T.; Darweesh, Ahmad A.; Herzog, Joseph B.

2017-01-01

This work investigates a new design for a plasmonic SERS biosensor via computational electromagnetic models. It utilizes a dual-width plasmonic grating design, which has two different metallic widths per grating period. These types of plasmonic gratings have shown larger optical enhancement than standard single-width gratings. The new structures have additional increased enhancement when the spacing between the metal decreases to sub-10 nm dimensions. This work integrates an oxide layer to improve the enhancement even further by carefully studying the effects of the substrate oxide thickness on the enhancement and reports ideal substrate parameters. The combined effects of varying the substrate and the grating geometry are studied to fully optimize the device’s enhancement for SERS biosensing and other plasmonic applications. The work reports the ideal widths and substrate thickness for both a standard and a dual-width plasmonic grating SERS biosensor. The ideal geometry, comprising a dual-width grating structure atop an optimal SiO2 layer thickness, improves the enhancement by 800%, as compared to non-optimized structures with a single-width grating and a non-optimal oxide thickness. PMID:28665308

Laser remote sensing of backscattered light from a target sample

DOEpatents

Sweatt, William C [Albuquerque, NM; Williams, John D [Albuquerque, NM

2008-02-26

A laser remote sensing apparatus comprises a laser to provide collimated excitation light at a wavelength; a sensing optic, comprising at least one optical element having a front receiving surface to focus the received excitation light onto a back surface comprising a target sample and wherein the target sample emits a return light signal that is recollimated by the front receiving surface; a telescope for collecting the recollimated return light signal from the sensing optic; and a detector for detecting and spectrally resolving the return light signal. The back surface further can comprise a substrate that absorbs the target sample from an environment. For example the substrate can be a SERS substrate comprising a roughened metal surface. The return light signal can be a surface-enhanced Raman signal or laser-induced fluorescence signal. For fluorescence applications, the return signal can be enhanced by about 10.sup.5, solely due to recollimation of the fluorescence return signal. For SERS applications, the return signal can be enhanced by 10.sup.9 or more, due both to recollimation and to structuring of the SERS substrate so that the incident laser and Raman scattered fields are in resonance with the surface plasmons of the SERS substrate.

SERS-Active Nanoinjector for Intracellular Spectroscopy

NASA Astrophysics Data System (ADS)

Vitol, Elina; Orynbayeva, Zulfiya; Bouchard, Michael; Azizkhan-Clifford, Jane; Friedman, Gary; Gogotsi, Yury

2009-03-01

We developed a multifunctional nanopipette which allows simultaneous cell injection and intacellular surface-enhanced Raman spectroscopy (SERS) analysis. SERS spectra contain the characteristic frequencies of molecular bond vibrations. This is a unique method for studying cell biochemistry and physiology on a single organelle level. Unlike the fluorescence spectroscopy, it does not require any specific staining. The principle of SERS is based on very large electromagnetic field enhancement localized around a nano-rough metallic surface. Gold colloids are widely used SERS substrates. Previously, the colloidal nanoparticles were introduced into a cell by the mechanism of endocytosis. The disadvantage of this method is the uncontrollable aggregation and distribution of gold nanoparticles inside a cell which causes a significant uncertainty in the origin of the acquired data. At the same time, the nanoparticle uptake is irreversible. We present a SERS-active nanoinjector, coated with gold nanoparticles, which enables selective signal acquisition from any point-of-interest inside a cell. The nanoinjector provides a highly localized SERS signal with sub-nanometer resolution in real time.

Assessing Telomere Length Using Surface Enhanced Raman Scattering

NASA Astrophysics Data System (ADS)

Zong, Shenfei; Wang, Zhuyuan; Chen, Hui; Cui, Yiping

2014-11-01

Telomere length can provide valuable insight into telomeres and telomerase related diseases, including cancer. Here, we present a brand-new optical telomere length measurement protocol using surface enhanced Raman scattering (SERS). In this protocol, two single strand DNA are used as SERS probes. They are labeled with two different Raman molecules and can specifically hybridize with telomeres and centromere, respectively. First, genome DNA is extracted from cells. Then the telomere and centromere SERS probes are added into the genome DNA. After hybridization with genome DNA, excess SERS probes are removed by magnetic capturing nanoparticles. Finally, the genome DNA with SERS probes attached is dropped onto a SERS substrate and subjected to SERS measurement. Longer telomeres result in more attached telomere probes, thus a stronger SERS signal. Consequently, SERS signal can be used as an indicator of telomere length. Centromere is used as the inner control. By calibrating the SERS intensity of telomere probe with that of the centromere probe, SERS based telomere measurement is realized. This protocol does not require polymerase chain reaction (PCR) or electrophoresis procedures, which greatly simplifies the detection process. We anticipate that this easy-operation and cost-effective protocol is a fine alternative for the assessment of telomere length.

Development of a surface-enhanced Raman technique for biomarker studies on Mars.

PubMed

Dunn, Darrell S; Sridhar, Narasi; Miller, Michael A; Price, Kendra T; Pabalan, Roberto; Abrajano, Teofilo A

2007-01-01

Raman spectroscopy has been identified as a potentially useful tool to collect evidence of past or present life on extraterrestrial bodies. However, it is limited by its inherently low signal strength. In this investigation, laboratory tests were conducted using surface-enhanced Raman spectroscopy (SERS) in an "inverted" mode to detect the presence of organic compounds that may be similar to possible biomarkers present on Mars. SERS was used to overcome the inherently low signal intensity of Raman spectroscopy and was an effective method for detecting small concentrations of organic compounds on a number of surfaces. For small organic molecules, dissolution of the molecule to be analyzed in a suitable solvent and depositing it on a prepared SERS substrate for analysis is possible. However, for larger molecules, an "inverted" SERS (iSERS) technique was shown to be effective. In iSERS, nanoparticles of silver or gold were deposited on the mineral substrate/organic compound to be analyzed. Benzotriazole, benzoic acid, and phthalic acid were used as test organic analogs and the iSERS technique was able to detect femtomole levels of the analytes. The interference from various mineral substrates was also examined. Different methods of depositing silver particles were evaluated, including ion beam-assisted vapor deposition and deposition from aqueous colloidal suspensions.

Surface Enhanced Raman Scattering (SERS)-Based Next Generation Commercially Available Substrate: Physical Characterization and Biological Application

DTIC Science & Technology

2011-09-01

the spore and the active areas on the Klarite surface. For these experiments an aliquot of the common bacillus spore B. coagulans was drop...suspension B. coagulans (ATCC SUS-CG) was purchased from Raven Biologicals and used at a log 4 or 6 population per 0.1 mL of solution. For experiments...Klarite substrates were evaluated with the spore sample B. coagulans . In these experiments different substrates and the changes in overall band

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.

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.

Micro-nano zinc oxide film fabricated by biomimetic mineralization: Designed architectures for SERS substrates

NASA Astrophysics Data System (ADS)

Lu, Fei; Guo, Yue; Wang, Yunxin; Song, Wei; Zhao, Bing

2018-05-01

In this study, we have investigated the effect of the surface morphologies of the zinc oxide (ZnO) substrates on surface enhanced Raman spectroscopy (SERS). During synthetic process, the self-assembly monolayers (SAMs) with different terminal groups are used as templates to induce the nucleation and growth of Zn(NO3)2·6H2O crystals, then different morphologies micro-nano ZnO powders are obtained by annealing Zn(NO3)2·6H2O crystals at 450 °C. The products obtained at different conditions are characterized by means of X-ray diffraction (XRD) patterns, scanning electron microscopy (SEM) and Raman spectra. The as-prepared ZnO micro-sized particles have been used the efficient Surface enhanced Raman scattering (SERS) substrates, and the SERS signals of 4-mercaptopyridine (Mpy) probe molecules are much influenced by the morphologies of the ZnO structures. Results indicated that the more (0001) facets appear in the of ZnO morphology, the greater degree of charge-transfer (PCT) for the SERS enhancement on the surface of semiconductors is achieved. The chemical interaction between ZnO structures and Mpy molecules plays a very important role in the SERS enhancement.

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.

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

Designing of a novel gold nanodumbbells SERS substrate for detection of prohibited colorants in drinks

NASA Astrophysics Data System (ADS)

Meng, Juan; Qin, Suhua; Zhang, Li; Yang, Liangbao

2016-03-01

It is reported that the use of gold nanodumbbells as surface-enhanced Raman spectroscopy (SERS) substrates for the detection of ultra-low levels of four different food colorants: sunset yellow, lemon yellow, orange II and chrysoidin. Gold nanodumbbells are suitable to on-site detection because which have a λmax of 785 nm that tune the surface plasmon resonance of the nanoparticles to the laser excitation wavelength of the Raman spectrometer equipped with a 785 nm diode laser. In order to investigate the on-site application of the gold nanodumbbells substrate, four pigments in the orange juice and coke were detected by the portable Raman instrument. The results showed that this novel SERS platform can be used as an effective method in detecting prohibited additive colorants in food. This SERS platform provides valuable and powerful analytical tool in real-world applications in food analysis.

Assessing the Location of Surface Plasmons Over Nanotriangle and Nanohole Arrays of Different Size and Periodicity

PubMed Central

Correia-Ledo, Debby; Gibson, Kirsty F.; Dhawan, Anuj; Couture, Maxime; Vo-Dinh, Tuan; Graham, Duncan; Masson, Jean-Francois

2012-01-01

The increasing popularity of surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) sensor design based on nanotriangle or nanohole arrays, and the possibility to manufacture substrates at the transition between these plasmonic substrates, makes them ideal candidates for the establishment of structure-property relationships. This work features near diffraction-limited Raman images and FDTD simulations of nanotriangle and nanohole arrays substrates, which clearly demonstrate that the localization of the hot spot on these SERS substrates is significantly influenced by the ratio of diameter/periodicity (D/P). The experimental and simulation data reveal that the hot spots are located around nanotriangles (D/P = 1), characteristic of localized SPR. Decreasing the D/P ratio to 0.75-0.7 led to the creation of nanohole arrays, which promoted the excitation of a propagating surface plasmon (SP) delocalized over the metal network. The optimal SERS intensity was consistently achieved at this transition from nanotriangles to nanoholes, for every periodicity (650 nm to 1.5 μm) and excitation wavelength (633 and 785 nm) investigated, despite the presence or absence of a plasmonic band near the laser excitation. Further decreasing the D/P ratio led to excitation of a localized SP located around the rim of nanohole arrays for D/P of 0.5-0.6, in agreement with previous reports. In addition, this manuscript provides the first evidence that the hot spots are positioned inside the hole for D/P of 0.4, with the center being the region of highest electric field and Raman intensity. The compelling experimental evidence and FDTD simulations offer an overall understanding of the plasmonic properties of nanohole arrays as SERS and SPR sensors, which is of significant value in advancing the diversity of applications from such surfaces. PMID:23977402

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.

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

Raman and SERS microspectroscopy on living cells: a promising tool toward cellular drug response and medical diagnosis

NASA Astrophysics Data System (ADS)

Beljebbar, Abdelilah; Sockalingum, Ganesh D.; Morjani, Hamid; Manfait, Michel

1999-04-01

Raman spectroscopy has been sued to differentiate between sensitive and MDR-resistant cells using Raman spectral imaging with a 632.8 nm excitation wavelength. The comparison between two spectral images allowed to quantify the differences between sensitive and resistant cell lines in term of proteins, lipids when MDR phenotype is expressed. SER spectroscopy has become a powerful and non-invasive probe for investigating the molecular and cellular interaction of drugs with their targets. The comparison between these models allow to elucidate the biological effect of the drugs. The development of new types of SERS- active substrates has extended the applicability of this technique to medical diagnosis. Two kinds of SERS active substrates, characterized as 'bio-compatible' systems, can be used for investigation on single living cells: colloid suspensions and microelectrodes and island films. This methodology is used for the study of cell membrane components in interaction with the SERS substrates with the aim to understand the resistance mechanism. The constitution of a data bank will allow the follow-up of cancer and future monitoring of therapeutic intervention.

Facile one-step synthesis of Ag@Fe3O4 core-shell nanospheres for reproducible SERS substrates

NASA Astrophysics Data System (ADS)

Sun, Lijuan; He, Jiang; An, Songsong; Zhang, Junwei; Ren, Dong

2013-08-01

A facile approach has been developed to synthesize Ag@Fe3O4 core-shell nanospheres, in which the Ag nanoparticle core was well wrapped by a permeable Fe3O4 shell. An in situ reduction of AgNO3 and Fe(NO3)3 was the basis of this one-step method with ethylene glycol as the reducing agent. The as-obtained Ag@Fe3O4 nanospheres were a highly efficient surface-enhanced Raman scattering (SERS) substrate; high reproducibility, stability, and reusability were obtained by employing 4-aminothiophenol (4-ATP) and rhodamine 6G (R6G) as the Raman probe molecules. It was revealed that the SERS signals of 4-ATP and R6G on the Ag@Fe3O4 nanospheres were much stronger than those on the pure Ag nanoparticles, demonstrating that the magnetic enrichment procedures can improve SERS detection sensitivity efficiently. A highly efficient and recyclable SERS substrate was produced by the new model system that has potential applications in chemical and biomolecular assays.

Modification of the SERS spectrum of cyanide traces due to complex formation between cyanide and silver

NASA Astrophysics Data System (ADS)

Cao Dao, Tran; Kieu, Ngoc Minh; Quynh Ngan Luong, Truc; Cao, Tuan Anh; Hai Nguyen, Ngoc; Le, Van Vu

2018-06-01

It is well known that cyanide is an extremely toxic lethal poison with human death within minutes after exposure to only 300 ppm cyanide. On the other hand, cyanide is released into the environment (mainly through waste water) every day from various human activities. Therefore, rapid, sensitive and cost-effective cyanide trace detection is an urgent need. Surface-enhanced Raman scattering (SERS) is a method that meets these requirements. It should be noted, however, that in this technique SERS substrates, which are usually made of gold or silver, will be leached with aqueous cyanide by the formation of complexes between gold or silver with cyanide. This will cause the SERS spectrum of cyanide to be modified. When determining cyanide concentrations by SERS analysis, this spectral modification should be taken into account. This report presents the SERS spectral modification of aqueous cyanide traces (in ppm and lower concentration range) when the SERS substrates used are flower-like silver micro-structures.

Low-cost silver capped polystyrene nanotube arrays as super-hydrophobic substrates for SERS applications.

PubMed

Lovera, Pierre; Creedon, Niamh; Alatawi, Hanan; Mitchell, Micki; Burke, Micheal; Quinn, Aidan J; O'Riordan, Alan

2014-05-02

In this paper, we describe the fabrication, simulation and characterization of dense arrays of freestanding silver capped polystyrene nanotubes, and demonstrate their suitability for surface enhanced Raman scattering (SERS) applications. Substrates are fabricated in a rapid, low-cost and scalable way by melt wetting of polystyrene (PS) in an anodized alumina (AAO) template, followed by silver evaporation. Scanning electron microscopy reveals that substrates are composed of a dense array of freestanding polystyrene nanotubes topped by silver nanocaps. SERS characterization of the substrates, employing a monolayer of 4-aminothiophenol (4-ABT) as a model molecule, exhibits an enhancement factor of ∼1.6 × 10(6), in agreement with 3D finite difference time domain simulations. Contact angle measurements of the substrates revealed super-hydrophobic properties, allowing pre-concentration of target analyte into a small volume. These super-hydrophobic properties of the samples are taken advantage of for sensitive detection of the organic pollutant crystal violet, with detection down to ∼400 ppt in a 2 μl aliquot demonstrated.

Far-side geometrical enhancement in surface-enhanced Raman scattering with Ag plasmonic films

NASA Astrophysics Data System (ADS)

Perera, M. Nilusha M. N.; Gibbs, W. E. Keith; Juodkazis, Saulius; Stoddart, Paul R.

2018-01-01

Surface-enhanced Raman scattering (SERS) is a surface sensitive technique where the large increase in scattering has primarily been attributed to electromagnetic and chemical enhancements. While smaller geometrical enhancements due to thin film interference and cavity resonances have also been reported, an additional enhancement in the SERS signal, referred to as the `far-side geometrical enhancement', occurs when the SERS substrate is excited through an underlying transparent dielectric substrate. Here the far-side geometrically-enhanced SERS signal has been explored experimentally in more detail. Thermally evaporated Ag plasmonic films functionalised with thiophenol were used to study the dependence of the geometrically-enhanced SERS signal on the excitation wavelength, supporting substrate material and excitation angle of incidence. The results were interpreted using a `geometrical enhancement factor' (GEF), defined as the ratio of far-side to near-side SERS signal intensity. The experimental results confirmed that the highest GEFs of 3.2-3.5× are seen closer to the localized surface plasmon resonance peak of the Ag metallic nanostructures. Interestingly, the GEF for Ag plasmonic films deposited on glass and sapphire were the same within the measurement errors, whereas increasing angle of incidence showed a decrease in the GEF. Given this improved understanding of the far-side geometrical SERS enhancement, the potential for further signal amplification and optimisation for practical sensing applications can now be considered, especially for SERS detection modes at the farend of optical fibre probes and through process windows.

Gold Nanorods as Surface-Enhanced Raman Spectroscopy Substrates for Rapid and Sensitive Analysis of Allura Red and Sunset Yellow in Beverages.

PubMed

Ou, Yiming; Wang, Xiaohui; Lai, Keqiang; Huang, Yiqun; Rasco, Barbara A; Fan, Yuxia

2018-03-21

Synthetic colorants in food can be a potential threat to human health. In this study, surface-enhanced Raman spectroscopy (SERS) coupled with gold nanorods as substrates is proposed to analyze allura red and sunset yellow in beverages. The gold nanorods with different aspect ratios were synthesized, and their long-term stability, SERS activity, and the effect of the different salts on the SERS signal were investigated. The results demonstrate that gold nanorods have a satisfactory stability (stored up to 28 days). SERS coupled with gold nanorods exhibit stronger sensitivity. MgSO 4 was chosen to improve the SERS signal of sunset yellow, and no salts could enhance the SERS signal of allura red. The lowest concentration was 0.10 mg/L for both colorant standard solutions. The successful prediction results using SERS were much closer to those obtained by high-performance liquid chromatography for the sample in beverages. SERS combined with gold nanorods shows potential for analyzing food colorants and other food additives as a rapid, convenient, and sensitive method.

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.

Highly efficient SERS substrate for direct detection of explosive TNT using popcorn-shaped gold nanoparticle-functionalized SWCNT hybrid.

PubMed

Demeritte, Teresa; Kanchanapally, Rajashekhar; Fan, Zhen; Singh, Anant Kumar; Senapati, Dulal; Dubey, Madan; Zakar, Eugene; Ray, Paresh Chandra

2012-11-07

This paper reports for the first time the development of a large-scale SERS substrate from a popcorn-shaped gold nanoparticle-functionalized single walled carbon nanotubes hybrid thin film for the selective and highly sensitive detection of explosive TNT material at a 100 femtomolar (fM) level.

In situ surface-enhanced Raman scattering monitoring of reduction of 4-nitrothiophenol on bifunctional metallic nanostructure

NASA Astrophysics Data System (ADS)

Du, Pan; Zhang, Xin; Yin, Hongjun; Zhao, Yongmei; Liu, Luo; Wu, Zhenglong; Xu, Haijun

2018-03-01

Bifunctional Au/Ag nanoparticle-decorated silicon nanowire arrays (Au/Ag@SiNWAs) were prepared using a facile wet chemical method. This surface-enhanced Raman scattering (SERS) substrate not only showed excellent reutilization capabilities by the simple NaBH4 washing, but also could reach a detection limit for drop-dried rhodamine 6G molecules as low as 10-16 M. More importantly, this substrate could be used to monitor the in situ reduction of 4-nitrothiophenol by NaBH4 using SERS spectroscopy. Our findings demonstrate that the bifunctional substrate can serve as a powerful system for the real-time in situ SERS monitoring of catalytic reactions, which should be beneficial for new catalyst exploration.

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

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.

SERS Detection of Biomolecules by Highly Sensitive and Reproducible Raman-Enhancing Nanoparticle Array

NASA Astrophysics Data System (ADS)

Chan, Tzu-Yi; Liu, Ting-Yu; Wang, Kuan-Syun; Tsai, Kun-Tong; Chen, Zhi-Xin; Chang, Yu-Chi; Tseng, Yi-Qun; Wang, Chih-Hao; Wang, Juen-Kai; Wang, Yuh-Lin

2017-05-01

This paper describes the preparation of nanoarrays composed of silver nanoparticles (AgNPs: 20-50 nm) for use as surface-enhanced Raman scattering (SERS) substrates. The AgNPs were grown on porous anodic aluminum oxide (AAO) templates by electrochemical plating, and the inter-channel gap of AAO channels is between 10 and 20 nm. The size and interparticle gap of silver particles were adjusted in order to achieve optimal SERS signals and characterized by scanning electron microscopy, atomic force microscopy, and Raman spectroscopy. The fluctuation of SERS intensity is about 10-20% when measuring adenine solutions, showing a great reproducible SERS sensing. The nanoparticle arrays offer a large potential for practical applications as shown by the SERS-based quantitative detection and differentiation of adenine (A), thymine (T), cytosine (C), guanine (G), β-carotene, and malachite green. The respective detection limits are <1 ppb for adenine and <0.63 ppm for β-carotene and malachite green, respectively.

Low-cost and large-scale flexible SERS-cotton fabric as a wipe substrate for surface trace analysis

NASA Astrophysics Data System (ADS)

Chen, Yanmin; Ge, Fengyan; Guang, Shanyi; Cai, Zaisheng

2018-04-01

The large-scale surface enhanced Raman scattering (SERS) cotton fabrics were fabricated based on traditional woven ones using a dyeing-like method of vat dyes, where silver nanoparticles (Ag NPs) were in-situ synthesized by 'dipping-reducing-drying' process. By controlling the concentration of AgNO3 solution, the optimal SERS cotton fabric was obtained, which had a homogeneous close packing of Ag NPs. The SERS cotton fabric was employed to detect p-Aminothiophenol (PATP). It was found that the new fabric possessed excellent reproducibility (about 20%), long-term stability (about 57 days) and high SERS sensitivity with a detected concentration as low as 10-12 M. Furthermore, owing to the excellent mechanical flexibility and good absorption ability, the SERS cotton fabric was employed to detect carbaryl on the surface of an apple by simply swabbing, which showed great potential in fast trace analysis. More importantly, this study may realize large-scale production with low cost by a traditional cotton fabric.

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

A Crosslinker Based on a Tethered Electrophile for Mapping Kinase-Substrate Networks

PubMed Central

Riel-Mehan, Megan M; Shokat, Kevan M

2014-01-01

SUMMARY Despite the continuing progress made towards mapping kinase signaling networks, there are still many phosphorylation events for which the responsible kinase has not yet been identified. We are interested in addressing this problem through forming covalent crosslinks between a peptide substrate and the corresponding phosphorylating kinase. Previously we reported a dialdehyde-based kinase binding probe capable of such a reaction with a peptide containing a cysteine substituted for the phosphorylatable ser/thr/tyr residue. Here, we examine the yield of a previously reported dialdehyde-based probe, and report that the dialdehyde based probes possesses a significant limitation in terms of crosslinked kinase-substrate product yield. To address this limitation, we develop a crosslinking scheme based on a kinase activity-based probe, and this new cross-linker provides an increase in efficiency and substrate specificity, including in the context of cell lysate. PMID:24746561

Highly Efficient SERS Nanowire/Ag Composites

DTIC Science & Technology

2007-01-01

Ga2O3 nanowires was performed by the vapor- liquid-solid (VLS) growth in a tube furnace, using Si(100) and Si(111) substrates and a 20 nm Au film3. Ga...Rhodamine 6G/methanol and DNT/methanol dilutions. The Ga2O3 /Ag nanowire composite substrates are shown in Figure 1a. As can be seen, they consist of a...significant improvement over nanosphere-type SERS substrates. Conclusion: Randomly oriented Ga2O3 /Ag nanowire networks have been formed and we

Point-of-care testing in the early diagnosis of acute pesticide intoxication: The example of paraquat.

PubMed

Wei, Ting-Yen; Yen, Tzung-Hai; Cheng, Chao-Min

2018-01-01

Acute pesticide intoxication is a common method of suicide globally. This article reviews current diagnostic methods and makes suggestions for future development. In the case of paraquat intoxication, it is characterized by multi-organ failure, causing substantial mortality and morbidity. Early diagnosis may save the life of a paraquat intoxication patient. Conventional paraquat intoxication diagnostic methods, such as symptom review and urine sodium dithionite assay, are time-consuming and impractical in resource-scarce areas where most intoxication cases occur. Several experimental and clinical studies have shown the potential of portable Surface Enhanced Raman Scattering (SERS), paper-based devices, and machine learning for paraquat intoxication diagnosis. Portable SERS and new SERS substrates maintain the sensitivity of SERS while being less costly and more convenient than conventional SERS. Paper-based devices provide the advantages of price and portability. Machine learning algorithms can be implemented as a mobile phone application and facilitate diagnosis in resource-limited areas. Although these methods have not yet met all features of an ideal diagnostic method, the combination and development of these methods offer much promise.

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.

Sensitive and fast detection of fructose in complex media via symmetry breaking and signal amplification using surface-enhanced Raman spectroscopy.

PubMed

Sun, Fang; Bai, Tao; Zhang, Lei; Ella-Menye, Jean-Rene; Liu, Sijun; Nowinski, Ann K; Jiang, Shaoyi; Yu, Qiuming

2014-03-04

A new strategy is proposed to sensitively and rapidly detect analytes with weak Raman signals in complex media using surface-enhanced Raman spectroscopy (SERS) via detecting the SERS signal changes of the immobilized probe molecules on SERS-active substrates upon binding of the analytes. In this work, 4-mercaptophenylboronic acid (4-MPBA) was selected as the probe molecule which was immobilized on the gold surface of a quasi-three-dimensional plasmonic nanostructure array (Q3D-PNA) SERS substrate to detect fructose. The molecule of 4-MPBA possesses three key functions: molecule recognition and reversible binding of the analyte via the boronic acid group, amplification of SERS signals by the phenyl group and thus shielding of the background noise of complex media, and immobilization on the surface of SERS-active substrates via the thiol group. Most importantly, the symmetry breaking of the 4-MPBA molecule upon fructose binding leads to the change of area ratio between totally symmetric 8a ring mode and nontotally symmetric 8b ring mode, which enables the detection. The detection curves were obtained in phosphate-buffered saline (PBS) and in undiluted artificial urine at clinically relevant concentrations, and the limit of detection of 0.05 mM was achieved.

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.

Nanoparticle-nanoparticle vs. nanoparticle-substrate hot spot contributions to the SERS signal: studying Raman labelled monomers, dimers and trimers.

PubMed

Sergiienko, Sergii; Moor, Kamila; Gudun, Kristina; Yelemessova, Zarina; Bukasov, Rostislav

2017-02-08

We used a combination of Raman microscopy, AFM and TEM to quantify the influence of dimerization on the surface enhanced Raman spectroscopy (SERS) signal for gold and silver nanoparticles (NPs) modified with Raman reporters and situated on gold, silver, and aluminum films and a silicon wafer. The overall increases in the mean SERS enhancement factor (EF) upon dimerization (up by 43% on average) and trimerisation (up by 96% on average) of AuNPs and AgNPs on the studied metal films are within a factor of two, which is moderate when compared to most theoretical models. However, the maximum ratio of EFs for some dimers to the mean EF of monomers can be as high as 5.5 for AgNPs on a gold substrate. In contrast, for dimerization and trimerization of gold and silver NPs on silicon, the mean EF increases by 1-2 orders of magnitude relative to the mean EF of single NPs. Therefore, hot spots in the interparticle gap between gold nanoparticles rather than hot spots between Au nanoparticles and the substrate dominate SERS enhancement for dimers and trimers on a silicon substrate. However, Raman labeled noble metal nanoparticles on plasmonic metal films generate on average SERS enhancement of the same order of magnitude for both types of hot spot zones (e.g. NP/NP and NP/metal film).

Iodide-induced organothiol desorption and photochemical reaction, gold nanoparticle (AuNP) fusion, and SERS signal reduction in organothiol-containing AuNP aggregates

USDA-ARS?s Scientific Manuscript database

Gold nanoparticles (AuNPs) have been used extensively as surface-enhanced Raman spectroscopic (SERS) substrates for their large SERS enhancements and widely believed chemical stability. Presented is the finding that iodide can rapidly reduce the SERS intensity of the ligands, including organothiols ...

Based on time and spatial-resolved SERS mapping strategies for detection of pesticides.

PubMed

Ma, Bingbing; Li, Pan; Yang, Liangbao; Liu, Jinhuai

2015-08-15

For the sensitive and convenient detection of pesticides, several sensing methods and materials have been widely explored. However, it is still a challenge to obtain sensitive, simple detection techniques for pesticides. Here, the simple and sensitive Time-resolved SERS mapping (T-SERS) and Spatial-resolved SERS mapping (S-SERS) are presented for detection of pesticides by using Au@Ag NPs as SERS substrate. The Time-resolved SERS mapping (T-SERS) is based on state translation nanoparticles from the wet state to the dry state to realize SERS measurements. During the SERS measurement, adhesive force drives the particles closer together and then average interparticle gap becomes smaller. Following, air then begins to intersperse into the liquid network and the particles are held together by adhesive forces at the solid-liquid-air interface. In the late stage of water evaporation, all particles are uniformly distributed. Thus, so called hotspots matrix that can hold hotspots between every two adjacent particles in efficient space with minimal polydispersity of particle size are achieved, accompanying the red-shift of surface plasmon peak and appearance of an optimal SPR resonated sharply with excitation wavelength. Here, we found that the T-SERS method exhibits the detection limits of 1-2 orders of magnitude higher than that of S-SERS. On the other hand, the T-SERS is very simple method with high detection sensitivity, better reproducibility (RSD=10.8%) and is beneficial to construction of a calibration curve in comparison with that of Spatial-resolved SERS mapping (S-SERS). Most importantly, as a result of its remarkable sensitivity, T-SERS mapping strategies have been applied to detection of several pesticides and the detect limit can down to 1nM for paraoxon, 0.5nM for sumithion. In short, T-SERS mapping measurement promises to open a market for SERS practical detection with prominent advantages. Copyright © 2015. Published by Elsevier B.V.

A reagent-assisted method in SERS detection of methyl salicylate

NASA Astrophysics Data System (ADS)

Li, Yali; Li, Qianwen; Wang, Yanan; Oh, Joohee; Jin, Sila; Park, Yeonju; Zhou, Tieli; Zhao, Bing; Ruan, Weidong; Jung, Young Mee

2018-04-01

With the explosive application of methyl salicylate (MS) molecules in food and cosmetics, the further detection of MS molecules becomes particularly important. Here we investigated the detection of MS molecules based on surface-enhanced Raman scattering (SERS) in a novel molecule/assistant/metal system constructed with MS, 4,4‧-(hexafluoroisopropylidene) bis (benzoic acid) and Ag nanoparticles (AgNPs). The minimum detection concentration is 10-4 M. To explore the function of assisted reagent, we also referred another system without assistant molecules. The result demonstrates that SERS signals were not acquired, which proves that the assistant molecules are critical for the capture of MS molecules. Two possible mechanisms of MS/assistant/AgNPs system were speculated through two patterns of hydrogen bonds. The linker molecules acted as the role of the bridge between metallic substrates and target molecules through the molecular recognition. This strategy is very beneficial to the expanding of MS detection techniques and other hydrogen bond based coupling detections with SERS.

A SERS biosensor with magnetic substrate CoFe2O4@Ag for sensitive detection of Hg2+

NASA Astrophysics Data System (ADS)

Yang, Xia; He, Yi; Wang, Xueling; Yuan, Ruo

2017-09-01

Mercuric ion (Hg2+) is one toxic metal ion existed in aquatic ecosystems which would seriously damage human central nervous system and other organs. So developing an approach to sensitively detect Hg2+ in our living environment is urgent and important. In this work, a novel surface enhancement Raman spectrum(SERS) sensor is fabricated for high selective and ultrasensitive detection of Hg2+ in aqueous solution, based on a stable thymine-Hg2+-thymine (T-Hg2+-T) structure and the π-π interaction between single-stranded DNA (ssDNA) and single walled carbon nanotubes (SWCNTs). Herein, SWCNTs act as Raman labels to produce characteristic Raman peaks which can be a beacon to quantitative detect Hg2+. In the presence of Hg2+, the ssDNA can capture Hg2+ forming T-Hg2+-T structure, which makes SWCNTs leave the hot spots of the SERS-based biosensor. With this design, the Raman intensity of SWCNTs decreased with the increasing concentration of Hg2+. At the same time, CoFe2O4@Ag as active SERS substrates can effectively enhance sensitivity and uniformity of the biosensor through aggregation by magnet. Under optimal conditions, this proposed biosensor can detect Hg2+ at a range from 1 pM to 100 nM with a detection limit of 0.84 pM. With the advantages of good sensitivity, selectivity, simplicity and rapidity, the biosensor is potentially suitable for monitoring of Hg2+ in environmental applications.

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

Competitive binding effects on surface-enhanced Raman scattering of peptide molecules

NASA Astrophysics Data System (ADS)

Seballos, Leo; Richards, Nicole; Stevens, Daniel J.; Patel, Mira; Kapitzky, Laura; Lokey, Scott; Millhauser, Glenn; Zhang, Jin Z.

2007-10-01

Surface enhanced Raman scattering (SERS) has been conducted on tryptophan (W), proline (P) and tyrosine (Y) containing peptides that include W-P-Y, Y-P-W, W-P-P-P-Y, Y-P-P-P-W, W-P-P-P-P-P-Y, and Y-P-P-P-P-P-W to gain insight into molecular binding behavior on a metal substrate to eventually apply in protein SERS detection. The peptides are shown to bind through the molecule's carboxylic end, but the strong affinity of the tryptophan residue to the substrate surface, in conjunction with its large polarizability, dominates each molecule's SERS signal with the strong presence of its ring modes in all samples. These results are important for understanding SERS of protein molecules.

Improving surface-enhanced Raman scattering properties of TiO(2) nanoparticles by metal Co doping.

PubMed

Yang, Libin; Qin, Xiaoyu; Gong, Mengdi; Jiang, Xin; Yang, Ming; Li, Xiuling; Li, Guangzhi

2014-04-05

In this paper, pure and different amount Co ions doped TiO2 nanoparticles were synthesized by a sol-hydrothermal method and were served as SERS-active substrate. The effect of metal Co doping on SERS properties of TiO2 nanoparticles was mostly investigated. The results indicate that abundant metal doping energy levels can be formed in the energy gap of TiO2 by an appropriate amount Co ions doping, which can promote the charge transfer from TiO2 to molecule, and subsequently enhance SERS signal of adsorbed molecule on TiO2 substrate, and improve remarkably SERS properties of TiO2 nanoparticles. Copyright © 2013 Elsevier B.V. All rights reserved.

DNA-based Nanoconstructs for the Detection of Ions and Biomolecules with Related Raman/SERS Signature Studies

NASA Astrophysics Data System (ADS)

Brenneman, Kimber L.

The utilization of DNA aptamers and semiconductor quantum dots (QDs) for the detection of ions and biomolecules was investigated. In recent years, there have been many studies based on the use of DNA and RNA aptamers, which are single stranded oligonucleotides capable of binding to biomolecules, other molecules, and ions. In many of these cases, the conformational changes of these DNA and RNA aptamers are suitable to use fluorescence resonant energy transfer (FRET) or nanometal surface energy transfer (NSET) techniques to detect such analytes. Coupled with this growth in such uses of aptamers, there has been an expanded use of semiconductor quantum dots as brighter, longer-lasting alternatives to fluorescent dyes in labeling and detection techniques of interest in biomedicine and environmental monitoring. Thrombin binding aptamer (TBA) and a zinc aptamer were used to detect mercury, lead, zinc, and cadmium. These probes were tested in a liquid assay as well as on a filter paper coupon. Biomolecules were also studied and detected using surface-enhanced Raman spectroscopy (SERS), including DNA aptamers and C-reactive protein (CRP). Raman spectroscopy is a useful tool for sensor development, label-free detection, and has the potential for remote sensing. Raman spectra provide information on the vibrational modes or phonons, between and within molecules. Therefore, unique spectral fingerprints for single molecules can be obtained. SERS is accomplished through the use of substrates with nanometer scale geometries made of metals with many free electrons, such as silver, gold, or copper. In this research silver SERS substrates were used to study the SERS signature of biomolecules that typically produce very weak Raman signals.

Sputtering-growth of seeded Au nanoparticles for nanogap-assisted surface-enhanced Raman scattering (SERS) biosensing

NASA Astrophysics Data System (ADS)

Fu, Chit Yaw; U. S., Dinish; Rautela, Shashi; Goh, Douglas Wenda; Olivo, Malini

2011-12-01

Gold-coated array patterned with tightly-packed nanospheres was developed as a substrate base for constructing SERSenriched nanogaps with Au-nanoparticles (GNPs). Using 1,2-ethanedithiol as a linker, Au-NPs (=17-40nm) were anchored covalently on the sphere-array. Thin Au layer was sputtered on the substrate to mask the citrate coating of GNPs that could demote the sensing mechanism. The negatively-charged GNP surface warrants the colloidal stability, but the resulting repulsive force keeps the immobilized NPs apart by about 40nm. The attained gap size is inadequately narrow to sustain any intense enhancement owing to the near-field nature of SERS. Minimal amount of NaCl was then added to slightly perturb the colloidal stability by reducing their surface charge. Notably, the interparticle-gap reduces at increasing amount of salt, giving rise to increased packing density of GNPs. The SERS enhancement is also found to exponentially increase at decreasing gap size. Nevertheless, the minimum gap achieved is limited to merely 7nm. Excessive addition of salt would eventually induce complete aggregation of particles, forming clustered NPs on the array. A simple sputtering-growth approach is therefore proposed to further minimize the interparticle gap by enlarging the seeded NPs based on mild sputtering. The SEM images confirm that the gap below 7nm is achievable. With advent of the colloidal chemistry, the combined salt-induced aggregation and sputtering-growth techniques can be applied to engineer interparticle gap that is crucial to realize an ultrasensitive SERS biosensor. The proposed two-step preparation can be potentially adopted to fabricate the SERS-enriched nanogaps on the microfluidics platform.

Template-free synthesis of porous ZnO/Ag microspheres as recyclable and ultra-sensitive SERS substrates

NASA Astrophysics Data System (ADS)

Liu, Yanjun; Xu, Chunxiang; Lu, Junfeng; Zhu, Zhu; Zhu, Qiuxiang; Manohari, A. Gowri; Shi, Zengliang

2018-01-01

The porous structured zinc oxide (ZnO) microspheres decorated with silver nanoparticles (Ag NPs) have been fabricated as surface-enhanced Raman scattering (SERS) substrate for ultra-sensitive, highly reproducible and stable biological/chemical sensing of various organic molecules. The ZnO microspheres were hydrothermally synthesized without any template, and the Ag NPs decorated on microspheres via photochemical reaction in situ, which provided stable Ag/ZnO contact to achieve a sensitive SERS response. It demonstrates a higher enhancement factor (EF) of 2.44 × 1011 and a lower detection limit of 10-11 M-10-12 M. This porous SERS substrate could also be self-cleaned through a photocatalytic process and then further recycled for the detection of same or different molecules, such as phenol red (PhR), dopamine (DA) and glucose (GLU) with ultra-low concentration and it possessed a sensitive response. The excellent performances are attributed to morphology of porous microspheres, hybrid structure of semiconductor/metal and corresponding localized field enhancement of surface plasmons. Therefore, it is expected to design the recyclable ultra-sensitive SERS sensors for the detection of biological molecules and organic pollutant monitoring.

Rapid detection of salmonella using SERS with silver nano-substrate

NASA Astrophysics Data System (ADS)

Sundaram, J.; Park, B.; Hinton, A., Jr.; Windham, W. R.; Yoon, S. C.; Lawrence, K. C.

2011-06-01

Surface Enhanced Raman Scattering (SERS) can detect the pathogen in rapid and accurate. In SERS weak Raman scattering signals are enhanced by many orders of magnitude. In this study silver metal with biopolymer was used. Silver encapsulated biopolymer polyvinyl alcohol nano-colloid was prepared and deposited on stainless steel plate. This was used as metal substrate for SERS. Salmonella typhimurium a common food pathogen was selected for this study. Salmonella typhimurium bacteria cells were prepared in different concentrations in cfu/mL. Small amount of these cells were loaded on the metal substrate individually, scanned and spectra were recorded using confocal Raman microscope. The cells were exposed to laser diode at 785 nm excitation and object 50x was used to focus the laser light on the sample. Raman shifts were obtained from 400 to 2400 cm-1. Multivariate data analysis was carried to predict the concentration of unknown sample using its spectra. Concentration prediction gave an R2 of 0.93 and standard error of prediction of 0.21. The results showed that it could be possible to find out the Salmonella cells present in a low concentration in food samples using SERS.

Large-scale fabrication of polymer/Ag core-shell nanorod array as flexible SERS substrate by combining direct nanoimprint and electroless deposition

NASA Astrophysics Data System (ADS)

Liu, Sisi; Xu, Zhimou; Sun, Tangyou; Zhao, Wenning; Wu, Xinghui; Ma, Zhichao; Xu, Haifeng; He, Jian; Chen, Cunhua

2014-06-01

We demonstrate a highly sensitive surface-enhanced Raman scattering (SERS) substrate, which consists of Ag nanoparticles (NPs) assembled on the surface of a nanopatterned polymer film. The fabrication route of a polymer/Ag core-shell nanorod (PACSN) array employed a direct nanoimprint technique to create a high-resolution polymer nanorod array. The obtained nanopatterned polymer film was subjected to electroless deposition to form a sea-cucumber-like Ag shell over the surface of the polymer nanorod. The morphology and structures of PACSNs were analyzed by using scanning electron microscopy and X-ray diffraction. The as-synthesized PACSNs exhibited a remarkable SERS activity and Raman signal reproducibility to rhodamine 6G, and a concentration down to 10-12 M can be identified. The effect of electroless deposition time of Ag NPs onto the polymer nanorod surface was investigated. It was found that the electroless deposition time played an important role in SERS activity. Our results revealed that the combination of direct nanoimprint and electroless deposition provided a convenient and cost-effective way for large-scale fabrication of reliable SERS substrates without the requirement of expensive instruments.

Experimental and density functional theory study of Raman and SERS spectra of 5-amino-2-mercaptobenzimidazole

NASA Astrophysics Data System (ADS)

Chen, Yufeng; Yang, Jin; Li, Zonglong; Li, Ran; Ruan, Weidong; Zhuang, Zhiping; Zhao, Bing

2016-01-01

Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS) and density functional theory (DFT) simulations were employed to study 5-amino-2-mercaptobenzimidazole (5-A-2MBI) molecules. Ag colloids were used as SERS substrates which were prepared by using hydroxylamine hydrochloride as reducing agent. Raman vibration modes and SERS characteristic peaks of 5-A-2MBI were assigned with the aid of DFT calculations. The molecular electrostatic potential (MEP) of 5-A-2MBI was used to discuss the possible adsorption behavior of 5-A-2MBI on Ag colloids. The spectral analysis showed that 5-A-2MBI molecules were slightly titled via the sulfur atoms adhering to the surfaces of Ag substrates. The obtained SERS spectral intensity decreased when lowering the 5-A-2MBI concentrations. A final detection limit on the concentration of 5 × 10- 7 mol · L- 1 was gained. SERS proved to be a simple, fast and reliable method for the detection and characterization of 5-A-2MBI molecules.

Review on SERS of Bacteria

PubMed Central

Mosier-Boss, Pamela A.

2017-01-01

Surface enhanced Raman spectroscopy (SERS) has been widely used for chemical detection. Moreover, the inherent richness of the spectral data has made SERS attractive for use in detecting biological materials, including bacteria. This review discusses methods that have been used to obtain SERS spectra of bacteria. The kinds of SERS substrates employed to obtain SERS spectra are discussed as well as how bacteria interact with silver and gold nanoparticles. The roll of capping agents on Ag/Au NPs in obtaining SERS spectra is examined as well as the interpretation of the spectral data. PMID:29137201

SERS Detection of Dopamine Using Label-Free Acridine Red as Molecular Probe in Reduced Graphene Oxide/Silver Nanotriangle Sol Substrate

NASA Astrophysics Data System (ADS)

Luo, Yanghe; Ma, Lu; Zhang, Xinghui; Liang, Aihui; Jiang, Zhiliang

2015-05-01

The reduced graphene oxide/silver nanotriangle (rGO/AgNT) composite sol was prepared by the reduction of silver ions with sodium borohydride in the presence of H2O2 and sodium citrate. In the nanosol substrate, the molecular probe of acridine red (AR) exhibited a weak surface-enhanced Raman scattering (SERS) peak at 1506 cm-1 due to its interaction with the rGO of rGO/AgNT. Upon addition of dopamine (DA), the competitive adsorption between DA and AR with the rGO took place, and the AR molecules were adsorbed on the AgNT aggregates with a strong SERS peak at 1506 cm-1 that caused the SERS peak increase. The increased SERS intensity is linear to the DA concentration in the range of 2.5-500 μmol/L. This new analytical system was investigated by SERS, fluorescence, absorption, transmission electron microscope (TEM), and scanning electron microscope (SEM) techniques, and a SERS quantitative analysis method for DA was established, using AR as a label-free molecular probe.

Graphene-Plasmonic Hybrid Platform for Label-Free SERS Biomedical Detection

NASA Astrophysics Data System (ADS)

Wang, Pu

Surface Enhanced Raman Scattering (SERS) has attracted explosive interest for the wealth of vibrational information it provides with minimal invasive effects to target analyte. Nanotechnology, especially in the form of noble metal nanoparticles exhibit unique electromagnetic and chemical characteristics that are explored to realize ultra-sensitive SERS detection in chemical and biological analysis. Graphene, atom-thick carbon monolayer, exhibits superior chemical stability and bio-compatibility. A combination of SERS-active metal nanostructures and graphene will create various synergies in SERS. The main objective of this research was to exploit the applications of the graphene-Au tip hybrid platform in SERS. The hybrid platform consists of a periodic Au nano-pyramid substrate to provide reproducible plasmonic enhancement, and the superimposed monolayer graphene sheet, serving as "built-in" Raman marker. Extensive theoretical and experimental studies were conducted to determine the potentials of the hybrid platform as SERS substrate. Results from both Finite-Domain Time-Domain (FDTD) numerical simulation and Raman scattering of graphene suggested that the hybrid platform boosted a high density of hotspots yielding 1000 times SERS enhancement of graphene bands. Ultra-high sensitivity of the hybrid platform was demonstrated by bio-molecules including dye, protein and neurotransmitters. Dopamine and serotonin can be detected and distinguished at 10-9 M concentration in the presence of human body fluid. Single molecule detection was obtained using a bi-analyte technique. Graphene supported a vibration mode dependent SERS chemical enhancement of ˜10 to the analyte. Quantitative evaluation of hotspots was presented using spatially resolved Raman mapping of graphene SERS enhancement. Graphene plays a crucial role in quantifying SERS hotspots and paves the path for defining SERS EF that could be universally applied to various SERS systems. A reproducible and statistically reliable SERS quantification approach using the hybrid platform was proposed. The SERS mapping based approach not only leverages the ultra-sensitivity but also minimizes the spot-to-spot variations. Feasibility of biomedical diagnosis with the hybrid platform was exploited by colon cancer cell sensing and time-dependent SERS of amyloid beta protein monomer. The capabilities of the platform are demonstrated by colon cancer cell detection in simulated body fluid background with cell concentration down to 50 cells /mL. Sensitivity of 95% was evidenced by Principle Components Analysis (PCA). Besides, a noticeable evolution profile of the Abeta SERS peaks was observed and attributed to the Abeta configurational change. Taken together, the results suggested the graphene-plasmonic hybrid platform can potentially deliver a biomedical detection and diagnostic imaging platform with superior sensitivity and resolution.

Quantification of Protein Biomarker Using SERS Nano-Stress Sensing with Peak Intensity Ratiometry

NASA Astrophysics Data System (ADS)

Goh, Douglas; Kong, Kien Voon; Jayakumar, Perumal; Gong, Tianxun; Dinish, U. S.; Olivo, Malini

We report a surface enhanced Raman spectroscopy (SERS) ratiometry method based on peak intensity coupled in a nano-stress sensing platform to detect and quantify biological molecules. Herein, we employed an antibody-conjugated p-aminothiophenol (ATP) functionalized on a bimetallic-film-over-nanosphere (BMFON) substrate as a sensitive SERS platform to detect human haptoglobin (Hp) protein, which is an acute phase protein and a biomarker for various cancers. Correlation between change in the ATP spectral characteristics and concentration of Hp protein was established by examining the peak intensity ratio at 1572cm-1 and 1592cm-1 that reflects the degree of stress experienced by the aromatic ring of ATP during Hp protein-antibody interaction. Development of this platform shows the potential in developing a low-cost and sensitive SERS sensor for the pre-screening of various biomarkers.

Paper membrane-based SERS platform for the determination of glucose in blood samples.

PubMed

Torul, Hilal; Çiftçi, Hakan; Çetin, Demet; Suludere, Zekiye; Boyacı, Ismail Hakkı; Tamer, Uğur

2015-11-01

In this report, we present a paper membrane-based surface-enhanced Raman scattering (SERS) platform for the determination of blood glucose level using a nitrocellulose membrane as substrate paper, and the microfluidic channel was simply constructed by wax-printing method. The rod-shaped gold nanorod particles were modified with 4-mercaptophenylboronic acid (4-MBA) and 1-decanethiol (1-DT) molecules and used as embedded SERS probe for paper-based microfluidics. The SERS measurement area was simply constructed by dropping gold nanoparticles on nitrocellulose membrane, and the blood sample was dropped on the membrane hydrophilic channel. While the blood cells and proteins were held on nitrocellulose membrane, glucose molecules were moved through the channel toward the SERS measurement area. Scanning electron microscopy (SEM) was used to confirm the effective separation of blood matrix, and total analysis is completed in 5 min. In SERS measurements, the intensity of the band at 1070 cm(-1) which is attributed to B-OH vibration decreased depending on the rise in glucose concentration in the blood sample. The glucose concentration was found to be 5.43 ± 0.51 mM in the reference blood sample by using a calibration equation, and the certified value for glucose was 6.17 ± 0.11 mM. The recovery of the glucose in the reference blood sample was about 88 %. According to these results, the developed paper-based microfluidic SERS platform has been found to be suitable for use for the detection of glucose in blood samples without any pretreatment procedure. We believe that paper-based microfluidic systems may provide a wide field of usage for paper-based applications.

Newly designed silver coated-magnetic, monodisperse polymeric microbeads as SERS substrate for low-level detection of amoxicillin

NASA Astrophysics Data System (ADS)

Kibar, Güneş; Topal, Ahmet Emin; Dana, Aykutlu; Tuncel, Ali

2016-09-01

We report the preparation of silver-coated magnetic polymethacrylate core-shell nanoparticles for use in surface-enhanced Raman scattering based drug detection. Monodisperse porous poly (mono-2-(methacryloyloxy)ethyl succinate-co-glycerol dimethacrylate), poly (MMES-co-GDMA) microbeads of ca. 5 μm diameter were first synthesized through a multistage microsuspension polymerization technique to serve as a carboxyl-bearing core region. Microspheres were subsequently magnetized by the co-precipitation of ferric ions, aminated through the surface hydroxyl groups and decorated with Au nanoparticles via electrostatic attraction. An Ag shell was then formed on top of the Au layer through a seed-mediated growth process, resulting in micron-sized monodisperse microbeads that exhibit Raman enhancement effects due to the roughness of the Ag surface layer. The core-shell microspheres were used as a new substrate for the detection of amoxicillin at trace concentrations up to 10-8 M by SERS. The proposed SERS platform can be evaluated as a useful tool for the follow-up amoxicillin pollution and low-level detection of amoxicillin in aqueous media.

Simple Approach for the Rapid Detection of Alternariol in Pear Fruit by Surface-Enhanced Raman Scattering with Pyridine-Modified Silver Nanoparticles.

PubMed

Pan, Ting-Tiao; Sun, Da-Wen; Pu, Hongbin; Wei, Qingyi

2018-03-07

A simple method based on surface-enhanced Raman scattering (SERS) was developed for the rapid determination of alternariol (AOH) in pear fruits using an easily prepared silver-nanoparticle (AgNP) substrate. The AgNP substrate was modified by pyridine to circumvent the weak affinity of the AOH molecules to the silver surface and to improve the sensitivity of detection. Quantitative analysis was performed in AOH solutions at concentrations ranging from 3.16 to 316.0 μg/L, and the limit of detection was 1.30 μg/L. The novel method was also applied to the detection of AOH residues in pear fruits purchased from the market and in pear fruits that were artificially inoculated with Alternaria alternata. AOH was not found in any of the fresh fruit, whereas it resided in the rotten and inoculated fruits. Finally, the SERS method was cross validated against HPLC. It was revealed that the SERS method has great potential utility in the rapid detection of AOH in pear fruits and other agricultural products.

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.

Nanomolar detection of glucose using SERS substrates fabricated with albumin coated gold nanoparticles

NASA Astrophysics Data System (ADS)

Perez-Mayen, Leonardo; Oliva, Jorge; Salas, P.; de La Rosa, Elder

2016-06-01

This work presents the design of substrates for Surface Enhanced Raman Scattering (SERS) using star-like gold nanoparticles synthesized by a wet chemical method. The SERS substrates were used for glucose detection for concentrations as low as 10-7 M, which represents an enhancement factor (EF) of 109, as a result of the hot spot formed by the spike termination and appropriate distribution of the gold nanoparticles. An improvement of two orders of magnitude was obtained by coating the gold nanoparticles with albumin with the configuration: glass/Au nanoparticles/albumin. In this case the lowest detection was at a concentration of 10-9 M for an EF of 1011. The albumin molecule allowed us to enhance the Raman signal because of the formation of peptide bonds (COOH-NH2) generated due to the interaction of glucose with albumin, and the appropriate separation distance between the glucose molecules and gold nanoparticles. The presence of such peptide conjugates was confirmed by FTIR spectra. Thus, our results suggest that our SERS substrates can be useful for the detection of very low concentrations of glucose, which is important for the diagnosis of diabetes in the field of medicine.This work presents the design of substrates for Surface Enhanced Raman Scattering (SERS) using star-like gold nanoparticles synthesized by a wet chemical method. The SERS substrates were used for glucose detection for concentrations as low as 10-7 M, which represents an enhancement factor (EF) of 109, as a result of the hot spot formed by the spike termination and appropriate distribution of the gold nanoparticles. An improvement of two orders of magnitude was obtained by coating the gold nanoparticles with albumin with the configuration: glass/Au nanoparticles/albumin. In this case the lowest detection was at a concentration of 10-9 M for an EF of 1011. The albumin molecule allowed us to enhance the Raman signal because of the formation of peptide bonds (COOH-NH2) generated due to the interaction of glucose with albumin, and the appropriate separation distance between the glucose molecules and gold nanoparticles. The presence of such peptide conjugates was confirmed by FTIR spectra. Thus, our results suggest that our SERS substrates can be useful for the detection of very low concentrations of glucose, which is important for the diagnosis of diabetes in the field of medicine. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00163g

Ultra-high sensitive substrates for surface enhanced Raman scattering, made of 3 nm gold nanoparticles embedded on SiO2 nanospheres

NASA Astrophysics Data System (ADS)

Phatangare, A. B.; Dhole, S. D.; Dahiwale, S. S.; Bhoraskar, V. N.

2018-05-01

The surface properties of substrates made of 3 nm gold nanoparticles embedded on SiO2 nanospheres enabled fingerprint detection of thiabendazole (TBZ), crystal violet (CV) and 4-Aminothiophenol (4-ATP) at an ultralow concentration of ∼10-18 M by surface enhanced Raman spectroscopy (SERS). Gold nanoparticles of an average size of ∼3 nm were synthesized and simultaneously embedded on SiO2 nanospheres by the electron irradiation method. The substrates made from the 3 nm gold nanoparticles embedded on SiO2 nanospheres were successfully used for recording fingerprint SERS spectra of TBZ, CV and 4-ATP over a wide range of concentrations from 10-6 M to 10-18 M using 785 nm laser. The unique features of these substrates are roughness near the surface due to the inherent structural defects of 3 nm gold nanoparticles, nanogaps of ≤ 1 nm between the embedded nanoparticles and their high number. These produced an abundance of nanocavities which act as active centers of hot-spots and provided a high electric field at the reporter molecules and thus an enhancement factor required to record the SERS spectra at ultra low concentration of 10-18 M. The SERS spectra recorded by the substrates of 4 nm and 6 nm gold nanoparticles are discussed.

Fabrication and characterization of homogeneous surface-enhanced Raman scattering substrates by single pulse UV-laser treatment of gold and silver films.

PubMed

Christou, Konstantin; Knorr, Inga; Ihlemann, Jürgen; Wackerbarth, Hainer; Beushausen, Volker

2010-12-07

The fabrication of SERS-active substrates, which offer high enhancement factors as well as spatially homogeneous distribution of the enhancement, plays an important role in the expansion of surface-enhanced Raman scattering (SERS) spectroscopy to a powerful, quantitative, and noninvasive measurement technique for analytical applications. In this paper, a novel method for the fabrication of SERS-active substrates by laser treatment of 20, 40, and 60 nm thick gold and of 40 nm thick silver films supported on quartz glass is presented. Single 308 nm UV-laser pulses were applied to melt the thin gold and silver films. During the cooling process of the noble metal, particles were formed. The particle size and density were imaged by atomic force microscopy. By varying the fluence, the size of the particles can be controlled. The enhancement factors of the nanostructures were determined by recording self-assembled monolayers of benzenethiol. The intensity of the SERS signal from benzenethiol is correlated to the mean particle size and thus to the fluence. Enhancement factors up to 10(6) with a high reproducibility were reached. Finally we have analyzed the temperature dependence of the SERS effect by recording the intensity of benzenethiol vibrations from 300 to 120 K. The temperature dependence of the SERS effect is discussed with regard to the metal properties.

Identification of Multiple Phosphorylation Sites on Maize Endosperm Starch Branching Enzyme IIb, a Key Enzyme in Amylopectin Biosynthesis

PubMed Central

Makhmoudova, Amina; Williams, Declan; Brewer, Dyanne; Massey, Sarah; Patterson, Jenelle; Silva, Anjali; Vassall, Kenrick A.; Liu, Fushan; Subedi, Sanjeena; Harauz, George; Siu, K. W. Michael; Tetlow, Ian J.; Emes, Michael J.

2014-01-01

Starch branching enzyme IIb (SBEIIb) plays a crucial role in amylopectin biosynthesis in maize endosperm by defining the structural and functional properties of storage starch and is regulated by protein phosphorylation. Native and recombinant maize SBEIIb were used as substrates for amyloplast protein kinases to identify phosphorylation sites on the protein. A multidisciplinary approach involving bioinformatics, site-directed mutagenesis, and mass spectrometry identified three phosphorylation sites at Ser residues: Ser649, Ser286, and Ser297. Two Ca2+-dependent protein kinase activities were partially purified from amyloplasts, termed K1, responsible for Ser649 and Ser286 phosphorylation, and K2, responsible for Ser649 and Ser297 phosphorylation. The Ser286 and Ser297 phosphorylation sites are conserved in all plant branching enzymes and are located at opposite openings of the 8-stranded parallel β-barrel of the active site, which is involved with substrate binding and catalysis. Molecular dynamics simulation analysis indicates that phospho-Ser297 forms a stable salt bridge with Arg665, part of a conserved Cys-containing domain in plant branching enzymes. Ser649 conservation appears confined to the enzyme in cereals and is not universal, and is presumably associated with functions specific to seed storage. The implications of SBEIIb phosphorylation are considered in terms of the role of the enzyme and the importance of starch biosynthesis for yield and biotechnological application. PMID:24550386

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.

Silver Nanoparticle-Decorated Shape-Memory Polystyrene Sheets as Highly Sensitive Surface-Enhanced Raman Scattering Substrates with a Thermally Inducible Hot Spot Effect.

PubMed

Mengesha, Zebasil Tassew; Yang, Jyisy

2016-11-15

In this study, an active surface-enhanced Raman scattering (SERS) substrate with a thermally inducible hot spot effect for sensitive measurement of Raman-active molecules was successfully fabricated from silver nanoparticle (AgNP)-decorated shape-memory polystyrene (SMP) sheets. To prepare the SERS substrate, SMP sheets were first pretreated with n-octylamine for effective decoration with AgNPs. By varying the formulation and condition of the reduction reaction, AgNP-decorated SMP (Ag@SMP) substrates were successfully prepared with optimized particle gaps to produce inducible hot spot effects on thermal shrink. High-quality SERS spectra were easily obtained with enhancement factors higher than 10 8 by probing with aromatic thiols. Several Ag@SMP substrates produced under different reaction conditions were explored for the creation of inducible hot spot effects. The results indicated that AgNP spacing is crucial for strong hot spot effects. The suitability of Ag@SMP substrates for quantification was also evaluated according to the detection of adenine. Results confirmed that prepared Ag@SMP substrates were highly suitable for quantitative analysis because they yielded an estimated limit of detection as low as 120 pg/cm 2 , a linear range of up to 7 ng/cm 2 , and a regression coefficient (R 2 ) of 0.9959. Ag@SMP substrates were highly reproducible; the average relative standard deviation for all measurements was less than 10%.

Highly sensitive and simple SERS substrate based on photochemically generated carbon nanotubes-gold nanorods hybrids.

PubMed

Caires, A J; Vaz, R P; Fantini, C; Ladeira, L O

2015-10-01

We report a simple and easy formation of hybrids between multi-wall carbon nanotubes and gold nanorods by one-pot in situ photochemical synthesis. Measurements of surface-enhanced Raman scattering (SERS) through the effect "coffee ring" in visible and near infrared (NIR) show high sensitivity with detection of nanomolar concentrations of aromatic dyes. The formation of nanocomposites between carbon nanotubes and gold nanorods without chemical binders simplifies the preparation. Photochemical synthesis is an advance over the techniques previously published. Copyright © 2015 Elsevier Inc. All rights reserved.

SERS activity studies of Ag/Au bimetallic films prepared by galvanic replacement

NASA Astrophysics Data System (ADS)

Wang, Chaonan; Fang, Jinghuai; Jin, Yonglong

2012-10-01

Ag films on Si substrates were fabricated by immersion plating, which served as sacrificial materials for preparation of Ag/Au bimetallic films by galvanic replacement method. SEM images displayed that the sacrificial Ag films presenting island morphology experienced interesting structural evolution process during galvanic replacement reaction, and nano-scaled holes were formed in the resultant bimetallic films. SERS measurements using crystal violet as an analyte showed that SERS intensities of bimetallic films were enhanced significantly compared with that of pure Ag films and related mechanisms were discussed. Immersion plating experiment carried out on Ag films on PEN substrates fabricated by photoinduced reduction method further confirmed that galvanic replacement is an easy method to fabricate Ag/Au bimetallic and a potential approach to improve the SERS performance of Ag films.

New SERS Substrates For Polycyclic Aromatic Hydrocarbon (PAH) Detection: Towards Quantitative SERS Sensors For Environmental Analysis

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

Peron, O.; Laboratoire de Nanotechnologie et d'instrumentation Optique, Institut Charles Delaunay, FRE 2848, Universite de technologie de Troyes, 12 rue Marie Curie, 10010 Troyes; Rinnert, E.

2010-08-06

In the investigation of chemical pollutions, such as PAHs (Polycyclic Aromatic Hydrocarbons) at low concentration in aqueous medium, surface-enhanced Raman scattering (SERS) stands for an alternative to the inherent low cross-section of normal Raman scattering. Indeed, SERS is a very sensitive spectroscopic technique due to the excitation of the surface plasmon modes of the nanostructured metallic film.

Sputtered gold-coated ITO nanowires by alternating depositions from Indium and ITO targets for application in surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Setti, Grazielle O.; Mamián-López, Mónica B.; Pessoa, Priscila R.; Poppi, Ronei J.; Joanni, Ednan; Jesus, Dosil P.

2015-08-01

Indium Tin oxide (ITO) nanowires were deposited by RF sputtering over oxidized silicon using ITO and Indium targets. The nanowires grew on the substrate with a catalyst layer of Indium by the vapor-liquid-solid (VLS) mechanism. Modifications in the deposition conditions affected the morphology and dimensions of the nanowires. The samples, after being covered with gold, were evaluated as surface-enhanced Raman scattering (SERS) substrates for detection of dye solutions and very good intensifications of the Raman signal were obtained. The SERS performance of the samples was also compared to that of a commercial SERS substrate and the results achieved were similar. To the best of our knowledge, this is the first time ITO nanowires were grown by the sputtering technique using oxide and metal targets.

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.

Investigating Nanoscale Electrochemistry with Surface- and Tip-Enhanced Raman Spectroscopy.

PubMed

Zaleski, Stephanie; Wilson, Andrew J; Mattei, Michael; Chen, Xu; Goubert, Guillaume; Cardinal, M Fernanda; Willets, Katherine A; Van Duyne, Richard P

2016-09-20

The chemical sensitivity of surface-enhanced Raman spectroscopy (SERS) methodologies allows for the investigation of heterogeneous chemical reactions with high sensitivity. Specifically, SERS methodologies are well-suited to study electron transfer (ET) reactions, which lie at the heart of numerous fundamental processes: electrocatalysis, solar energy conversion, energy storage in batteries, and biological events such as photosynthesis. Heterogeneous ET reactions are commonly monitored by electrochemical methods such as cyclic voltammetry, observing billions of electrochemical events per second. Since the first proof of detecting single molecules by redox cycling, there has been growing interest in examining electrochemistry at the nanoscale and single-molecule levels. Doing so unravels details that would otherwise be obscured by an ensemble experiment. The use of optical spectroscopies, such as SERS, to elucidate nanoscale electrochemical behavior is an attractive alternative to traditional approaches such as scanning electrochemical microscopy (SECM). While techniques such as single-molecule fluorescence or electrogenerated chemiluminescence have been used to optically monitor electrochemical events, SERS methodologies, in particular, have shown great promise for exploring electrochemistry at the nanoscale. SERS is ideally suited to study nanoscale electrochemistry because the Raman-enhancing metallic, nanoscale substrate duly serves as the working electrode material. Moreover, SERS has the ability to directly probe single molecules without redox cycling and can achieve nanoscale spatial resolution in combination with super-resolution or scanning probe microscopies. This Account summarizes the latest progress from the Van Duyne and Willets groups toward understanding nanoelectrochemistry using Raman spectroscopic methodologies. The first half of this Account highlights three techniques that have been recently used to probe few- or single-molecule electrochemical events: single-molecule SERS (SMSERS), superlocalization SERS imaging, and tip-enhanced Raman spectroscopy (TERS). While all of the studies we discuss probe model redox dye systems, the experiments described herein push the study of nanoscale electrochemistry toward the fundamental limit, in terms of both chemical sensitivity and spatial resolution. The second half of this Account discusses current experimental strategies for studying nanoelectrochemistry with SERS techniques, which includes relevant electrochemically and optically active molecules, substrates, and substrate functionalization methods. In particular, we highlight the wide variety of SERS-active substrates and optically active molecules that can be implemented for EC-SERS, as well as the need to carefully characterize both the electrochemistry and resultant EC-SERS response of each new redox-active molecule studied. Finally, we conclude this Account with our perspective on the future directions of studying nanoscale electrochemistry with SERS/TERS, which includes the integration of SECM with TERS and the use of theoretical methods to further describe the fundamental intricacies of single-molecule, single-site electrochemistry at the nanoscale.

Application of SERS spectroscopy to the identification of (3,4-methylenedioxy)amphetamine in forensic samples utilizing matrix stabilized silver halides.

PubMed

Sägmüller, B; Schwarze, B; Brehm, G; Schneider, S

2001-11-01

A method based on surface-enhanced Raman scattering (SERS) spectroscopy was developed to meet the need for the reliable and rapid identification of illicit drugs such as the 'designer drug' XTC, preferably to increase the security of legal certificates. A matrix stabilized silver halide dispersion on a microtiter plate is used as the SERS-active substrate, providing an easy to use system for sample preparation and probing by means of a Raman microscope. The potential of the method is demonstrated by applying it to the identification of the psychoactive ingredients of drug containing tablets which were confiscated by the local police at techno-music events. The samples of interest were 26 different brands of XTC tablets and several pieces of evidence (powders) containing amphetamine. For reference, we show SERS and Raman spectra of pristine amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethamphetamine.

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.

Laser ablation surface-enhanced Raman microspectroscopy.

PubMed

Londero, Pablo S; Lombardi, John R; Leona, Marco

2013-06-04

Improved identification of trace organic compounds in complex matrixes is critical for a variety of fields such as material science, heritage science, and forensics. Surface-enhanced Raman scattering (SERS) is a vibrational spectroscopy technique that can attain single-molecule sensitivity and has been shown to complement mass spectrometry, but lacks widespread application without a robust method that utilizes the effect. We demonstrate a new, highly sensitive, and widely applicable approach to SERS analysis based on laser ablation in the presence of a tailored plasmonic substrate. We analyze several challenging compounds, including non-water-soluble pigments and dyed leather from an ancient Egyptian chariot, achieving sensitivity as high as 120 amol for a 1:1 signal-to-noise ratio and 5 μm spatial resolution. This represents orders of magnitude improvement in spatial resolution and sensitivity compared to those of other SERS approaches intended for widespread application, greatly increasing the applicability of SERS.

A Nanosensor for TNT Detection Based on Molecularly Imprinted Polymers and Surface Enhanced Raman Scattering

PubMed Central

Holthoff, Ellen L.; Stratis-Cullum, Dimitra N.; Hankus, Mikella E.

2011-01-01

We report on a new sensor strategy that integrates molecularly imprinted polymers (MIPs) with surface enhanced Raman scattering (SERS). The sensor was developed to detect the explosive, 2,4,6-trinitrotoluene (TNT). Micron thick films of sol gel-derived xerogels were deposited on a SERS-active surface as the sensing layer. Xerogels were molecularly imprinted for TNT using non-covalent interactions with the polymer matrix. Binding of the TNT within the polymer matrix results in unique SERS bands, which allow for detection and identification of the molecule in the MIP. This MIP-SERS sensor exhibits an apparent dissociation constant of (2.3 ± 0.3) × 10−5 M for TNT and a 3 μM detection limit. The response to TNT is reversible and the sensor is stable for at least 6 months. Key challenges, including developing a MIP formulation that is stable and integrated with the SERS substrate, and ensuring the MIP does not mask the spectral features of the target analyte through SERS polymer background, were successfully met. The results also suggest the MIP-SERS protocol can be extended to other target analytes of interest. PMID:22163761

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.

Green synthesis of gold nanoparticles by Allium sativum extract and their assessment as SERS substrate

NASA Astrophysics Data System (ADS)

Coman, Cristina; Leopold, Loredana Florina; Rugină, Olivia Dumitriţa; Barbu-Tudoran, Lucian; Leopold, Nicolae; Tofană, Maria; Socaciu, Carmen

2014-01-01

A green synthesis was used for preparing stable colloidal gold nanoparticles by using Allium sativum aqueous extract both as reducing and capping agent. The obtained nanoparticles were characterized by UV-Vis spectroscopy, Fourier-transform infrared spectroscopy (FTIR), and transmission electron microscopy. Moreover, their potential to be used as surface-enhanced Raman scattering (SERS) substrate was investigated. The obtained gold nanoparticles have spherical shape with mean diameters of 9-15 nm (depending on the amount of reducing agent used under boiling conditions) and are stable up to several months. FTIR spectroscopy shows that the nanoparticles are capped by protein molecules from the extract. The protein shell offers a protective coating, relatively impervious to external molecules, thus, rendering the nanoparticles stable and quite inert. These nanoparticles have the potential to be used as SERS substrates, both in solution and inside human fetal lung fibroblast HFL-1 living cells. We were able to demonstrate both the internalization of the nanoparticles inside HFL-1 cells and their ability to preserve the SERS signal after cellular internalization.

Self-assembled two-dimensional gold nanoparticle film for sensitive nontargeted analysis of food additives with surface-enhanced Raman spectroscopy.

PubMed

Wu, Yiping; Yu, Wenfang; Yang, Benhong; Li, Pan

2018-05-15

The use of different food additives and their active metabolites has been found to cause serious problems to human health. Thus, considering the potential effects on human health, developing a sensitive and credible analytical method for different foods is important. Herein, the application of solvent-driven self-assembled Au nanoparticles (Au NPs) for the rapid and sensitive detection of food additives in different commercial products is reported. The assembled substrates are highly sensitive and exhibit excellent uniformity and reproducibility because of uniformly distributed and high-density hot spots. The sensitive analyses of ciprofloxacin (CF), diethylhexyl phthalate (DEHP), tartrazine and azodicarbonamide at the 0.1 ppm level using this surface-enhanced Raman spectroscopy (SERS) substrate are given, and the results show that Au NP arrays can serve as efficient SERS substrates for the detection of food additives. More importantly, SERS spectra of several commercial liquors and sweet drinks are obtained to evaluate the addition of illegal additives. This SERS active platform can be used as an effective strategy in the detection of prohibited additives in food.

Rapid Determination of Thiabendazole Pesticides in Rape by Surface Enhanced Raman Spectroscopy

PubMed Central

Lin, Lei; Nie, Pengcheng; Qu, Fangfang; Chu, Bingquan; Xiao, Shupei

2018-01-01

Thiabendazole is widely used in sclerotium blight, downy mildew and black rot prevention and treatment in rape. Accurate monitoring of thiabendazole pesticides in plants will prevent potential adverse effects to the Environment and human health. Surface Enhanced Raman Spectroscopy (SERS) is a highly sensitive fingerprint with the advantages of simple operation, convenient portability and high detection efficiency. In this paper, a rapid determination method of thiabendazole pesticides in rape was conducted combining SERS with chemometric methods. The original SERS were pretreated and the partial least squares (PLS) was applied to establish the prediction model between SERS and thiabendazole pesticides in rape. As a result, the SERS enhancing effect based on silver Nano-substrate was better than that of gold Nano-substrate, where the detection limit of thiabendazole pesticides in rape could reach 0.1 mg/L. Moreover, 782, 1007 and 1576 cm−1 could be determined as thiabendazole pesticides Raman characteristic peaks in rape. The prediction effect of thiabendazole pesticides in rape was the best (Rp2 = 0.94, RMSEP = 3.17 mg/L) after the original spectra preprocessed with 1st-Derivative, and the linear relevance between thiabendazole pesticides concentration and Raman peak intensity at 782 cm−1 was the highest (R2 = 0.91). Furthermore, five rape samples with unknown thiabendazole pesticides concentration were used to verify the accuracy and reliability of this method. It was showed that prediction relative standard deviation was 0.70–9.85%, recovery rate was 94.71–118.92% and t value was −1.489. In conclusion, the thiabendazole pesticides in rape could be rapidly and accurately detected by SERS, which was beneficial to provide a rapid, accurate and reliable scheme for the detection of pesticides residues in agriculture products. PMID:29617288

Rapid Determination of Thiabendazole Pesticides in Rape by Surface Enhanced Raman Spectroscopy.

PubMed

Lin, Lei; Dong, Tao; Nie, Pengcheng; Qu, Fangfang; He, Yong; Chu, Bingquan; Xiao, Shupei

2018-04-04

Thiabendazole is widely used in sclerotium blight, downy mildew and black rot prevention and treatment in rape. Accurate monitoring of thiabendazole pesticides in plants will prevent potential adverse effects to the Environment and human health. Surface Enhanced Raman Spectroscopy (SERS) is a highly sensitive fingerprint with the advantages of simple operation, convenient portability and high detection efficiency. In this paper, a rapid determination method of thiabendazole pesticides in rape was conducted combining SERS with chemometric methods. The original SERS were pretreated and the partial least squares (PLS) was applied to establish the prediction model between SERS and thiabendazole pesticides in rape. As a result, the SERS enhancing effect based on silver Nano-substrate was better than that of gold Nano-substrate, where the detection limit of thiabendazole pesticides in rape could reach 0.1 mg/L. Moreover, 782, 1007 and 1576 cm −1 could be determined as thiabendazole pesticides Raman characteristic peaks in rape. The prediction effect of thiabendazole pesticides in rape was the best ( R p 2 = 0.94, RMSEP = 3.17 mg/L) after the original spectra preprocessed with 1st-Derivative, and the linear relevance between thiabendazole pesticides concentration and Raman peak intensity at 782 cm −1 was the highest ( R² = 0.91). Furthermore, five rape samples with unknown thiabendazole pesticides concentration were used to verify the accuracy and reliability of this method. It was showed that prediction relative standard deviation was 0.70–9.85%, recovery rate was 94.71–118.92% and t value was −1.489. In conclusion, the thiabendazole pesticides in rape could be rapidly and accurately detected by SERS, which was beneficial to provide a rapid, accurate and reliable scheme for the detection of pesticides residues in agriculture products.

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.

Plasmonic Hotspots in Air: An Omnidirectional Three-Dimensional Platform for Stand-Off In-Air SERS Sensing of Airborne Species.

PubMed

Phan-Quang, Gia Chuong; Lee, Hiang Kwee; Teng, Hao Wen; Koh, Charlynn Sher Lin; Yim, Barnabas Qinwei; Tan, Eddie Khay Ming; Tok, Wee Lee; Phang, In Yee; Ling, Xing Yi

2018-05-14

Molecular-level airborne sensing is critical for early prevention of disasters, diseases, and terrorism. Currently, most 2D surface-enhanced Raman spectroscopy (SERS) substrates used for air sensing have only one functional surface and exhibit poor SERS-active depth. "Aerosolized plasmonic colloidosomes" (APCs) are introduced as airborne plasmonic hotspots for direct in-air SERS measurements. APCs function as a macroscale 3D and omnidirectional plasmonic cloud that receives laser irradiation and emits signals in all directions. Importantly, it brings about an effective plasmonic hotspot in a length scale of approximately 2.3 cm, which affords 100-fold higher tolerance to laser misalignment along the z-axis compared with 2D SERS substrates. APCs exhibit an extraordinary omnidirectional property and demonstrate consistent SERS performance that is independent of the laser and analyte introductory pathway. Furthermore, the first in-air SERS detection is demonstrated in stand-off conditions at a distance of 200 cm, highlighting the applicability of 3D omnidirectional plasmonic clouds for remote airborne sensing in threatening or inaccessible areas. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron layer-dependent surface-enhanced raman scattering of hierarchical nanocap arrays

NASA Astrophysics Data System (ADS)

Chen, Lei; Sun, Huanhuan; Zhao, Yue; Gao, Renxian; Wang, Yaxin; Liu, Yang; Zhang, Yongjun; Hua, Zhong; Yang, Jinghai

2017-11-01

In this report, we fabricated the multi-layer Ag/Fe/Ag sandwich cap-shaped films on monolayer non-closed packed (ncp) polystyrene colloidal particle (PSCP) templates through a layer-by-layer (LBL) depositing method. This research focused on the surface-enhanced Raman scattering (SERS) effect of the thickness of the deposited Fe film which was controlled by the sputtering time. The SERS intensities were increased firstly, and then decreased as the thickness of Fe layer grows gradually, which is attributed to the charge transition from the Fermi level of the Ag NPs to Fe layer. The use of multi-layer Ag/Fe/Ag sandwich cap-shaped films enables us to evaluate the contribution of surface plasmon resonance and charge distribution between Ag and Fe to SERS enhancement. Our work introduced a novel system (Ag/Fe/Ag) for high performance SERS and extended the SERS application of Fe. Furthermore, we have designed the Ag/Fe/Ag SERS-active substrate as the immunoassay chip for quantitative determination of AFP-L3 which is the biomarker of hepatocellular carcinoma (HCC). The proposed research demonstrates that the SERS substrates with Ag/Fe/Ag sandwich cap-shaped arrays have a high sensitivity for bioassay.

SERS substrates fabricated using ceramic filters for the detection of bacteria: Eliminating the citrate interference

NASA Astrophysics Data System (ADS)

Mosier-Boss, P. A.; Sorensen, K. C.; George, R. D.; Sims, P. C.; O'braztsova, A.

2017-06-01

It was found that spectra obtained for bacteria on SERS substrates fabricated by filtering citrate-generated Ag nanoparticles (NPs) onto rigid, ceramic filters exhibited peaks due to citrate as well as the bacteria. In many cases the citrate spectrum overwhelmed that of the bacteria. Given the simplicity of the method to prepare these substrates, means of eliminating this citrate interference were explored. It was found that allowing a mixture of bacteria suspension and citrate-generated Ag NPs to incubate prior to filtering onto the ceramic filter eliminated this interference.

Transport of estradiol-17β-glucuronide, estrone-3-sulfate and taurocholate across the endoplasmic reticulum membrane: evidence for different transport systems☆

PubMed Central

Wlcek, Katrin; Hofstetter, Lia; Stieger, Bruno

2014-01-01

Important reactions of drug metabolism, including UGT mediated glucuronidation and steroidsulfatase mediated hydrolysis of sulfates, take place in the endoplasmic reticulum (ER) of hepatocytes. Consequently, UGT generated glucuronides, like estradiol-17β-glucuronide, have to be translocated back into the cytoplasm to reach their site of excretion. Also steroidsulfatase substrates, including estrone-3-sulfate, have to cross the ER membrane to reach their site of hydrolysis. Based on their physicochemical properties such compounds are not favored for passive diffusion and therefore likely necessitate transport system(s) to cross the ER membrane in either direction. The current study aims to investigate the transport of taurocholate, estradiol-17β-glucuronide, and estrone-3-sulfate in smooth (SER) and rough (RER) endoplasmic reticulum membrane vesicles isolated from Wistar and TR− rat liver. Time-dependent and bidirectional transport was demonstrated for taurocholate, showing higher uptake rates in SER than RER vesicles. For estradiol-17β-glucuronide a fast time-dependent efflux with similar efficiencies from SER and RER but no clear protein-mediated uptake was shown, indicating an asymmetric transport system for this substrate. Estrone-3-sulfate uptake was time-dependent and higher in SER than in RER vesicles. Inhibition of steroidsulfatase mediated estrone-3-sulfate hydrolysis decreased estrone-3-sulfate uptake but had no effect on taurocholate or estradiol-17β-glucuronide transport. Based on inhibition studies and transport characteristics, three different transport mechanisms are suggested to be involved in the transport of taurocholate, estrone-3-sulfate and estradiol-17β-glucuronide across the ER membrane. PMID:24406246

Development of surface enhanced Raman scattering (SERS) spectroscopy monitoring of fuel markers to prevent fraud

NASA Astrophysics Data System (ADS)

Wilkinson, Timothy; Clarkson, John; White, Peter C.; Meakin, Nicholas; McDonald, Ken

2013-05-01

Governments often tax fuel products to generate revenues to support and stimulate their economies. They also subsidize the cost of essential fuel products. Fuel taxation and subsidization practices are both subject to fraud. Oil marketing companies also suffer from fuel fraud with loss of legitimate sales and additional quality and liability issues. The use of an advanced marking system to identify and control fraud has been shown to be effective in controlling illegal activity. DeCipher has developed surface enhanced Raman scattering (SERS) spectroscopy as its lead technology for measuring markers in fuel to identify and control malpractice. SERS has many advantages that make it highly suitable for this purpose. The SERS instruments are portable and can be used to monitor fuel at any point in the supply chain. SERS shows high specificity for the marker, with no false positives. Multiple markers can also be detected in a single SERS analysis allowing, for example, specific regional monitoring of fuel. The SERS analysis from fuel is also quick, clear and decisive, with a measurement time of less than 5 minutes. We will present results highlighting our development of the use of a highly stable silver colloid as a SERS substrate to measure the markers at ppb levels. Preliminary results from the use of a solid state SERS substrate to measure fuel markers will also be presented.

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.

SERS Engineering Collaboration

DTIC Science & Technology

2012-06-01

laser beam. In the second approach, a pulsed laser was used to texture a silicon wafer to form sharp features. Silver was evaporated onto the wafer...orders of magnitude larger than that measured on a gold nanoparticle array on a glass substrate. The largest SERS enhancement for a silver device was...surface plasmons," Yizhuo Chu and Kenneth B. Crozier, Optics Letters vol. 34, 244 (2009) K3. "Gold nanorings as substrates for surface-enhanced Raman

Facile chemical routes to mesoporous silver substrates for SERS analysis

PubMed Central

Tastekova, Elina A; Polyakov, Alexander Yu; Goldt, Anastasia E; Sidorov, Alexander V; Oshmyanskaya, Alexandra A; Sukhorukova, Irina V; Shtansky, Dmitry V; Grünert, Wolgang

2018-01-01

Mesoporous silver nanoparticles were easily synthesized through the bulk reduction of crystalline silver(I) oxide and used for the preparation of highly porous surface-enhanced Raman scattering (SERS)-active substrates. An analogous procedure was successfully performed for the production of mesoporous silver films by chemical reduction of oxidized silver films. The sponge-like silver blocks with high surface area and the in-situ-prepared mesoporous silver films are efficient as both analyte adsorbents and Raman signal enhancement mediators. The efficiency of silver reduction was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The developed substrates were applied for SERS detection of rhodamine 6G (enhancement factor of about 1–5 × 105) and an anti-ischemic mildronate drug (meldonium; enhancement factor of ≈102) that is known for its ability to increase the endurance performance of athletes. PMID:29600149

Mimicking phosphorylation of Ser-74 on human deoxycytidine kinase selectively increases catalytic activity for dC and dC analogues.

PubMed

McSorley, Theresa; Ort, Stephan; Hazra, Saugata; Lavie, Arnon; Konrad, Manfred

2008-03-05

Intracellular phosphorylation of dCK on Ser-74 results in increased nucleoside kinase activity. We mimicked this phosphorylation by a Ser-74-Glu mutation in bacterially produced dCK and investigated kinetic parameters using various nucleoside substrates. The S74E mutation increases the k(cat) values 11-fold for dC, and 3-fold for the anti-cancer analogues dFdC and AraC. In contrast, the rate is decreased for the purine substrates. In HEK293 cells, we found that by comparing transiently transfected dCK(S74E)-GFP and wild-type dCK-GFP, mimicking the phosphorylation of Ser-74 has no effect on cellular localisation. We note that phosphorylation may represent a mechanism to enhance the catalytic activity of the relatively slow dCK enzyme.

A three-dimensional silver nanoparticles decorated plasmonic paper strip for SERS detection of low-abundance molecules.

PubMed

Li, Yixin; Zhang, Kun; Zhao, Jingjing; Ji, Ji; Ji, Chang; Liu, Baohong

2016-01-15

The fabrication of SERS substrates, which can offer the advantages of strong Raman signal enhancement with good reproducibility and low cost, is still a challenge for practical applications. In this work, a simple three-dimensional (3D) paper-based SERS substrate, which contains plasmonic silver-nanoparticles (AgNPs), has been developed by the silver mirror reaction. This paper strip was characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), etc. Pretreatment of the paper as well as the reaction time, temperature, and reagent concentrations for the silver mirror reaction were varied for further studies. With the optimized experimental parameters, the AgNPs synthesized and distributed in-situ on the paper strip could give more favorable SERS performance. The limit of detection (LOD) as low as 10(-11)M for Rhodamine 6G (R6G) and 10(-9)M for p-aminothiophenol (p-ATP) plus wide linear range for the log-log plot of Raman intensity versus analyte concentration were achieved. The detection of R6G in rain water was also carried out successfully. The merits of this protocol include low cost, easy operation, high sensitivity and acceptable stability, which make it ideal for the detection of environmental samples in trace amounts. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Ad-hoc surface-enhanced Raman spectroscopy methodologies for the detection of artist dyestuffs: thin layer chromatography-surface enhanced Raman spectroscopy and in situ on the fiber analysis.

PubMed

Brosseau, Christa L; Gambardella, Alessa; Casadio, Francesca; Grzywacz, Cecily M; Wouters, Jan; Van Duyne, Richard P

2009-04-15

Tailored ad-hoc methods must be developed for successful identification of minute amounts of natural dyes on works of art using Surface-Enhanced Raman Spectroscopy (SERS). This article details two of these successful approaches using silver film over nanosphere (AgFON) substrates and silica gel coupled with citrate-reduced Ag colloids. The latter substrate functions as the test system for the coupling of thin-layer chromatography and SERS (TLC-SERS), which has been used in the current research to separate and characterize a mixture of several artists' dyes. The poor limit of detection of TLC is overcome by coupling with SERS, and dyes which co-elute to nearly the same spot can be distinguished from each other. In addition, in situ extractionless non-hydrolysis SERS was used to analyze dyed reference fibers, as well as historical textile fibers. Colorants such as alizarin, purpurin, carminic acid, lac dye, crocin, and Cape jasmine were thus successfully identified.

Silver nanowires as infrared-active materials for surface-enhanced Raman scattering.

PubMed

Becucci, Maurizio; Bracciali, Monica; Ghini, Giacomo; Lofrumento, Cristiana; Pietraperzia, Giangaetano; Ricci, Marilena; Tognaccini, Lorenzo; Trigari, Silvana; Gellini, Cristina; Feis, Alessandro

2018-05-17

Surface-enhanced Raman scattering (SERS) is increasing in significance as a bioanalytical tool. Novel nanostructured metal substrates are required to improve performances and versatility of SERS spectroscopy. In particular, as biological tissues are relatively transparent in the infrared wavelength range, SERS-active materials suitable for infrared laser excitation are needed. Nanowires appear interesting in this respect as they show a very broad localized surface plasmon resonance band, ranging from near UV to near infrared wavelengths. The SERS activity of silver nanowires has been tested at three wavelengths and a fair enhancement at 1064 and 514 nm has been observed, whereas a very weak enhancement was present when exciting close to the nanowire extinction maximum. These experimentally measured optical properties have been contrasted with finite element method simulations. Furthermore, laser-induced optoacoustic spectroscopy measurements have shown that the extinction at 1064 nm is completely due to scattering. This result has an important implication that no heating occurs when silver nanowires are utilized as SERS-active substrates, thereby preventing possible thermal damage.

Probing the effect of charge transfer enhancement in off resonance mode SERS via conjugation of the probe dye between silver nanoparticles and metal substrates.

PubMed

Selvakannan, Pr; Ramanathan, Rajesh; Plowman, Blake J; Sabri, Ylias M; Daima, Hemant K; O'Mullane, Anthony P; Bansal, Vipul; Bhargava, Suresh K

2013-08-21

The charge transfer-mediated surface enhanced Raman scattering (SERS) of crystal violet (CV) molecules that were chemically conjugated between partially polarized silver nanoparticles and optically smooth gold and silver substrates has been studied under off-resonant conditions. Tyrosine molecules were used as a reducing agent to convert silver ions into silver nanoparticles where oxidised tyrosine caps the silver nanoparticle surface with its semiquinone group. This binding through the quinone group facilitates charge transfer and results in partially oxidised silver. This establishes a chemical link between the silver nanoparticles and the CV molecules, where the positively charged central carbon of CV molecules can bind to the terminal carboxylate anion of the oxidised tyrosine molecules. After drop casting Ag nanoparticles bound with CV molecules it was found that the free terminal amine groups tend to bind with the underlying substrates. Significantly, only those CV molecules that were chemically conjugated between the partially polarised silver nanoparticles and the underlying gold or silver substrates were found to show SERS under off-resonant conditions. The importance of partial charge transfer at the nanoparticle/capping agent interface and the resultant conjugation of CV molecules to off resonant SERS effects was confirmed by using gold nanoparticles prepared in a similar manner. In this case the capping agent binds to the nanoparticle through the amine group which does not facilitate charge transfer from the gold nanoparticle and under these conditions SERS enhancement in the sandwich configuration was not observed.

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.

Detecting explosive molecules from nanoliter solution: A new paradigm of SERS sensing on hydrophilic photonic crystal biosilica.

PubMed

Kong, Xianming; Xi, Yuting; Le Duff, Paul; Chong, Xinyuan; Li, Erwen; Ren, Fanghui; Rorrer, Gregory L; Wang, Alan X

2017-02-15

We demonstrate a photonic crystal biosilica surface-enhanced Raman scattering (SERS) substrate based on a diatom frustule with in-situ synthesized silver nanoparticles (Ag NPs) to detect explosive molecules from nanoliter (nL) solution. By integrating high density Ag NPs inside the nanopores of diatom biosilica, which is not achievable by traditional self-assembly techniques, we obtained ultra-high SERS sensitivity due to dual enhancement mechanisms. First, the hybrid plasmonic-photonic crystal biosilica with three dimensional morphologies was obtained by electroless-deposited Ag seeds at nanometer sized diatom frustule surface, which provides high density hot spots as well as strongly coupled optical resonances with the photonic crystal structure of diatom frustules. Second, we discovered that the evaporation-driven microscopic flow combined with the strong hydrophilic surface of diatom frustules is capable of concentrating the analyte molecules, which offers a simple yet effective mechanism to accelerate the mass transport into the SERS substrate. Using the inkjet printing technology, we are able to deliver multiple 100pico-liter (pL) volume droplets with pinpoint accuracy into a single diatom frustule with dimension around 30µm×7µm×5µm, which allows for label-free detection of explosive molecules such as trinitrotoluene (TNT) down to 10 -10 M in concentration and 2.7×10 -15 g in mass from 120nL solution. Our research illustrates a new paradigm of SERS sensing to detect trace level of chemical compounds from minimum volume of analyte using nature created photonic crystal biosilica materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Detecting explosive molecules from nanoliter solution: A new paradigm of SERS sensing on hydrophilic photonic crystal biosilica

PubMed Central

Kong, Xianming; Xi, Yuting; Le Duff, Paul; Chong, Xinyuan; Li, Erwen; Ren, Fanghui; Rorrer, Gregory L.; Wang, Alan X.

2017-01-01

We demonstrate a photonic crystal biosilica surface-enhanced Raman scattering (SERS) substrate based on a diatom frustule with in-situ synthesized silver nanoparticles (Ag NPs) to detect explosive molecules from nanoliter (nL) solution. By integrating high density Ag NPs inside the nanopores of diatom biosilica, which is not achievable by traditional self-assembly techniques, we obtained ultra-high SERS sensitivity due to dual enhancement mechanisms. First, the hybrid plasmonic-photonic crystal biosilica with three dimensional morphologies was obtained by electroless-deposited Ag seeds at nanometer sized diatom frustule surface, which provides high density hot spots as well as strongly coupled optical resonances with the photonic crystal structure of diatom frustules. Second, we discovered that the evaporation-driven microscopic flow combined with the strong hydrophilic surface of diatom frustules is capable of concentrating the analyte molecules, which offers a simple yet effective mechanism to accelerate the mass transport into the SERS substrate. Using the inkjet printing technology, we are able to deliver multiple 100 pico-liter (pL) volume droplets with pinpoint accuracy into a single diatom frustule with dimension around 30 μm × 7 μm × 5 μm, which allows for label-free detection of explosive molecules such as trinitrotoluene (TNT) down to 10−10 M in concentration and 2.7 × 10−15 g in mass from 120 nL solution. Our research illustrates a new paradigm of SERS sensing to detect trace level of chemical compounds from minimum volume of analyte using nature created photonic crystal biosilica materials. PMID:27471144

SERS strategy based on the modified Au nanoparticles for highly sensitive detection of bisphenol A residues in milk.

PubMed

Yang, Libin; Chen, Yongliang; Shen, Yu; Yang, Ming; Li, Xiuling; Han, Xiaoxia; Jiang, Xin; Zhao, Bing

2018-03-01

Bisphenol A (BPA) is a highly toxic chemical, and its residue in milk product is threatening people's health due to its possible leaching from the packagings and cans with BPA coating. In this work, halides modified Au nanoparticles (NPs) as the modification substrates were first designed for rapid and sensitive determination of BPA residue in real milk by SERS method with the assistance of aggregation agents (Zn 2+ ). It can be concluded that Au NPs modification substrate with assistance of the aggregation agent can remarkably improve the detection sensitivity of BPA residue, which can significantly enhance the SERS signal of BPA and achieve the trace-level detection of BPA residue. Under the optimal conditions, the limit of detection of BPA residue can be as low as to 4.3 × 10 -9 mol/L (equal to 0.98 × 10 -3 mg/kg), which is much less than the standard of European Union (0.6mg/kg). And, there is a good linear relationship (R 2 = 0.990) between the intensity of SERS signal and the logarithm of BPA concentration in the range of 1.0 × 10 -8 -1.0 × 10 -3 mol/L. By this method, the recovery of BPA residue ranges from 89.5% to 100.2% with relative standard deviation between 4.6% and 2.7%. The proposed SERS method proves to be reliable, highly sensitive and possesses good reproducibility, which is very promising for sensitive detection of bisphenols residue in foodstuff. Copyright © 2017 Elsevier B.V. All rights reserved.

Growth graphene on silver-copper nanoparticles by chemical vapor deposition for high-performance surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Zhang, Xiumei; Xu, Shicai; Jiang, Shouzhen; Wang, Jihua; Wei, Jie; Xu, Shida; Gao, Shoubao; Liu, Hanping; Qiu, Hengwei; Li, Zhen; Liu, Huilan; Li, Zhenhua; Li, Hongsheng

2015-10-01

We present a graphene/silver-copper nanoparticle hybrid system (G/SCNPs) to be used as a high-performance surface-enhanced Raman scattering (SERS) substrate. The silver-copper nanoparticles wrapped by a monolayer graphene layer are directly synthesized on SiO2/Si substrate by chemical vapor deposition in a mixture of methane and hydrogen. The G/SCNPs shows excellent SERS enhancement activity and high reproducibility. The minimum detected concentration of R6G is as low as 10-10 M and the calibration curve shows a good linear response from 10-6 to 10-10 M. The date fluctuations from 20 positions of one SERS substrate are less than 8% and from 20 different substrates are less than 10%. The high reproducibility of the enhanced Raman signals could be due to the presence of an ultrathin graphene layer and uniform morphology of silver-copper nanoparticles. The use of G/SCNPs for detection of nucleosides extracted from human urine demonstrates great potential for the practical applications on a variety of detection in medicine and biotechnology field.

Superhydrophobic Analyte Concentration Utilizing Colloid-Pillar Array SERS Substrates

DOE PAGES

Wallace, Ryan A.; Charlton, Jennifer J.; Kirchner, Teresa B.; ...

2014-11-04

In order to detect a few molecules present in a large sample it is important to know the trace components in the medicinal and environmental sample. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. Moreover, the following work involves superhydrophobic surfaces that includes silicon pillar arrays formed by lithographic and dewetting protocols. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added tomore » the functionalized pillar array system via soaking. The pillars are used native and with hydrophobic modification. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 10-12 M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up applications in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.« less

Superhydrophobic Analyte Concentration Utilizing Colloid-Pillar Array SERS Substrates

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

Wallace, Ryan A.; Charlton, Jennifer J.; Kirchner, Teresa B.

In order to detect a few molecules present in a large sample it is important to know the trace components in the medicinal and environmental sample. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. Moreover, the following work involves superhydrophobic surfaces that includes silicon pillar arrays formed by lithographic and dewetting protocols. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added tomore » the functionalized pillar array system via soaking. The pillars are used native and with hydrophobic modification. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 10-12 M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up applications in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.« less

A 5000-Fold Increase in the Specificity of a Bacterial Phosphotriesterase for Malathion through Combinatorial Active Site Mutagenesis

PubMed Central

Naqvi, Tatheer; Warden, Andrew C.; French, Nigel; Sugrue, Elena; Carr, Paul D.; Jackson, Colin J.; Scott, Colin

2014-01-01

Phosphotriesterases (PTEs) have been isolated from a range of bacterial species, including Agrobcaterium radiobacter (PTEAr), and are efficient enzymes with broad substrate ranges. The turnover rate of PTEAr for the common organophosphorous insecticide malathion is lower than expected based on its physical properties; principally the pka of its leaving group. In this study, we rationalise the turnover rate of PTEAr for malathion using computational docking of the substrate into a high resolution crystal structure of the enzyme, suggesting that malathion is too large for the PTEAr binding pocket. Protein engineering through combinatorial active site saturation testing (CASTing) was then used to increase the rate of malathion turnover. Variants from a CASTing library in which Ser308 and Tyr309 were mutated yielded variants with increased activity towards malathion. The most active PTEAr variant carried Ser308Leu and Tyr309Ala substitutions, which resulted in a ca. 5000-fold increase in k cat/K M for malathion. X-ray crystal structures for the PTEAr Ser308Leu\\Tyr309Ala variant demonstrate that the access to the binding pocket was enhanced by the replacement of the bulky Tyr309 residue with the smaller alanine residue. PMID:24721933

SERS based immuno-microwell arrays for multiplexed detection of foodborne pathogenic bacteria

NASA Astrophysics Data System (ADS)

Sun, Jian; Hankus, Mikella E.; Cullum, Brian M.

2009-05-01

A novel surface enhanced Raman scattering (SERS)-based immuno-microwell array has been developed for multiplexed detection of foodborne pathogenic bacteria. The immuno-microwell array was prepared by immobilizing the optical addressable immunomagnetic beads (IMB) into the microwell array on one end of a fiber optic bundle. The IMBs, magnetic beads coated with specific antibody to specific bacteria, were used for immunomagnetic separation (IMS) of corresponding bacteria. The magnetic separation by the homemade magnetic separation system was evaluated in terms of the influences of several important parameters including the beads concentration, the sample volume and the separation time. IMS separation efficiency of the model bacteria E.coli O157:H7 was 63% in 3 minutes. The microwell array was fabricated on hydrofluoric acid etched end of a fiber optic bundle containing 30,000 fiber elements. After being coated with silver, the microwell array was used as a uniform SERS substrate with the relative standard deviation of the SERS enhancement across the microwell array < 2% and the enhancement factor as high as 2.18 x 107. The antibody modified microwell array was prepared for bacteria immobilization into the microwell array, which was characterized by a sandwich immunoassay. To demonstrate the potential of multiplexed SERS detection with the immuno-microwell array, the SERS spectra of different Raman dye labeled magnetic beads as well as mixtures were measured on the mircrowell array. In bead mixture, different beads were identified by the characteristic SERS bands of the corresponding Raman label.

Soft nanoimprint lithography on SiO2 sol-gel to elaborate sensitive substrates for SERS detection

NASA Astrophysics Data System (ADS)

Hamouda, Frédéric; Bryche, Jean-François; Aassime, Abdelhanin; Maillart, Emmanuel; Gâté, Valentin; Zanettini, Silvia; Ruscica, Jérémy; Turover, Daniel; Bartenlian, Bernard

2017-12-01

This paper presents a new alternative fabrication of biochemical sensor based on surface enhanced Raman scattering (SERS) by soft nanoimprint lithography (S-NIL) on SiO2 sol-gel. Stabilization of the sol-gel film is obtained by annealing which simplifies the manufacturing of these biosensors and is compatible with mass production at low cost. This detector relies on a specific pattern of gold nanodisks on a thin gold film to obtain a better sensitivity of molecules' detection. Characterizations of SERS devices were performed on a confocal Raman microspectrophotometer after a chemical functionalization. We report a lateral collapse effect on poly(diméthylsiloxane) (PDMS) stamp for specific nanostructure dimensions. This unintentional effect is used to evaluate S-NIL resolution in SiO2 sol-gel.

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.

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

Applications of Quantum Cascade Laser Scanners for Remote Detection of Chemical and Biological Threats and Weapons of Mass Destruction

DTIC Science & Technology

2014-07-09

Rivera. Highly Sensitive Filter Paper Substrate for SERS Trace Explosives Detection , International Journal of Spectroscopy, (09 2012): 0. doi: 10.1155...Highly Sensitive Filter Paper Substrate for SERS Field Detection of Trace Threat Chemicals”, PITTCON-2013: Forensic Analysis in the Lab and Crime Scene...the surface. In addition, built-in algorithms were used for nearly real-time sample detection . Trace and bulk concentrations of the other substances

Microwave-assisted synthesis of sensitive silver substrate for surface-enhanced Raman scattering spectroscopy

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

Xia Lixin; Wang Haibo; Wang Jian

A sensitive silver substrate for surface-enhanced Raman scattering (SERS) spectroscopy is synthesized under multimode microwave irradiation. The microwave-assisted synthesis of the SERS-active substrate was carried out in a modified domestic microwave oven of 2450 MHz, and the reductive reaction was conducted in a polypropylene container under microwave irradiation with a power of 100 W for 5 min. Formaldehyde was employed as both the reductant and microwave absorber in the reductive process. The effects of different heating methods (microwave dielectric and conventional) on the properties of the SERS-active substrates were investigated. Samples obtained with 5 min of microwave irradiation at amore » power of 100 W have more well-defined edges, corners, and sharper surface features, while the samples synthesized with 1 h of conventional heating at 40 deg. C consist primarily of spheroidal nanoparticles. The SERS peak intensity of the {approx}1593 cm{sup -1} band of 4-mercaptobenzoic acid adsorbed on silver nanoparticles synthesized with 5 min of microwave irradiation at a power of 100 W is about 30 times greater than when it is adsorbed on samples synthesized with 1 h of conventional heating at 40 deg. C. The results of quantum chemical calculations are in good agreement with our experimental data. This method is expected to be utilized for the synthesis of other metal nanostructural materials.« less

Tracking the intracellular drug release from graphene oxide using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Jie; Zong, Cheng; Shen, He; Cao, Yuhua; Ren, Bin; Zhang, Zhijun

2013-10-01

We have developed a graphene oxide (GO)-based nanoplatform simultaneously loaded with a chemical drug and Ag nanoparticles (NPs), and employed it to study the drug release from GO in living cells by surface-enhanced Raman spectroscopy (SERS). In our strategy, doxorubicin (DOX), a typical model anticancer drug, was loaded onto chemically prepared GO by means of π-π stacking, while the Ag NPs were covalently modified onto GO. After incubation of the DOX- and Ag NPs-loaded GO with Ca Ski cells for several hours, DOX will detach from the GO in an acidic environment due to the pH-dependent π-π interaction between DOX and GO. Real-time measurement of SERS signals of DOX using the GO loaded with Ag NPs as a SERS-active substrate allows us to monitor the process of the drug release inside the living cell. The SERS results reveal that DOX is initially released from the GO surface inside the lysosomes, then escapes into the cytoplasm, and finally enters the nucleus, while GO, the nanocarrier, remains within the cytoplasm, without entering the nucleus.We have developed a graphene oxide (GO)-based nanoplatform simultaneously loaded with a chemical drug and Ag nanoparticles (NPs), and employed it to study the drug release from GO in living cells by surface-enhanced Raman spectroscopy (SERS). In our strategy, doxorubicin (DOX), a typical model anticancer drug, was loaded onto chemically prepared GO by means of π-π stacking, while the Ag NPs were covalently modified onto GO. After incubation of the DOX- and Ag NPs-loaded GO with Ca Ski cells for several hours, DOX will detach from the GO in an acidic environment due to the pH-dependent π-π interaction between DOX and GO. Real-time measurement of SERS signals of DOX using the GO loaded with Ag NPs as a SERS-active substrate allows us to monitor the process of the drug release inside the living cell. The SERS results reveal that DOX is initially released from the GO surface inside the lysosomes, then escapes into the cytoplasm, and finally enters the nucleus, while GO, the nanocarrier, remains within the cytoplasm, without entering the nucleus. Electronic supplementary information (ESI) available: Cytotoxicity of Ag-GO SERS image after the cell incubated with Ag-GO for 2 h fluorescence images of Ca Ski cells. See DOI: 10.1039/c3nr03264g

Insulin and Metabolic Stress Stimulate Multisite Serine/Threonine Phosphorylation of Insulin Receptor Substrate 1 and Inhibit Tyrosine Phosphorylation*

PubMed Central

Hançer, Nancy J.; Qiu, Wei; Cherella, Christine; Li, Yedan; Copps, Kyle D.; White, Morris F.

2014-01-01

IRS1 and IRS2 are key substrates of the insulin receptor tyrosine kinase. Mass spectrometry reveals more than 50 phosphorylated IRS1 serine and threonine residues (Ser(P)/Thr(P) residues) in IRS1 from insulin-stimulated cells or human tissues. We investigated a subset of IRS1 Ser(P)/Thr(P) residues using a newly developed panel of 25 phospho-specific monoclonal antibodies (αpS/TmAbIrs1). CHO cells overexpressing the human insulin receptor and rat IRS1 were stimulated with insulin in the absence or presence of inhibitors of the PI3K → Akt → mechanistic target of rapamycin (mTOR) → S6 kinase or MEK pathways. Nearly all IRS1 Ser(P)/Thr(P) residues were stimulated by insulin and significantly suppressed by PI3K inhibition; fewer were suppressed by Akt or mTOR inhibition, and none were suppressed by MEK inhibition. Insulin-stimulated Irs1 tyrosine phosphorylation (Tyr(P)Irs1) was enhanced by inhibition of the PI3K → Akt → mTOR pathway and correlated with decreased Ser(P)-302Irs1, Ser(P)-307Irs1, Ser(P)-318Irs1, Ser(P)-325Irs1, and Ser(P)-346Irs1. Metabolic stress modeled by anisomycin, thapsigargin, or tunicamycin increased many of the same Ser(P)/Thr(P) residues as insulin, some of which (Ser(P)-302Irs1, Ser(P)-307Irs1, and four others) correlated significantly with impaired insulin-stimulated Tyr(P)Irs1. Thus, IRS1 Ser(P)/Thr(P) is an integrated response to insulin stimulation and metabolic stress, which associates with reduced Tyr(P)Irs1 in CHOIR/IRS1 cells. PMID:24652289

Ultrasensitive sliver nanorods array SERS sensor for mercury ions.

PubMed

Song, Chunyuan; Yang, Boyue; Zhu, Yu; Yang, Yanjun; Wang, Lianhui

2017-01-15

With years of outrageous mercury emissions, there is an urgent need to develop convenient and sensitive methods for detecting mercury ions in response to increasingly serious mercury pollution in water. In the present work, a portable, ultrasensitive SERS sensor is proposed and utilized for detecting trace mercury ions in water. The SERS sensor is prepared on an excellent sliver nanorods array SERS substrate by immobilizing T-component oligonucleotide probes labeled with dye on the 3'-end and -SH on the 5'-end. The SERS sensor responses to the specific chemical bonding between thymine and mercury ions, which causes the previous flexible single strand of oligonucleotide probe changing into rigid and upright double chain structure. Such change in the structure drives the dyes far away from the excellent SERS substrate and results in a SERS signal attenuation of the dye. Therefore, by monitoring the decay of SERS signal of the dye, mercury ions in water can be detected qualitatively and quantitatively. The experimental results indicate that the proposed optimal SERS sensor owns a linear response with wide detecting range from 1pM to 1μM, and a detection limit of 0.16pM is obtained. In addition, the SERS sensor demonstrates good specificity for Hg 2+ , which can accurately identify trace mercury ions from a mixture of ten kinds of other ions. The SERS sensor has been further executed to analyze the trace mercury ions in tap water and lake water respectively, and good recovery rates are obtained for sensing both kinds of water. With its high selectivity and good portability, the ultrasensitive SERS sensor is expected to be a promising candidate for discriminating mercury ions in the fields of environmental monitoring and food safety. Copyright © 2016 Elsevier B.V. All rights reserved.

Large-area surface-enhanced Raman spectroscopy imaging of brain ischemia by gold nanoparticles grown on random nanoarrays of transparent boehmite.

PubMed

Yamazoe, Shogo; Naya, Masayuki; Shiota, Megumi; Morikawa, Takayuki; Kubo, Akiko; Tani, Takeharu; Hishiki, Takako; Horiuchi, Tadashi; Suematsu, Makoto; Kajimura, Mayumi

2014-06-24

Although SERS spectroscopy, which is sensitive to molecular vibration states, offers label-free visualization of molecules, identification of molecules and their reliable large-area imaging remains to be developed. Limitation comes from difficulties in fabricating a SERS-active substrate with homogeneity over a large area. Here, we overcome this hurdle by utilizing a self-assembled nanostructure of boehmite that is easily achieved by a hydrothermal preparation of aluminum as a template for subsequent gold (Au) deposition. This approach brought about random arrays of Au-nanostructures with a diameter of ∼125 nm and a spacing of <10 nm, ideal for the hot-spots formation. The substrate, which we named "gold nanocoral" (GNC) after its coral reef-like shape, exhibited a small variability of signal intensities (coefficient value <11.2%) in detecting rhodamine 6G molecule when 121 spots were measured over an area of 10 × 10 mm(2), confirming high uniformity. The transparent nature of boehmite enabled us to conduct the measurement from the back-side of the substrate as efficiently as that from the front-side. We then conducted tissue imaging using the mouse ischemic brain adhered on the GNC substrate. Through nontargeted construction of two-dimensional-Raman-intensity map using differential bands from two metabolically distinct regions, that is, ischemic core and contralateral-control areas, we found that mapping using the adenine ring vibration band at 736 cm(-1) clearly demarcated ischemic core where high-energy adenine phosphonucleotides were degraded as judged by imaging mass spectrometry. Such a detection capability makes the GNC-based SERS technology especially promising for revealing acute energy derangement of tissues.

Surface-enhanced Raman spectroscopic and surface plasmon resonance in situ study of self-assembly of 4-mercaptobenzoic acid on gold surface

NASA Astrophysics Data System (ADS)

Thi, Minh Do; Volka, Karel

2010-07-01

A feasibility study has been undertaken to assess the suitability of a commercially available SERS substrate for monitoring of self-assembling deposition process. Monolayer self-assembly of 4-mercaptobenzoic acid on SERS active substrate Klarite™ from absolute and acidified ethanol was studied and compared with deposition on SPR substrate from absolute ethanol. Changes in integral intensity of the phenyl bands at 1587 and 1076 cm -1 and ethanol band at 1451 cm -1 allow to follow structural changes in the monolayer. Stability of the monolayer assembled from acidified ethanol in contrast to the pure ethanol was demonstrated.

SERS substrates fabricated using ceramic filters for the detection of bacteria: Eliminating the citrate interference.

PubMed

Mosier-Boss, P A; Sorensen, K C; George, R D; Sims, P C; O'braztsova, A

2017-06-05

It was found that spectra obtained for bacteria on SERS substrates fabricated by filtering citrate-generated Ag nanoparticles (NPs) onto rigid, ceramic filters exhibited peaks due to citrate as well as the bacteria. In many cases the citrate spectrum overwhelmed that of the bacteria. Given the simplicity of the method to prepare these substrates, means of eliminating this citrate interference were explored. It was found that allowing a mixture of bacteria suspension and citrate-generated Ag NPs to incubate prior to filtering onto the ceramic filter eliminated this interference. Copyright © 2017 Elsevier B.V. All rights reserved.

Controllable Ag nanostructure patterning in a microfluidic channel for real-time SERS systems.

PubMed

Leem, Juyoung; Kang, Hyun Wook; Ko, Seung Hwan; Sung, Hyung Jin

2014-03-07

We present a microfluidic patterning system for fabricating nanostructured Ag thin films via a polyol method. The fabricated Ag thin films can be used immediately in a real-time SERS sensing system. The Ag thin films are formed on the inner surfaces of a microfluidic channel so that a Ag-patterned Si wafer and a Ag-patterned PDMS channel are produced by the fabrication. The optimum sensing region and fabrication duration for effective SERS detection were determined. As SERS active substrates, the patterned Ag thin films exhibit an enhancement factor (EF) of 4.25 × 10(10). The Ag-patterned polymer channel was attached to a glass substrate and used as a microfluidic sensing system for the real-time monitoring of biomolecule concentrations. This microfluidic patterning system provides a low-cost process for the fabrication of materials that are useful in medical and pharmaceutical detection and can be employed in mass production.

Mimicking phosphorylation of Ser-74 on human deoxycytidine kinase selectively increases catalytic activity for dC and dC analogues

PubMed Central

McSorley, Theresa; Ort, Stephan; Hazra, Saugata; Lavie, Arnon; Konrad, Manfred

2009-01-01

Intracellular phosphorylation of dCK on Ser-74 results in increased nucleoside kinase activity. We mimicked this phosphorylation by a Ser-74-Glu mutation in bacterially produced dCK and investigated kinetic parameters using various nucleoside substrates. The S74E mutation increases the kcat values 11-fold for dC, and 3-fold for the anti-cancer analogues dFdC and AraC. In contrast, the rate is decreased for the purine substrates. In HEK293 cells, we found that by comparing transiently transfected dCK(S74E)-GFP and wild-type dCK-GFP, mimicking the phosphorylation of Ser-74 has no effect on cellular localisation. We note that phosphorylation may represent a mechanism to enhance the catalytic activity of the relatively slow dCK enzyme. PMID:18258203

Facile fabrication of homogeneous 3D silver nanostructures on gold-supported polyaniline membranes as promising SERS substrates.

PubMed

Xu, Ping; Mack, Nathan H; Jeon, Sea-Ho; Doorn, Stephen K; Han, Xijiang; Wang, Hsing-Lin

2010-06-01

We report a facile synthesis of large-area homogeneous three-dimensional (3D) Ag nanostructures on Au-supported polyaniline (PANI) membranes through a direct chemical reduction of metal ions by PANI. The citric acid absorbed on the Au nuclei that are prefabricated on PANI membranes directs Ag nanoaprticles (AgNPs) to self-assemble into 3D Ag nanosheet structures. The fabricated hybrid metal nanostructures display uniform surface-enhanced Raman scattering (SERS) responses throughout the whole surface area, with an average enhancement factor of 10(6)-10(7). The nanocavities formed by the stereotypical stacking of these Ag nanosheets and the junctions and gaps between two neighboring AgNPs are believed to be responsible for the strong SERS response upon plasmon absorption. These homogeneous metal nanostructure decorated PANI membranes can be used as highly efficient SERS substrates for sensitive detection of chemical and biological analytes.

Reversible gating of smart plasmonic molecular traps using thermoresponsive polymers for single-molecule detection

PubMed Central

Zheng, Yuanhui; Soeriyadi, Alexander H.; Rosa, Lorenzo; Ng, Soon Hock; Bach, Udo; Justin Gooding, J.

2015-01-01

Single-molecule surface-enhanced Raman spectroscopy (SERS) has attracted increasing interest for chemical and biochemical sensing. Many conventional substrates have a broad distribution of SERS enhancements, which compromise reproducibility and result in slow response times for single-molecule detection. Here we report a smart plasmonic sensor that can reversibly trap a single molecule at hotspots for rapid single-molecule detection. The sensor was fabricated through electrostatic self-assembly of gold nanoparticles onto a gold/silica-coated silicon substrate, producing a high yield of uniformly distributed hotspots on the surface. The hotspots were isolated with a monolayer of a thermoresponsive polymer (poly(N-isopropylacrylamide)), which act as gates for molecular trapping at the hotspots. The sensor shows not only a good SERS reproducibility but also a capability to repetitively trap and release molecules for single-molecular sensing. The single-molecule sensitivity is experimentally verified using SERS spectral blinking and bianalyte methods. PMID:26549539

Design of Hybrid Nanostructural Arrays to Manipulate SERS-Active Substrates by Nanosphere Lithography.

PubMed

Zhao, Xiaoyu; Wen, Jiahong; Zhang, Mengning; Wang, Dunhui; Wang, Yaxin; Chen, Lei; Zhang, Yongjun; Yang, Jinghai; Du, Youwei

2017-03-01

An easy-handling and low-cost method is utilized to controllably fabricate nanopattern arrays as the surface-enhanced Raman scattering (SERS) active substrates with high density of SERS-active areas (hot spots). A hybrid silver array of nanocaps and nanotriangles are prepared by combining magnetron sputtering and plasma etching. By adjusting the etching time of polystyrene (PS) colloid spheres array in silver nanobowls, the morphology of the arrays can be easily manipulated to control the formation and distribution of hot spots. The experimental results show that the hybrid nanostructural arrays have large enhancement factor, which is estimated to be seven times larger than that in the array of nanocaps and three times larger than that in the array of nanorings and nanoparticles. According to the results of finite-difference time-domain simulation, the excellent SERS performance of this array is ascribed to the high density of hot spots and enhanced electromagnetic field.

Towards the development of a rapid, portable, surface enhanced Raman spectroscopy based cleaning verification system for the drug nelarabine.

PubMed

Corrigan, Damion K; Salton, Neale A; Preston, Chris; Piletsky, Sergey

2010-09-01

Cleaning verification is a scientific and economic problem for the pharmaceutical industry. A large amount of potential manufacturing time is lost to the process of cleaning verification. This involves the analysis of residues on spoiled manufacturing equipment, with high-performance liquid chromatography (HPLC) being the predominantly employed analytical technique. The aim of this study was to develop a portable cleaning verification system for nelarabine using surface enhanced Raman spectroscopy (SERS). SERS was conducted using a portable Raman spectrometer and a commercially available SERS substrate to develop a rapid and portable cleaning verification system for nelarabine. Samples of standard solutions and swab extracts were deposited onto the SERS active surfaces, allowed to dry and then subjected to spectroscopic analysis. Nelarabine was amenable to analysis by SERS and the necessary levels of sensitivity were achievable. It is possible to use this technology for a semi-quantitative limits test. Replicate precision, however, was poor due to the heterogeneous drying pattern of nelarabine on the SERS active surface. Understanding and improving the drying process in order to produce a consistent SERS signal for quantitative analysis is desirable. This work shows the potential application of SERS for cleaning verification analysis. SERS may not replace HPLC as the definitive analytical technique, but it could be used in conjunction with HPLC so that swabbing is only carried out once the portable SERS equipment has demonstrated that the manufacturing equipment is below the threshold contamination level.

Preparation of sensitive and recyclable porous Ag/TiO2 composite films for SERS detection

NASA Astrophysics Data System (ADS)

Zhang, Zhengyi; Yu, Jiajie; Yang, Jingying; Lv, Xiang; Wang, Tianhe

2015-12-01

Porous Ag/TiO2 composite films were prepared by spin coating of titania on normal glass slides and subsequent photochemical deposition of silver nanoparticles (AgNPs). The films were characterized by XRD and FESEM to reveal micro structural and morphological differences between films obtained under varied conditions. The SERS properties of these films were investigated using aqueous crystal violet (CV) as probe molecules. The results indicate that the content of polyethylene glycol (PEG) and photo-reduction time had significant influences on both the microstructure and SERS performance of Ag/TiO2 films. The highest SERS sensitivity that allowed as low as 10-10 M aqueous CV to be detected, was achieved with the PEG/(C4H9O)4Ti molar ratio being 0.08% and with 30 min of UV irradiation. With this film a linear relationship was established through experiment between SERS intensity and CV concentration from 10-10 to 10-5 M, which could be used as a calibration curve for CV concentration measurement. In addition, the film could be reused as a SERS substrate for up to four times without significantly losing SERS sensitivity if a simple regeneration was followed. It is visualized that the Ag/TiO2 film on glass has potentials for being developed into a practical SERS substrate with high sensitivity and good reusability.

Preparation and evaluation of nanocellulose-gold nanoparticle nanocomposites for SERS applications.

PubMed

Wei, Haoran; Rodriguez, Katia; Renneckar, Scott; Leng, Weinan; Vikesland, Peter J

2015-08-21

Nanocellulose is of research interest due to its extraordinary optical, thermal, and mechanical properties. The incorporation of guest nanoparticles into nanocellulose substrates enables production of novel nanocomposites with a broad range of applications. In this study, gold nanoparticle/bacterial cellulose (AuNP/BC) nanocomposites were prepared and evaluated for their applicability as surface-enhanced Raman scattering (SERS) substrates. The nanocomposites were prepared by citrate mediated in situ reduction of Au(3+) in the presence of a BC hydrogel at 303 K. Both the size and morphology of the AuNPs were functions of the HAuCl4 and citrate concentrations. At high HAuCl4 concentrations, Au nanoplates form within the nanocomposites and are responsible for high SERS enhancements. At lower HAuCl4 concentrations, uniform nanospheres form and the SERS enhancement is dependent on the nanosphere size. The time-resolved increase in the SERS signal was probed as a function of drying time with SERS 'hot-spots' primarily forming in the final minutes of nanocomposite drying. The application of the AuNP/BC nanocomposites for detection of the SERS active dyes MGITC and R6G as well as the environmental contaminant atrazine is illustrated as is its use under low and high pH conditions. The results indicate the broad applicability of this nanocomposite for analyte detection.

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.

Super-SERS-active and highly effective antimicrobial Ag nanodendrites

NASA Astrophysics Data System (ADS)

Li, H. B.; Liu, P.; Liang, Y.; Xiao, J.; Yang, G. W.

2012-07-01

We have developed simple and green electrochemistry to synthesize Ag nanostructures with high purity, good crystallinity and smooth surface for applications as super-SERS (surface-enhanced Raman scattering), SERS-active substrates and with highly effective antimicrobial activities. This synthesis takes place in a clean and slow reaction environment without any chemical additives, which ensures an ultrahigh active surface of the as-synthesized Ag nanostructures owing to their purity, good crystallinity and smooth morphology. Using this method, we synthesized nearly perfect Ag nanodendrites (NDs), which exhibit super-SERS sensitivity when they are used to detect the SERS spectra of rhodamine 6G at concentrations as low as 5 × 10-16 M, and have an ultrahigh electromagnetic (EM) enhancement factor of the order of 1013, breaking through the theoretical limit of EM enhancement. Meanwhile, the as-synthesized Ag NDs possess highly effective antimicrobial activities for Escherichia coli, Candida albicans and Staphylococcus aureus, which are over 10 times that of silver nanoparticles. Additionally, the basic physics and chemistry involved in the fabrication of Ag nanostructures are pursued. These investigations show that silver nanostructures with highly active surfaces can make the most of Ag nanostructures functioning as super-SERS-active substrates and multiple antibiotics.

Innovative nanostructures for highly sensitive vibrational biosensing (Conference Presentation)

NASA Astrophysics Data System (ADS)

Popp, Juergen; Mayerhöfer, Thomas; Cialla-May, Dana; Weber, Karina; Huebner, Uwe

2016-03-01

Employing vibrational spectroscopy (IR-absorption and Raman spectroscopy) allows for the labelfree detection of molecular specific fingerprints of inorganic, organic and biological substances. The sensitivity of vibrational spectroscopy can be improved by several orders of magnitude via the application of plasmonic active surfaces. Within this contribution we will discuss two such approaches, namely surface enhanced Raman spectroscopy (SERS) as well as surface enhanced IR absorption (SEIRA). It will be shown that SERS using metal colloids as SERS active substrate in combination with a microfluidic lab-on-a-chip (LOC) device enables high throughput and reproducible measurements with highest sensitivity and specificity. The application of such a LOC-SERS approach for therapeutic drug monitoring (e.g. quantitative detection of antibiotics in a urine matrix) will be presented. Furthermore, we will introduce innovative bottom-up strategies to prepare SERS-active nanostructures coated with a lipophilic sensor layer as one-time use SERS substrates for specific food analysis (e.g. quantitative detection of toxic food colorants). The second part of this contribution presents a slit array metamaterial perfect absorber for IR sensing applications consisting of a dielectric layer sandwiched between two metallic layers of which the upper layer is perforated with a periodic array of slits. Light-matter interaction is greatly amplified in the slits, where also the analyte is concentrated, as the surface of the substrate is covered by a thin silica layer. Thus, already small concentrations of analytes down to a monolayer can be detected by refractive index sensing and identified by their spectral fingerprints with a standard mid-infrared lab spectrometer.

In vitro phosphorylation of insulin receptor substrate 1 by protein kinase C-zeta: functional analysis and identification of novel phosphorylation sites.

PubMed

Sommerfeld, Mark R; Metzger, Sabine; Stosik, Magdalene; Tennagels, Norbert; Eckel, Jürgen

2004-05-18

Protein kinase C-zeta (PKC-zeta) participates both in downstream insulin signaling and in the negative feedback control of insulin action. Here we used an in vitro approach to identify PKC-zeta phosphorylation sites within insulin receptor substrate 1 (IRS-1) and to characterize the functional implications. A recombinant IRS-1 fragment (rIRS-1(449)(-)(664)) containing major tyrosine motifs for interaction with phosphatidylinositol (PI) 3-kinase strongly associated to the p85alpha subunit of PI 3-kinase after Tyr phosphorylation by the insulin receptor. Phosphorylation of rIRS-1(449)(-)(664) by PKC-zeta induced a prominent inhibition of this process with a mixture of classical PKC isoforms being less effective. Both PKC-zeta and the classical isoforms phosphorylated rIRS-1(449)(-)(664) on Ser(612). However, modification of this residue did not reduce the affinity of p85alpha binding to pTyr-containing peptides (amino acids 605-615 of rat IRS-1), as determined by surface plasmon resonance. rIRS-1(449)(-)(664) was then phosphorylated by PKC-zeta using [(32)P]ATP and subjected to tryptic phosphopeptide mapping based on two-dimensional HPLC coupled to mass spectrometry. Ser(498) and Ser(570) were identified as novel phosphoserine sites targeted by PKC-zeta. Both sites were additionally confirmed by phosphopeptide mapping of the corresponding Ser --> Ala mutants of rIRS-1(449)(-)(664). Ser(570) was specifically targeted by PKC-zeta, as shown by immunoblotting with a phosphospecific antiserum against Ser(570) of IRS-1. Binding of p85alpha to the S570A mutant was less susceptible to inhibition by PKC-zeta, when compared to the S612A mutant. In conclusion, our in vitro data demonstrate a strong inhibitory action of PKC-zeta at the level of IRS-1/PI 3-kinase interaction involving multiple serine phosphorylation sites. Whereas Ser(612) appears not to participate in the negative control of insulin signaling, Ser(570) may at least partly contribute to this process.

Recent Progress in SERS Biosensing

PubMed Central

Bantz, Kyle C.; Meyer, Audrey F.; Wittenberg, Nathan J.; Im, Hyungsoon; Kurtuluş, Özge; Lee, Si Hoon; Lindquist, Nathan C.

2011-01-01

This perspective gives an overview of recent developments in surface-enhanced Raman scattering (SERS) for biosensing. We focus this review on SERS papers published in the last 10 years and to specific applications of detecting biological analytes. Both intrinsic and extrinsic SERS biosensing schemes have been employed to detect and identify small molecules, nucleic acids, lipids, peptides, and proteins, as well as for in vivo and cellular sensing. Current SERS substrate technologies along with a series of advancements in surface chemistry, sample preparation, intrinsic/extrinsic signal transduction schemes, and tip-enhanced Raman spectroscopy are discussed. The progress covered herein shows great promise for widespread adoption of SERS biosensing. PMID:21509385

Effect of Crossing Geometry on the Plasmonic Behavior of Dielectric Core/Metal Sheath Nanowires

DTIC Science & Technology

2009-03-01

uniform SERS substrate. The growth of the Ga2O3 nanowires was achieved by the controlled oxidation of pure Ga metal in a vacuum tube furnace.14 The...equations.15 We have previously shown that Ga2O3 /Ag nanowire composites can be very efficient SERS substrates,11,12 and we suggested that the nanowire...detail, we used these Au lithographically produced lines, combined with the placement of individual Ga2O3 /Ag nanowires in specific crossing angles

Transport of estradiol-17β-glucuronide, estrone-3-sulfate and taurocholate across the endoplasmic reticulum membrane: evidence for different transport systems.

PubMed

Wlcek, Katrin; Hofstetter, Lia; Stieger, Bruno

2014-03-01

Important reactions of drug metabolism, including UGT mediated glucuronidation and steroidsulfatase mediated hydrolysis of sulfates, take place in the endoplasmic reticulum (ER) of hepatocytes. Consequently, UGT generated glucuronides, like estradiol-17β-glucuronide, have to be translocated back into the cytoplasm to reach their site of excretion. Also steroidsulfatase substrates, including estrone-3-sulfate, have to cross the ER membrane to reach their site of hydrolysis. Based on their physicochemical properties such compounds are not favored for passive diffusion and therefore likely necessitate transport system(s) to cross the ER membrane in either direction. The current study aims to investigate the transport of taurocholate, estradiol-17β-glucuronide, and estrone-3-sulfate in smooth (SER) and rough (RER) endoplasmic reticulum membrane vesicles isolated from Wistar and TR(-) rat liver. Time-dependent and bidirectional transport was demonstrated for taurocholate, showing higher uptake rates in SER than RER vesicles. For estradiol-17β-glucuronide a fast time-dependent efflux with similar efficiencies from SER and RER but no clear protein-mediated uptake was shown, indicating an asymmetric transport system for this substrate. Estrone-3-sulfate uptake was time-dependent and higher in SER than in RER vesicles. Inhibition of steroidsulfatase mediated estrone-3-sulfate hydrolysis decreased estrone-3-sulfate uptake but had no effect on taurocholate or estradiol-17β-glucuronide transport. Based on inhibition studies and transport characteristics, three different transport mechanisms are suggested to be involved in the transport of taurocholate, estrone-3-sulfate and estradiol-17β-glucuronide across the ER membrane. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

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.

Hand-Held Femtogram Detection of Hazardous Picric Acid with Hydrophobic Ag Nanopillar SERS Substrates and Mechanism of Elasto-Capillarity.

PubMed

Hakonen, Aron; Wang, FengChao; Andersson, Per Ola; Wingfors, Håkan; Rindzevicius, Tomas; Schmidt, Michael Stenbæk; Soma, Venugopal Rao; Xu, Shicai; Li, YingQi; Boisen, Anja; Wu, HengAn

2017-02-24

Picric acid (PA) is a severe environmental and security risk due to its unstable, toxic, and explosive properties. It is also challenging to detect in trace amounts and in situ because of its highly acidic and anionic character. Here, we assess sensing of PA under nonlaboratory conditions using surface-enhanced Raman scattering (SERS) silver nanopillar substrates and hand-held Raman spectroscopy equipment. The advancing elasto-capillarity effects are explained by molecular dynamics simulations. We obtain a SERS PA detection limit on the order of 20 ppt, corresponding attomole amounts, which together with the simple analysis methodology demonstrates that the presented approach is highly competitive for ultrasensitive analysis in the field.

SERS and DFT study of copper surfaces coated with corrosion inhibitor

PubMed Central

Muniz-Miranda, Francesco; Caporali, Stefano

2014-01-01

Summary Azole derivatives are common inhibitors of copper corrosion due to the chemical adsorption occurring on the metal surface that gives rise to a protective film. In particular, 1,2,4-triazole performs comparable to benzotriazole, which is much more widely used, but is by no means an environmentally friendly agent. In this study, we have analyzed the adsorption of 1,2,4-triazole on copper by taking advantage of the surface-enhanced Raman scattering (SERS) effect, which highlights the vibrational features of organic ligand monolayers adhering to rough surfaces of some metals such as gold, silver and copper. To ensure the necessary SERS activation, a roughening procedure was implemented on the copper substrates, resulting in nanoscale surface structures, as evidenced by microscopic investigation. To obtain sufficient information on the molecule–metal interaction and the formation of an anticorrosive thin film, the SERS spectra were interpreted with the aid of theoretical calculations based on the density functional theory (DFT) approach. PMID:25671144

Hierarchical zwitterionic modification of a SERS substrate enables real-time drug monitoring in blood plasma

NASA Astrophysics Data System (ADS)

Sun, Fang; Hung, Hsiang-Chieh; Sinclair, Andrew; Zhang, Peng; Bai, Tao; Galvan, Daniel David; Jain, Priyesh; Li, Bowen; Jiang, Shaoyi; Yu, Qiuming

2016-11-01

Surface-enhanced Raman spectroscopy (SERS) is an ultrasensitive analytical technique with molecular specificity, making it an ideal candidate for therapeutic drug monitoring (TDM). However, in critical diagnostic media including blood, nonspecific protein adsorption coupled with weak surface affinities and small Raman activities of many analytes hinder the TDM application of SERS. Here we report a hierarchical surface modification strategy, first by coating a gold surface with a self-assembled monolayer (SAM) designed to attract or probe for analytes and then by grafting a non-fouling zwitterionic polymer brush layer to effectively repel protein fouling. We demonstrate how this modification can enable TDM applications by quantitatively and dynamically measuring the concentrations of several analytes--including an anticancer drug (doxorubicin), several TDM-requiring antidepressant and anti-seizure drugs, fructose and blood pH--in undiluted plasma. This hierarchical surface chemistry is widely applicable to many analytes and provides a generalized platform for SERS-based biosensing in complex real-world media.

Hierarchical zwitterionic modification of a SERS substrate enables real-time drug monitoring in blood plasma

PubMed Central

Sun, Fang; Hung, Hsiang-Chieh; Sinclair, Andrew; Zhang, Peng; Bai, Tao; Galvan, Daniel David; Jain, Priyesh; Li, Bowen; Jiang, Shaoyi; Yu, Qiuming

2016-01-01

Surface-enhanced Raman spectroscopy (SERS) is an ultrasensitive analytical technique with molecular specificity, making it an ideal candidate for therapeutic drug monitoring (TDM). However, in critical diagnostic media including blood, nonspecific protein adsorption coupled with weak surface affinities and small Raman activities of many analytes hinder the TDM application of SERS. Here we report a hierarchical surface modification strategy, first by coating a gold surface with a self-assembled monolayer (SAM) designed to attract or probe for analytes and then by grafting a non-fouling zwitterionic polymer brush layer to effectively repel protein fouling. We demonstrate how this modification can enable TDM applications by quantitatively and dynamically measuring the concentrations of several analytes—including an anticancer drug (doxorubicin), several TDM-requiring antidepressant and anti-seizure drugs, fructose and blood pH—in undiluted plasma. This hierarchical surface chemistry is widely applicable to many analytes and provides a generalized platform for SERS-based biosensing in complex real-world media. PMID:27834380

Tunable Electromagnetic Coupling in Plasmonic Nanostructures Mediated by Thermoresponsive Polymer Brushes.

PubMed

Nguyen, Mai; Kanaev, Andrei; Sun, Xiaonan; Lacaze, Emmanuelle; Lau-Truong, Stéphanie; Lamouri, Aazdine; Aubard, Jean; Felidj, Nordin; Mangeney, Claire

2015-11-24

A smart and highly SERS-active plasmonic platform was designed by coupling regular arrays of nanotriangles to colloidal gold nanorods via a thermoresponsive polymer spacer (poly(N-isopropylacrylamide), PNIPAM). The substrates were prepared by combining a top-down and a bottom-up approach based on nanosphere lithography, surface-initiated controlled radical polymerization, and colloidal assembly. This multistep strategy provided regular hexagonal arrays of nanotriangles functionalized by polymer brushes and colloidal gold nanorods, confined exclusively on the nanotriangle surface. Interestingly, one could finely tune the gold nanorod impregnation on the polymer-coated nanostructures by adjusting the polymer layer thickness, leading to highly coupled plasmonic systems for intense SERS signal. Moreover, the thermoresponsive properties of the PNIPAM brushes could be wisely handled in order to monitor the SERS activity of the nanostructures coupled via this polymer spacer. The coupled hybrid plasmonic nanostructures designed in this work are therefore very promising smart platforms for the sensitive detection of analytes by SERS.

Performance characteristics of bio-inspired metal nanostructures as surface-enhanced Raman scattered (SERS) substrates

DOE PAGES

Areizaga-Martinez, Hector I.; Kravchenko, Ivan; Lavrik, Nickolay V.; ...

2016-08-26

The fabrication of high-performance plasmonic nanomaterials for bio-sensing and trace chemical detection is a field of intense theoretical and experimental research. The use of metal-silicon nanopillar arrays as analytical sensors has been reported with reasonable results in recent years. The use of bio-inspired nanocomposite structures that follow the Fibonacci numerical architecture offers the opportunity to develop nanostructures with theoretically higher and more reproducible plasmonic fields over extended areas. The work presented here describes the nanofabrication process for a series of 40 µm × 40 µm bio-inspired arrays classified as asymmetric fractals (sunflower seeds and romanesco broccoli), bilaterally symmetric (acacia leavesmore » and honeycombs), and radially symmetric (such as orchids and lily flowers) using electron beam lithography. In addition, analytical capabilities were evaluated using surface-enhanced Raman scattering (SERS). Here, the substrate characterization and SERS performance of the developed substrates as the strategies to assess the design performance are presented and discussed.« less

Performance characteristics of bio-inspired metal nanostructures as surface-enhanced Raman scattered (SERS) substrates

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

Areizaga-Martinez, Hector I.; Kravchenko, Ivan; Lavrik, Nickolay V.

The fabrication of high-performance plasmonic nanomaterials for bio-sensing and trace chemical detection is a field of intense theoretical and experimental research. The use of metal-silicon nanopillar arrays as analytical sensors has been reported with reasonable results in recent years. The use of bio-inspired nanocomposite structures that follow the Fibonacci numerical architecture offers the opportunity to develop nanostructures with theoretically higher and more reproducible plasmonic fields over extended areas. The work presented here describes the nanofabrication process for a series of 40 µm × 40 µm bio-inspired arrays classified as asymmetric fractals (sunflower seeds and romanesco broccoli), bilaterally symmetric (acacia leavesmore » and honeycombs), and radially symmetric (such as orchids and lily flowers) using electron beam lithography. In addition, analytical capabilities were evaluated using surface-enhanced Raman scattering (SERS). Here, the substrate characterization and SERS performance of the developed substrates as the strategies to assess the design performance are presented and discussed.« less

Performance Characteristics of Bio-Inspired Metal Nanostructures as Surface-Enhanced Raman Scattered (SERS) Substrates.

PubMed

Areizaga-Martinez, Hector I; Kravchenko, Ivan; Lavrik, Nickolay V; Sepaniak, Michael J; Hernández-Rivera, Samuel P; De Jesús, Marco A

2016-09-01

The fabrication of high-performance plasmonic nanomaterials for bio-sensing and trace chemical detection is a field of intense theoretical and experimental research. The use of metal-silicon nanopillar arrays as analytical sensors has been reported with reasonable results in recent years. The use of bio-inspired nanocomposite structures that follow the Fibonacci numerical architecture offers the opportunity to develop nanostructures with theoretically higher and more reproducible plasmonic fields over extended areas. The work presented here describes the nanofabrication process for a series of 40 µm × 40 µm bio-inspired arrays classified as asymmetric fractals (sunflower seeds and romanesco broccoli), bilaterally symmetric (acacia leaves and honeycombs), and radially symmetric (such as orchids and lily flowers) using electron beam lithography. In addition, analytical capabilities were evaluated using surface-enhanced Raman scattering (SERS). The substrate characterization and SERS performance of the developed substrates as the strategies to assess the design performance are presented and discussed. © The Author(s) 2016.

Gold nanoparticles-decorated electrospun poly(N-vinyl-2-pyrrolidone) nanofibers with tunable size and coverage density for nanomolar detection of single and binary component dyes by surface-enhanced raman spectroscopy

NASA Astrophysics Data System (ADS)

Kurniawan, Alfin; Wang, Meng-Jiy

2017-09-01

The application of the electrospun nanomaterials to surface-enhanced Raman spectroscopy (SERS) is a rapidly evolving field which holds potential for future developments in the generation of portable plasmonic-based detection platforms. In this study, a simple approach to fabricate electrospun poly(N-vinylpyrrolidone) (PVP) mats decorated with gold nanoparticles (AuNPs) by combining electrospinning and calcination was presented. AuNPs were decorated on the fiber mat surface through electrostatic interactions between positively charged aminosilane groups and negatively charged AuNPs. The size and coverage density of AuNPs on the fiber mats could be tuned by varying the calcination temperature. Calcination of AuNPs-decorated PVP fibers at 500 °C-700 °C resulted in the uniform decoration of high density AuNPs with very narrow gaps on every single fiber, which in turn contribute to strong electromagnetic SERS enhancement. The robust free-standing AuNPs-decorated mat which calcined at 500 °C (500/AuNPs-F) exhibited high SERS activity toward cationic (methylene blue, MB) and anionic (methyl orange, MO) dyes in single and binary systems with a detection range from tens of nM to a few hundred μM. The fabricated SERS substrate demonstrated high reproducibility with the spot-to-spot variation in SERS signal intensities was ±10% and ±12% for single and binary dye systems, respectively. The determination of MB and MO in spiked river water and tap water with 500/AuNPs-F substrate gave satisfactory results in terms of the percent spike recoveries (ranging from 92.6%-96.6%) and reproducibility (%RSD values less than 15 for all samples).

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.

Electromagnetic field enhancement and spectrum shaping through plasmonically integrated optical vortices.

PubMed

Ahn, Wonmi; Boriskina, Svetlana V; Hong, Yan; Reinhard, Björn M

2012-01-11

We introduce a new design approach for surface-enhanced Raman spectroscopy (SERS) substrates that is based on molding the optical powerflow through a sequence of coupled nanoscale optical vortices "pinned" to rationally designed plasmonic nanostructures, referred to as Vortex Nanogear Transmissions (VNTs). We fabricated VNTs composed of Au nanodiscs by electron beam lithography on quartz substrates and characterized their near- and far-field responses through combination of computational electromagnetism, and elastic and inelastic scattering spectroscopy. Pronounced dips in the far-field scattering spectra of VNTs provide experimental evidence for an efficient light trapping and circulation within the nanostructures. Furthermore, we demonstrate that VNT integration into periodic arrays of Au nanoparticles facilitates the generation of high E-field enhancements in the VNTs at multiple defined wavelengths. We show that spectrum shaping in nested VNT structures is achieved through an electromagnetic feed-mechanism driven by the coherent multiple scattering in the plasmonic arrays and that this process can be rationally controlled by tuning the array period. The ability to generate high E-field enhancements at predefined locations and frequencies makes nested VNTs interesting substrates for challenging SERS applications. © 2011 American Chemical Society

Elucidation of hydrolysis mechanisms for fatty acid amide hydrolase and its Lys142Ala variant via QM/MM simulations.

PubMed

Tubert-Brohman, Ivan; Acevedo, Orlando; Jorgensen, William L

2006-12-27

Fatty acid amide hydrolase (FAAH) is a serine hydrolase that degrades anandamide, an endocannabinoid, and oleamide, a sleep-inducing lipid, and has potential applications as a therapeutic target for neurological disorders. Remarkably, FAAH hydrolyzes amides and esters with similar rates; however, the normal preference for esters reemerges when Lys142 is mutated to alanine. To elucidate the hydrolysis mechanisms and the causes behind this variation of selectivity, mixed quantum and molecular mechanics (QM/MM) calculations were carried out to obtain free-energy profiles for alternative mechanisms for the enzymatic hydrolyses. The methodology features free-energy perturbation calculations in Monte Carlo simulations with PDDG/PM3 as the QM method. For wild-type FAAH, the results support a mechanism, which features proton transfer from Ser217 to Lys142, simultaneous proton transfer from Ser241 to Ser217, and attack of Ser241 on the substrate's carbonyl carbon to yield a tetrahedral intermediate, which subsequently undergoes elimination with simultaneous protonation of the leaving group by a Lys142-Ser217 proton shuttle. For the Lys142Ala mutant, a striking multistep sequence is proposed with simultaneous proton transfer from Ser241 to Ser217, attack of Ser241 on the carbonyl carbon of the substrate, and elimination of the leaving group and its protonation by Ser217. Support comes from the free-energy results, which well reproduce the observation that the Lys142Ala mutation in FAAH decreases the rate of hydrolysis for oleamide significantly more than for methyl oleate.

C1qTNF-related protein 1 improve insulin resistance by reducing phosphorylation of serine 1101 in insulin receptor substrate 1.

PubMed

Xin, Yaping; Zhang, Dongming; Fu, Yanqin; Wang, Chongxian; Li, Qingju; Tian, Chenguang; Zhang, Suhe; Lyu, Xiaodong

2017-08-30

C1qTNF-related protein 1 (CTRP1) is independently associated with type 2 diabetes. However, the relationship between CTRP1 and insulin resistance is still not established. This study aimed to explore the role of CTRP1 under the situation of insulin resistance in adipose tissue. Plasma CTRP1 level was investigated in type 2 diabetic subjects (n = 35) and non-diabetic subjects (n = 35). The relationship between CTRP1 and phosphorylation of multi insulin receptor substrate 1 (IRS-1) serine (Ser) sites was further explored. Our data showed that Plasma CTRP1 was higher and negative correlation with insulin resistance in diabetic subjects (r = -0.283, p = 0.018). Glucose utilisation test revealed that the glucose utilisation rate of mature adipocytes was improved by CTRP1 in the presence of insulin. CTRP1 was not only related to IRS-1 protein, but also negatively correlated with IRS-1 Ser1101 phosphorylation (r = -0.398, p = 0.031). Furthermore, Phosphorylation levels of IRS-1 Ser1101 were significantly lower after incubation with 40 ng/mL CTRP1 in mature adipocytes than those with no intervention (p < 0.05). There was no significant correlation between CTRP1 and other IRS-1 serine sites (Ser302, Ser307, Ser612, Ser636/639, and Ser789). Collectively, our results suggested that CTRP1 might improve insulin resistance by reducing the phosphorylation of IRS-1 Ser1101, induced in the situation of insulin resistance as a feedback adipokine.

Superhydrophobic analyte concentration utilizing colloid-pillar array SERS substrates.

PubMed

Wallace, Ryan A; Charlton, Jennifer J; Kirchner, Teresa B; Lavrik, Nickolay V; Datskos, Panos G; Sepaniak, Michael J

2014-12-02

The ability to detect a few molecules present in a large sample is of great interest for the detection of trace components in both medicinal and environmental samples. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. The following work involves superhydrophobic surfaces that have as a framework deterministic or stochastic silicon pillar arrays formed by lithographic or metal dewetting protocols, respectively. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added to the functionalized pillar array system via soaking. Native pillars and pillars with hydrophobic modification are used. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A ≥ 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 × 10(-12) M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up uses in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.

Fiber sensors for molecular detection

NASA Astrophysics Data System (ADS)

Gu, Claire; Yang, Xuan; Zhang, Jin; Newhouse, Rebecca; Cao, Liangcai

2010-11-01

The demand on sensors for detecting chemical and biological agents is greater than ever before, including medical, environmental, food safety, military, and security applications. At present, most detection or sensing techniques tend to be either non-molecular specific, bulky, expensive, relatively inaccurate, or unable to provide real time data. Clearly, alternative sensing technologies are urgently needed. Recently, we have been working to develop a compact fiber optic surface enhanced Raman scattering (SERS) sensor system that integrates various novel ideas to achieve compactness, high sensitivity and consistency, molecular specificity, and automatic preliminary identification capabilities. The unique sensor architecture is expected to bring SERS sensors to practical applications due to a combination of 1) novel SERS substrates that provide the high sensitivity and consistency, molecular specificity, and applicability to a wide range of compounds; 2) a unique hollow core optical fiber probe with double SERS substrate structure that provides the compactness, reliability, low cost, and ease of sampling; and 3) an innovative matched spectral filter set that provides automatic preliminary molecule identification. In this paper, we will review the principle of operation and some of the important milestones of fiber SERS sensor development with emphasis on our recent work to integrate photonic crystal fiber SERS probes with a portable Raman spectrometer and to demonstrate a matched spectral filter for molecule identification.

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

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.

Fabrication and surface-enhanced Raman scattering (SERS) of Ag/Au bimetallic films on Si substrates

NASA Astrophysics Data System (ADS)

Wang, Chaonan; Fang, Jinghuai; Jin, Yonglong; Cheng, Mingfei

2011-11-01

Ag films on Si substrates were fabricated by immersion plating and served as sacrificial materials for preparation of Ag/Au bimetallic films by galvanic replacement reaction. The formation procedure of films on the surface of Si was studied by scanning electron microscopy (SEM), which revealed Ag films with island and dendritic morphologies experienced novel structural evolution process during galvanic replacement reaction, and nanostructures with holes were produced within the resultant Ag/Au bimetallic films. SERS activity both of sacrificial Ag films and resultant Ag/Au bimetallic films was investigated by using crystal violet as an analyte. It has been shown that SERS signals increased with the process of galvanic substitution and reached intensity significantly stronger than that obtained from pure Ag films.

3D hierarchical Ag nanostructures formed on poly(acrylic acid) brushes grafted graphene oxide as promising SERS substrates

NASA Astrophysics Data System (ADS)

Xing, Guoke; Wang, Ke; Li, Ping; Wang, Wenqin; Chen, Tao

2018-03-01

In this study, in situ generation of Ag nanostructures with various morphology on poly(acrylic acid) (PAA) brushes grafted onto graphene oxide (GO), for use as substrates for surface-enhanced Raman scattering (SERS), is demonstrated. The overall synthetic strategy involves the loading of Ag precursor ions ((Ag+ and [Ag(NH3)2]+) onto PAA brush-grafted GO, followed by their in situ reduction to Ag nanostructures of various morphology using a reducing agent (NaBH4 or ascorbic acid). Novel 3D hierarchical flowerlike Ag nanostructures were obtained by using AgNO3 as precursor and ascorbic acid as reducing agent. Using 4-aminothiophenol as probe molecules, the as-prepared hierarchical Ag nanostructures exhibited excellent SERS performance, providing enhancement factors of ˜107.

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.

SERS study of riboflavin on green-synthesized silver nanoparticles prepared by reduction using different flavonoids: What is the role of flavonoid used?

NASA Astrophysics Data System (ADS)

Švecová, Marie; Ulbrich, Pavel; Dendisová, Marcela; Matějka, Pavel

2018-04-01

Spectroscopy of surface-enhanced Raman scattering (SERS) is nowadays widely used in the field of bio-science and medicine. These applications require new enhancing substrates with special properties. They should be non-toxic, environmentally friendly and (bio-) compatible with examined samples. Flavonoids are natural antioxidants with many positive effects on human health. Simultaneously, they can be used as reducing agent in preparation procedure of plasmonic enhancing substrate for SERS spectroscopy. The best amplifiers of Raman vibrational spectroscopic signal are generally silver nanoparticles (AgNPs). In this study, several flavonoids (forming a logical set) were used as reducing agent in AgNPs preparation procedures. Reactivity of 10 structurally arranged flavonoids (namely flavone, chrysin, apigenin, luteolin, tricetin, 3-hydroxyflavone, galangin, kaempferol, quercetin and myricetin) was compared and SERS-activity of prepared AgNPs was tested using model analyte riboflavin. Riboflavin was detected down to concentration 10-9 mol/l.

Two-step fabrication of nanoporous copper films with tunable morphology for SERS application

NASA Astrophysics Data System (ADS)

Diao, Fangyuan; Xiao, Xinxin; Luo, Bing; Sun, Hui; Ding, Fei; Ci, Lijie; Si, Pengchao

2018-01-01

It is important to design and fabricate nanoporous metals (NPMs) with optimized microstructures for specific applications. In this contribution, nanoporous coppers (NPCs) with controllable thicknesses and pore sizes were fabricated via the combination of a co-sputtering of Cu/Ti with a subsequent dealloying process. The effect of dealloying time on porous morphology and the corresponding surface enhanced Raman scattering (SERS) behaviors were systematically investigated. Transmission electron microscopy (TEM) identified the presences of the gaps formed between ligaments and also the nanobumps on the nanoparticle-aggregated ligament surface, which were likely to contribute as the ;hot spots; for electromagnetic enhancement. The optimal NPC film exhibited excellent SERS performance towards Rhodamine 6G (R6G) with a low limiting detection (10-9 M), along with good uniformity and reproducibility. The calculated enhancement factor of ca. 4.71 × 107 was over Au substrates and comparable to Ag systems, promising the proposed NPC as a cheap candidate for high-performance SERS substrate.

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.

Universal surface-enhanced Raman scattering amplification detector for ultrasensitive detection of multiple target analytes.

PubMed

Zheng, Jing; Hu, Yaping; Bai, Junhui; Ma, Cheng; Li, Jishan; Li, Yinhui; Shi, Muling; Tan, Weihong; Yang, Ronghua

2014-02-18

Up to now, the successful fabrication of efficient hot-spot substrates for surface-enhanced Raman scattering (SERS) remains an unsolved problem. To address this issue, we describe herein a universal aptamer-based SERS biodetection approach that uses a single-stranded DNA as a universal trigger (UT) to induce SERS-active hot-spot formation, allowing, in turn, detection of a broad range of targets. More specifically, interaction between the aptamer probe and its target perturbs a triple-helix aptamer/UT structure in a manner that activates a hybridization chain reaction (HCR) among three short DNA building blocks that self-assemble into a long DNA polymer. The SERS-active hot-spots are formed by conjugating 4-aminobenzenethiol (4-ABT)-encoded gold nanoparticles with the DNA polymer through a specific Au-S bond. As proof-of-principle, we used this approach to quantify multiple target analytes, including thrombin, adenosine, and CEM cancer cells, achieving lowest limit of detection values of 18 pM, 1.5 nM, and 10 cells/mL, respectively. As a universal SERS detector, this prototype can be applied to many other target analytes through the use of suitable DNA-functional partners, thus inspiring new designs and applications of SERS for bioanalysis.

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.

Deduced catalytic mechanism of d-amino acid amidase from Ochrobactrum anthropi SV3

PubMed Central

Okazaki, Seiji; Suzuki, Atsuo; Komeda, Hidenobu; Asano, Yasuhisa; Yamane, Takashi

2008-01-01

d-Amino acid amidase (DAA) from Ochrobactrum anthropi SV3 catalyzes d-stereospecific hydrolysis of amino acid amides. DAA has attracted attention as a catalyst for the stereospecific production of d-amino acids, although the mechanism that drives the reaction has not been clear. Previously, the structure of DAA was classified into two types, a substrate-bound state with an ordered Ω loop, and a ground state with a disordered Ω loop. Because the binding of the substrate facilitates ordering, this transition was regarded to be induced fit motion. The angles and distances of hydrogen bonds at Tyr149 Oη, Ser60 Oγ and Lys63 Nζ revealed that Tyr149 Oη donates an H atom to a water molecule in the substrate-bound state, and that Tyr149 Oη donates an H atom to Ser60 Oγ or Lys63 Nζ in the ground state. Taking into consideration the locations of the H atoms of Tyr149 Oη, Ser60 Oγ and Lys63 Nζ, a catalytic mechanism of DAA activity is presented, wherein a shift of an H atom at Tyr149 Oη in the substrate-bound versus the ground state plays a significant role in the reaction. This mechanism explains well why acylation proceeds and deacylation does not proceed in the substrate-bound state. PMID:18421151

Reusable nanosilver-coated magnetic particles for ultrasensitive SERS-based detection of malachite green in water samples

NASA Astrophysics Data System (ADS)

Song, Dan; Yang, Rong; Wang, Chongwen; Xiao, Rui; Long, Feng

2016-03-01

A novel nanosilver-deposited silica-coated Fe3O4 magnetic particle (Fe3O4@SiO2@Ag) with uniform size, good SERS activity and magnetic responsiveness was synthesized using amination polymer. The Fe3O4@SiO2@Ag magnetic particles have been successfully applied for ultrasensitive SERS detection of malachite green (MG) in water samples. The mechanism is that MG can be adsorbed on the silver surface of nanosilver-coated magnetic particles via one nitrogen atom, and the Raman signal intensity of MG is significantly enhanced by the nanosilver layer formed on the magnetic particles. The developed sensing system exhibited a sensitive response to MG in the range of 10 fM to 100 μM with a low limit of detection (LOD) 2 fM under optimal conditions. The LOD was several orders of magnitude lower than those of other methods. This SERS-based sensor showed good reproducibility and stability for MG detection. The silver-coated magnetic particles could easily be regenerated as SERS substrates only using low pH solution for multiple sensing events. The recovery of MG added to several water samples at different concentrations ranged from 90% to 110%. The proposed method facilitates the ultrasensitive analysis of dyes to satisfy the high demand for ensuring the safety of water sources.

Reusable nanosilver-coated magnetic particles for ultrasensitive SERS-based detection of malachite green in water samples

PubMed Central

Song, Dan; Yang, Rong; Wang, Chongwen; Xiao, Rui; Long, Feng

2016-01-01

A novel nanosilver-deposited silica-coated Fe3O4 magnetic particle (Fe3O4@SiO2@Ag) with uniform size, good SERS activity and magnetic responsiveness was synthesized using amination polymer. The Fe3O4@SiO2@Ag magnetic particles have been successfully applied for ultrasensitive SERS detection of malachite green (MG) in water samples. The mechanism is that MG can be adsorbed on the silver surface of nanosilver-coated magnetic particles via one nitrogen atom, and the Raman signal intensity of MG is significantly enhanced by the nanosilver layer formed on the magnetic particles. The developed sensing system exhibited a sensitive response to MG in the range of 10 fM to 100 μM with a low limit of detection (LOD) 2 fM under optimal conditions. The LOD was several orders of magnitude lower than those of other methods. This SERS-based sensor showed good reproducibility and stability for MG detection. The silver-coated magnetic particles could easily be regenerated as SERS substrates only using low pH solution for multiple sensing events. The recovery of MG added to several water samples at different concentrations ranged from 90% to 110%. The proposed method facilitates the ultrasensitive analysis of dyes to satisfy the high demand for ensuring the safety of water sources. PMID:26964502

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

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.

Quantitative SERS detection of low-concentration aromatic polychlorinated biphenyl-77 and 2,4,6-trinitrotoluene.

PubMed

Bao, Zhi Yong; Liu, Xin; Chen, Y; Wu, Yucheng; Chan, Helen L W; Dai, Jiyan; Lei, Dang Yuan

2014-09-15

This paper reports a simple label-free high-sensitive method for detecting low-concentration persistent organic pollutants and explosive materials. The proposed method combines surface-enhanced Raman spectroscopy (SERS) and magnetomotive enrichment of the target molecules on the surface of Ag nanoparticles (NPs). This structure can be achieved through self-assembling integration of Ag NPs with ferromagnetic Fe3O4 microspheres, forming a hybrid SERS nanoprobe with both optical and magnetic properties. Moreover, the magnetic response of ferromagnetic Fe3O4 microspheres can be used to dynamically modulate the optical property of Ag NPs through controlling their geometric arrangement on the substrate by applying an external magnetic field. It is also demonstrated from the full-wave numerical simulation results that the maximum electromagnetic field enhancement can be greatly increased by shortening the distance of neighboring Ag NPs and therefore resulting in an improved SERS detecting limit. More importantly, by using the prepared substrate, the SERS signals from organic pollution substances, i.e. aromatic polychlorinated biphenyl-77 and 2,4,6-trinitrotoluene, were quantitatively analyzed. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Controllable fabrication of large-scale hierarchical silver nanostructures for long-term stable and ultrasensitive SERS substrates

NASA Astrophysics Data System (ADS)

Wu, Jing; Fang, Jinghuai; Cheng, Mingfei; Gong, Xiao

2016-09-01

In this work, we aim to prepare effective and long-term stable hierarchical silver nanostructures serving as surface-enhanced Raman scattering (SERS) substrates simply via displacement reaction on Aluminum foils. In our experiments, Hexadecyltrimethylammonium bromide (CTAB) is used as cationic surfactant to control the velocity of displacement reaction as well as the hierarchical morphology of the resultant. We find that the volume ratio of CTAB to AgNO3 plays a dominant role in regulating the hierarchical structures besides the influence of displacement reaction time. These as-prepared hierarchical morphologies demonstrate excellent SERS sensitivity, structural stability and reproducibility with low values of relative standard deviation less than 20 %. The high SERS analytical enhancement factor of ~6.7 × 108 is achieved even at the concentration of Crystal Violet (CV) as low as 10-7 M, which is sufficient for single-molecule detection. The detection limit of CV is 10-9 M in this study. We believe that this simple and rapid approach integrating advantages of low-cost production and high reproducibility would be a promising way to facilitate routine SERS detection and will get wide applications in chemical synthesis.

Facile synthesis of silver nanoparticles/carbon dots for a charge transfer study and peroxidase-like catalytic monitoring by surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Zhao, Hongyue; Guo, Yue; Zhu, Shoujun; Song, Yubin; Jin, Jing; Ji, Wei; Song, Wei; Zhao, Bing; Yang, Bai; Ozaki, Yukihiro

2017-07-01

In this work, carbon dots (CDs) were combined with Ag nanoparticles (NPs) by a chemical reaction to form Ag NPs/CDs hybrid, which was then used as a novel surface-enhanced Raman scattering (SERS) substrate. During the synthetic process, carboxyl groups on the surface of Ag NPs were reacted with amino groups of CDs in an amidation reaction. The D and G bands of CDs in the Ag NPs/CDs hybrid could be easily detected by SERS. By employing p-aminothiophenol (PATP) molecules as SERS probes, the Ag NPs/CDs hybrid substrate could detect PATP in diluted solutions of concentration as low as 10-9 M. The charge transfer (CT) effect on SERS spectra with different excitation wavelengths in the prepared Ag NPs/CDs hybrid and PATP system was also investigated. It was found that addition of CDs changes the degree of CT between Ag NPs and PATP molecules. Since the prepared Ag NPs/CDs hybrid also showed a peroxidase-like activity toward the oxidation of 3,3‧,5,5‧-tetramethylbenzidine using H2O2, which can provide the sensitive detection of H2O2 by SERS technique.

Highly reproducible and sensitive silver nanorod array for the rapid detection of Allura Red in candy

NASA Astrophysics Data System (ADS)

Yao, Yue; Wang, Wen; Tian, Kangzhen; Ingram, Whitney Marvella; Cheng, Jie; Qu, Lulu; Li, Haitao; Han, Caiqin

2018-04-01

Allura Red (AR) is a highly stable synthetic red azo dye, which is widely used in the food industry to dye food and increase its attraction to consumers. However, the excessive consumption of AR can result in adverse health effects to humans. Therefore, a highly reproducible silver nanorod (AgNR) array was developed for surface enhanced Raman scattering (SERS) detection of AR in candy. The relative standard deviation (RSD) of AgNR substrate obtained from the same batch and different batches were 5.7% and 11.0%, respectively, demonstrating the high reproducibility. Using these highly reproducible AgNR arrays as the SERS substrates, AR was detected successfully, and its characteristic peaks were assigned by the density function theory (DFT) calculation. The limit of detection (LOD) of AR was determined to be 0.05 mg/L with a wide linear range of 0.8-100 mg/L. Furthermore, the AgNR SERS arrays can detect AR directly in different candy samples within 3 min without any complicated pretreatment. These results suggest the AgNR array can be used for rapid and qualitative SERS detection of AR, holding a great promise for expanding SERS application in food safety control field.

A silver nanoislands on silica spheres platform: enriching trace amounts of analytes for ultrasensitive and reproducible SERS detection.

PubMed

Wang, Zhongshun; Feng, Lei; Xiao, Dongyang; Li, Ning; Li, Yao; Cao, Danfeng; Shi, Zuosen; Cui, Zhanchen; Lu, Nan

2017-11-09

The performance of surface-enhanced Raman scattering (SERS) for detecting trace amounts of analytes depends highly on the enrichment of the diluted analytes into a small region that can be detected. A super-hydrophobic delivery (SHD) process is an excellent process to enrich even femtomolar analytes for SERS detection. However, it is still challenging to easily fabricate a low detection limit, high sensitivity and reproducible SHD-SERS substrate. In this article, we present a cost-effective and fewer-step method to fabricate a SHD-SERS substrate, named the "silver nanoislands on silica spheres" (SNOSS) platform. It is easily prepared via the thermal evaporation of silver onto a layer of super-hydrophobic paint, which contains single-scale surface-fluorinated silica spheres. The SNOSS platform performs reproducible detection, which brings the relative standard deviation down to 8.85% and 5.63% for detecting 10 -8 M R6G in one spot and spot-to-spot set-ups, respectively. The coefficient of determination (R 2 ) is 0.9773 for R6G. The SNOSS platform can be applied to the quantitative detection of analytes whose concentrations range from sub-micromolar to femtomolar levels.

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.

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.

Biocompatible 3D SERS substrate for trace detection of amino acids and melamine

NASA Astrophysics Data System (ADS)

Satheeshkumar, Elumalai; Karuppaiya, Palaniyandi; Sivashanmugan, Kundan; Chao, Wei-Ting; Tsay, Hsin-Sheng; Yoshimura, Masahiro

2017-06-01

A novel, low-cost and biocompatible three-dimensional (3D) substrate for surface-enhanced Raman spectroscopy (SERS) is fabricated using gold nanoparticles (AuNPs) loaded on cellulose paper for detection of amino acids and melamine. Dysosma pleiantha rhizome (Dp-Rhi) capped AuNPs (Dp-Rhi_AuNPs) were prepared by in situ using aqueous extract of Dp-Rhi and in situ functionalized Dp-Rhi on AuNPs surface was verified by Fourier transform infrared spectroscopy and zeta potentials analysis shows a negative (- 18.4 mV) surface charges, which confirm that presence of Dp-Rhi on AuNPs. The biocompatibility of Dp-Rhi_AuNPs is also examined by cell viability of FaDu cells using MTS assay and compared to control group. In conclusion, the SERS performance of AuNPs@cellulose paper substrates were systematically demonstrated and examined with different excitation wavelengths (i.e. 532, 632.8 and 785 nm lasers) and the as-prepared 3D substrates provided an enhancement factor approaching 7 orders of magnitude compared with conventional Raman intensity using para-nitrothiophenol (p-NTP), para-aminothiophenol (p-ATP) and para-mercaptobenzoic acid (p-MBA) as probe molecules. The strong electromagnetic effect was generated at the interface of AuNPs and pre-treated roughened cellulose paper is also investigated by simulation in which the formation of possible Raman hot-spot zone in fiber-like microstructure of cellulose paper decorated with AuNPs. Notably, with optimized condition of as-prepared 3D AuNPs@cellulose paper is highly sensitive in the SERS detection of aqueous tyrosine (10- 10 M) and melamine (10- 9 M).

Smart SERS Hot Spots: Single Molecules Can Be Positioned in a Plasmonic Nanojunction Using Host-Guest Chemistry.

PubMed

Kim, Nam Hoon; Hwang, Wooseup; Baek, Kangkyun; Rohman, Md Rumum; Kim, Jeehong; Kim, Hyun Woo; Mun, Jungho; Lee, So Young; Yun, Gyeongwon; Murray, James; Ha, Ji Won; Rho, Junsuk; Moskovits, Martin; Kim, Kimoon

2018-04-04

Single-molecule surface-enhanced Raman spectroscopy (SERS) offers new opportunities for exploring the complex chemical and biological processes that cannot be easily probed using ensemble techniques. However, the ability to place the single molecule of interest reliably within a hot spot, to enable its analysis at the single-molecule level, remains challenging. Here we describe a novel strategy for locating and securing a single target analyte in a SERS hot spot at a plasmonic nanojunction. The "smart" hot spot was generated by employing a thiol-functionalized cucurbit[6]uril (CB[6]) as a molecular spacer linking a silver nanoparticle to a metal substrate. This approach also permits one to study molecules chemically reluctant to enter the hot spot, by conjugating them to a moiety, such as spermine, that has a high affinity for CB[6]. The hot spot can accommodate at most a few, and often only a single, analyte molecule. Bianalyte experiments revealed that one can reproducibly treat the SERS substrate such that 96% of the hot spots contain a single analyte molecule. Furthermore, by utilizing a series of molecules each consisting of spermine bound to perylene bisimide, a bright SERS molecule, with polymethylene linkers of varying lengths, the SERS intensity as a function of distance from the center of the hot spot could be measured. The SERS enhancement was found to decrease as 1 over the square of the distance from the center of the hot spot, and the single-molecule SERS cross sections were found to increase with AgNP diameter.

Demonstration and Validation of a Portable Raman Sensor for In-Situ Detection and Monitoring of Perchlorate (ClO 4 -)

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

Hatzinger, Paul B.; Eres, Gyula; Gu, Baohua

Costs for environmental analysis and monitoring are increasing at a rapid rate and represent a significant percentage of the total and future remedial expenses at many U.S. Department of Defense (DoD) contaminated sites. It has been reported that about 30 to 40% of the remediation budget is usually spent on long-term monitoring (LTM), of which a large percentage represents laboratory analytical costs. Energetics such as perchlorate (ClO 4 -) are among the most frequently detected contaminants in groundwater and surface water at or near military installations due to their persistence and mobility. Currently, the standard protocol entails collecting samples inmore » the field, packaging them, and shipping them overnight to a designated laboratory for analysis. This process requires significant sample preparation and handling, and analytical results may not be available for several days to weeks. In this project, we developed and demonstrated a portable Raman sensor based on surface enhanced Raman scattering (SERS) technology to detect ClO 4 - in contaminated water. We summarize major accomplishments as follows: • A SERS sensor based on elevated gold (Au) nano-ellipse dimer architectures was designed and developed for ClO 4 - with a detection limit of ~10 -6 M (or 100 μg/L); The performance of these sensors was evaluated and optimized through variation of their geometric characteristics (i.e., dimer aspect ratio, dimer separation, etc.). • Large-scale commercial production of SERS substrate sensors via nanoimprinting by Nanova Inc. and Nanoimprint lithography (NIL) technology was successfully demonstrated. This is a substantial step forward toward the commercialization of the SERS sensors and may potentially lead to significantly reduced fabrication costs of SERS substrates. • Commercially produced SERS sensors were demonstrated to detect ClO 4 - at levels above 10 -6 M using a portable Raman analyzer. The performance of the commercial SERS sensors for ClO 4 - detection in the presence and absence of interferences was determined for a series of standard solutions. Sulfate (SO 4 2-) was found to exhibit the greatest interference for the anions tested, which included Cl-, NO 3 -, and SO 4 2-. • Field demonstration of the portable Raman sensor with commercially produced SERS substrates was completed at two Department of Defense (DoD) sites; twice at the Indian Head Naval Surface Warfare Center, Indian Head, MD, and once at Redstone Arsenal, Huntsville, AL. Multiple wells were sampled at both DoD sites, where a standard addition method was employed using the sensor to determine the ClO 4 -4 - and possibly other energetics that are both important for environmental monitoring and of interest for national security. However, we point out that SERS technology is also prone to interferences due to its sensitivity and responses to other ionic species, such as NO 3 -, SO 4 2-, and dissolved organics or co-contaminants present in the groundwater, which could potentially mask the SERS signal of the target analyte (i.e., ClO 4 -). As such, SERS analysis was subject to significant variations (e.g., ±20% or more), and its detection limit for ClO 4 --8 M) and was substantially higher than what we anticipated from laboratory studies. However, despite these complications, the portable Raman sensor developed in this project could be used as a rapid screening tool for ClO 4 - at concentrations above 10 -6 M. Future studies are warranted to further develop the technology and to optimize its performance, and eventually to bring the technology to the market. With additional development and demonstration, the sensor has the potential to reduce analytical costs by eliminating shipping and typical costs associated with laboratory analysis. A cost savings of 30–45% may be realized during a typical sampling event and, more importantly, the technology could allow rapid turn-around of information to decision makers for site characterization and remediation.« less

Electrospun Nanofibers Made of Silver Nanoparticles, Cellulose Nanocrystals, and Polyacrylonitrile as Substrates for Surface-Enhanced Raman Scattering

PubMed Central

Ren, Suxia; Dong, Lili; Zhang, Xiuqiang; Lei, Tingzhou; Ehrenhauser, Franz; Song, Kunlin; Li, Meichun; Sun, Xiuxuan; Wu, Qinglin

2017-01-01

Nanofibers with excellent activities in surface-enhanced Raman scattering (SERS) were developed through electrospinning precursor suspensions consisting of polyacrylonitrile (PAN), silver nanoparticles (AgNPs), silicon nanoparticles (SiNPs), and cellulose nanocrystals (CNCs). Rheology of the precursor suspensions, and morphology, thermal properties, chemical structures, and SERS sensitivity of the nanofibers were investigated. The electrospun nanofibers showed uniform diameters with a smooth surface. Hydrofluoric (HF) acid treatment of the PAN/CNC/Ag composite nanofibers (defined as p-PAN/CNC/Ag) led to rougher fiber surfaces with certain pores and increased mean fiber diameters. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results confirmed the existence of AgNPs that were formed during heat and HF acid treatment processes. In addition, thermal stability of the electrospun nanofibers increased due to the incorporation of CNCs and AgNPs. The p-PAN/CNC/Ag nanofibers were used as a SERS substrate to detect p-aminothiophenol (p-ATP) probe molecule. The results show that this substrate exhibited high sensitivity for the p-ATP probe detection. PMID:28772428

SERS activity of silver and gold nanostructured thin films deposited by pulsed laser ablation

NASA Astrophysics Data System (ADS)

Agarwal, N. R.; Tommasini, M.; Fazio, E.; Neri, F.; Ponterio, R. C.; Trusso, S.; Ossi, P. M.

2014-10-01

Nanostructured Au and Ag thin films were obtained by nanosecond pulsed laser ablation in presence of a controlled Ar atmosphere. Keeping constant other deposition parameters such as target-to-substrate distance, incidence angle, laser wavelength and laser fluence, the film morphology, revealed by SEM, ranges from isolated NPs to island structures and sensibly depends on gas pressure (10-100 Pa) and on the laser pulse number (500-3 × 10). The control of these two parameters allows tailoring the morphology and correspondingly the optical properties of the films. The position and width of the surface plasmon resonance peak, in fact, can be varied with continuity. The films showed remarkable surface-enhanced Raman activity (SERS) that depends on the adopted deposition conditions. Raman maps were acquired on micrometer-sized areas of both silver and gold substrates selected among those with the strongest SERS activity. Organic dyes of interest in cultural heritage studies (alizarin, purpurin) have been also considered for bench marking the substrates produced in this work. Also the ability to detect the presence of biomolecules was tested using lysozyme in a label free configuration.

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 ...

Probing the importance of hydrogen bonds in the active site of the subtilisin nattokinase by site-directed mutagenesis and molecular dynamics simulation

PubMed Central

Zheng, Zhong-liang; Ye, Mao-qing; Zuo, Zhen-yu; Liu, Zhi-gang; Tai, Keng-chang; Zou, Guo-lin

2006-01-01

Hydrogen bonds occurring in the catalytic triad (Asp32, His64 and Ser221) and the oxyanion hole (Asn155) are very important to the catalysis of peptide bond hydrolysis by serine proteases. For the subtilisin NK (nattokinase), a bacterial serine protease, construction and analysis of a three-dimensional structural model suggested that several hydrogen bonds formed by four residues function to stabilize the transition state of the hydrolysis reaction. These four residues are Ser33, Asp60, Ser62 and Thr220. In order to remove the effect of these hydrogen bonds, four mutants (Ser33→Ala33, Asp60→Ala60, Ser62→Ala62, and Thr220→Ala220) were constructed by site-directed mutagenesis. The results of enzyme kinetics indicated that removal of these hydrogen bonds increases the free-energy of the transition state (ΔΔGT). We concluded that these hydrogen bonds are more important for catalysis than for binding the substrate, because removal of these bonds mainly affects the kcat but not the Km values. A substrate, SUB1 (succinyl-Ala-Ala-Pro-Phe-p-nitroanilide), was used during enzyme kinetics experiments. In the present study we have also shown the results of FEP (free-energy perturbation) calculations with regard to the binding and catalysis reactions for these mutant subtilisins. The calculated difference in FEP also suggested that these four residues are more important for catalysis than binding of the substrate, and the simulated values compared well with the experimental values from enzyme kinetics. The results of MD (molecular dynamics) simulations further demonstrated that removal of these hydrogen bonds partially releases Asp32, His64 and Asn155 so that the stability of the transition state decreases. Another substrate, SUB2 (H-D-Val-Leu-Lys-p-nitroanilide), was used for FEP calculations and MD simulations. PMID:16411898

Probing the importance of hydrogen bonds in the active site of the subtilisin nattokinase by site-directed mutagenesis and molecular dynamics simulation.

PubMed

Zheng, Zhong-liang; Ye, Mao-qing; Zuo, Zhen-yu; Liu, Zhi-gang; Tai, Keng-chang; Zou, Guo-lin

2006-05-01

Hydrogen bonds occurring in the catalytic triad (Asp32, His64 and Ser221) and the oxyanion hole (Asn155) are very important to the catalysis of peptide bond hydrolysis by serine proteases. For the subtilisin NK (nattokinase), a bacterial serine protease, construction and analysis of a three-dimensional structural model suggested that several hydrogen bonds formed by four residues function to stabilize the transition state of the hydrolysis reaction. These four residues are Ser33, Asp60, Ser62 and Thr220. In order to remove the effect of these hydrogen bonds, four mutants (Ser33-->Ala33, Asp60-->Ala60, Ser62-->Ala62, and Thr220-->Ala220) were constructed by site-directed mutagenesis. The results of enzyme kinetics indicated that removal of these hydrogen bonds increases the free-energy of the transition state (DeltaDeltaG(T)). We concluded that these hydrogen bonds are more important for catalysis than for binding the substrate, because removal of these bonds mainly affects the kcat but not the K(m) values. A substrate, SUB1 (succinyl-Ala-Ala-Pro-Phe-p-nitroanilide), was used during enzyme kinetics experiments. In the present study we have also shown the results of FEP (free-energy perturbation) calculations with regard to the binding and catalysis reactions for these mutant subtilisins. The calculated difference in FEP also suggested that these four residues are more important for catalysis than binding of the substrate, and the simulated values compared well with the experimental values from enzyme kinetics. The results of MD (molecular dynamics) simulations further demonstrated that removal of these hydrogen bonds partially releases Asp32, His64 and Asn155 so that the stability of the transition state decreases. Another substrate, SUB2 (H-D-Val-Leu-Lys-p-nitroanilide), was used for FEP calculations and MD simulations.

Structural insights into the metabolism of 2-chlorodibenzofuran by an evolved biphenyl dioxygenase

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

Kumar, Pravindra; Department of Biotechnology, Indian Institute of Technology, Roorkee 247667; Mohammadi, Mahmood

2012-05-18

Highlights: Black-Right-Pointing-Pointer Regiospecificity of BphAE{sub RR41} toward dibenzofuran and 2-chlorodibenzofuran differs. Black-Right-Pointing-Pointer We compared the structures of the substrate-bound forms of the enzyme with both substrates. Black-Right-Pointing-Pointer Dibenzofuran is compelled to move during the catalytic reaction. Black-Right-Pointing-Pointer Ser283 contact with 2-chlorodibenzofuran helps prevent substrate movement during the reaction. -- Abstract: The biphenyl dioxygenase of Burkholderia xenovorans LB400 (BphAE{sub LB400}) is a Rieske-type oxygenase that catalyzes the stereospecific oxygenation of many heterocyclic aromatics including dibenzofuran. In a previous work, we evolved BphAE{sub LB400} and obtained BphAE{sub RR41}. This variant metabolizes dibenzofuran and 2-chlorodibenzofuran more efficiently than BphAE{sub LB400}. However, the regiospecificitymore » of BphAE{sub RR41} toward these substrates differs. Dibenzofuran is metabolized principally through a lateral dioxygenation whereas 2-chlorodibenzofuran is metabolized principally through an angular dioxygenation. In order to explain this difference, we examined the crystal structures of both substrate-bound forms of BphAE{sub RR41} obtained under anaerobic conditions. This structure analysis, in combination with biochemical data for a Ser283Gly mutant provided evidences that the substrate is compelled to move after oxygen-binding in BphAE{sub RR41}:dibenzofuran. In BphAE{sub RR41}:2-chlorodibenzofuran, the chlorine atom is close to the side chain of Ser283. This contact is missing in the BphAE{sub RR41}:dibenzofuran, and strong enough in the BphAE{sub RR41}:2-chlorodibenzofuran to help prevent substrate movement during the catalytic reaction.« less

Surface-enhanced Raman for monitoring toxins in water

NASA Astrophysics Data System (ADS)

Spencer, Kevin M.; Sylvia, James M.; Clauson, Susan L.; Bertone, Jane F.; Christesen, Steven D.

2004-02-01

Protection of the drinking water supply from a terrorist attack is of critical importance. Since the water supply is vast, contamination prevention is difficult. Therefore, rapid detection of contaminants, whether a military chemical/biological threat, a hazardous chemical spill, naturally occurring toxins, or bacterial build-up is a priority. The development of rapid environmentally portable and stable monitors that allow continuous monitoring of the water supply is ideal. EIC Laboratories has been developing Surface-Enhanced Raman Spectroscopy (SERS) to detect chemical agents, toxic industrial chemicals (TICs), viruses, cyanotoxins and bacterial agents. SERS is an ideal technique for the Joint Service Agent Water Monitor (JSAWM). SERS uses the enhanced Raman signals observed when an analyte adsorbs to a roughened metal substrate to enable trace detection. Proper development of the metal substrate will optimize the sensitivity and selectivity towards the analytes of interest.

SERS-Based Flavonoid Detection Using Ethylenediamine-β-Cyclodextrin as a Capturing Ligand

PubMed Central

Choi, Jae Min; Hahm, Eunil; Park, Kyeonghui; Jeong, Daham; Rho, Won-Yeop; Kim, Jaehi; Jeong, Dae Hong; Lee, Yoon-Sik; Jhang, Sung Ho; Chung, Hyun Jong; Cho, Eunae; Yu, Jae-Hyuk; Jun, Bong-Hyun; Jung, Seunho

2017-01-01

Ethylenediamine-modified β-cyclodextrin (Et-β-CD) was immobilized on aggregated silver nanoparticle (NP)-embedded silica NPs (SiO2@Ag@Et-β-CD NPs) for the effective detection of flavonoids. Silica NPs were used as the template for embedding silver NPs to create hot spots and enhance surface-enhanced Raman scattering (SERS) signals. Et-β-CD was immobilized on Ag NPs to capture flavonoids via host-guest inclusion complex formation, as indicated by enhanced ultraviolet absorption spectra. The resulting SiO2@Ag@Et-β-CD NPs were used as the SERS substrate for detecting flavonoids, such as hesperetin, naringenin, quercetin, and luteolin. In particular, luteolin was detected more strongly in the linear range 10−7 to 10−3 M than various organic molecules, namely ethylene glycol, β-estradiol, isopropyl alcohol, naphthalene, and toluene. In addition, the SERS signal for luteolin captured by the SiO2@Ag@Et-β-CD NPs remained even after repeated washing. These results indicated that the SiO2@Ag@Et-β-CD NPs can be used as a rapid, sensitive, and selective sensor for flavonoids. PMID:28336842

Methods and systems for Raman and optical cross-interrogation in flow-through silicon membranes

DOEpatents

Bond, Tiziana C.; Letant, Sonia E.

2014-09-09

Cross-interrogating photonic detection systems and methods are shown. A flow through photonic crystal membrane with a surface enhanced Raman scattering (SERS) substrate is provided with pores which are distributed along multiple regions. The pores of one region have walls to which a first type of target specific anchor can be attached, while pores of another region have walls to which a second type of target specific anchor can be attached. An optical arrangement out-of-plane to the SERS substrate is also provided for enhanced sensitivity and identification of target organisms.

Paper SERS chromatography for detection of trace analytes in complex samples

NASA Astrophysics Data System (ADS)

Yu, Wei W.; White, Ian M.

2013-05-01

We report the application of paper SERS substrates for the detection of trace quantities of multiple analytes in a complex sample in the form of paper chromatography. Paper chromatography facilitates the separation of different analytes from a complex sample into distinct sections in the chromatogram, which can then be uniquely identified using SERS. As an example, the separation and quantitative detection of heroin in a highly fluorescent mixture is demonstrated. Paper SERS chromatography has obvious applications, including law enforcement, food safety, and border protection, and facilitates the rapid detection of chemical and biological threats at the point of sample.

A study on the correlation between the dewetting temperature of Ag film and SERS intensity.

PubMed

Quan, Jiamin; Zhang, Jie; Qi, Xueqiang; Li, Junying; Wang, Ning; Zhu, Yong

2017-11-07

The thermally dewetted metal nano-islands have been actively investigated as cost-effective SERS-active substrates with a large area, good reproducibility and repeatability via simple fabrication process. However, the correlation between the dewetting temperature of metal film and SERS intensity hasn't been systematically studied. In this work, taking Ag nano-islands (AgNIs) as an example, we reported a strategy to investigate the correlation between the dewetting temperature of metal film and SERS intensity. We described the morphology evolution of AgNIs on the SiO 2 planar substrate in different temperatures and got the quantitative information in surface-limited diffusion process (SLDP) as a function of annealing temperature via classical mean-field nucleation theory. Those functions were further used in the simulation of electromagnetic field to obtain the correlation between the dewetting temperature of Ag film and theoretical analysis. In addition, Raman mapping was done on samples annealed at different temperatures, with R6G as an analyte, to accomplish the analysis of the correlation between the dewetting temperature of Ag film and SERS intensity, which is consistent with the theoretical analysis. For SLDP, we used the morphological characterization of five samples prepared by different annealing temperatures to successfully illustrate the change in SERS intensity with the temperature fluctuation, obtaining a small deviation between the experimental results and theoretic prediction.

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.

Improving the sensitivity of immunoassay based on MBA-embedded Au@SiO2 nanoparticles and surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Wei, Chao; Xu, Min-Min; Fang, Cong-Wei; Jin, Qi; Yuan, Ya-Xian; Yao, Jian-Lin

2017-03-01

Traditional "sandwich" structure immunoassay is mainly based on the self-assembly of "antibody on solid substrate-antigen-antibody with nanotags" architectures, and the sensitivity of this strategy is critically depended on the surface enhanced Raman scattering (SERS) activities and stability of nanotags. Therefore, the rational design and fabrication on the SERS nanotags attracts the common interests to the bio-related detecting and imaging. Herein, silica encapsulated Au with mercaptobenzoic acid (MBA) core-shell nanoparticles (Au-MBA@SiO2) are fabricated instead of the traditional naked Au or Ag nanoparticles for the SERS-based immunoassay on human and mouse IgG antigens. The MBA molecules facilitate the formation of continuous pinhole-free silica shell and are also used as SERS labels. The silica shell is employed to protect MBA labels and to isolate Au core from the ambient solution for blocking the aggregation. This shell also played the similar role to BSA in inhibiting the nonspecific bindings, which allowed the procedures for constructing "sandwich" structures to be simplified. All of these merits of the Au-MBA@SiO2 brought the high performance in the related immunoassay. Benefiting from the introduction of silica shell to encapsulate MBA labels, the detection sensitivity was improved by about 1- 2 orders of magnitude by comparing with the traditional approach based on naked Au-MBA nanoparticles. This kind of label-embedded core-shell nanoparticles could be developed as the versatile nanotags for the bioanalysis and bioimaging.

Fabrication of tunable plasmonic 3D nanostructures for SERS applications

NASA Astrophysics Data System (ADS)

Ozbay, Ayse; Yuksel, Handan; Solmaz, Ramazan; Kahraman, Mehmet

2016-03-01

Surface-enhanced Raman scattering (SERS) is a powerful technique used for characterization of biological and nonbiological molecules and structures. Since plasmonic properties of the nanomaterials is one of the most important factor influencing SERS activity, tunable plasmonic properties (wavelength of the surface plasmons and magnitude of the electromagnetic field generated on the surface) of SERS substrates are crucial in SERS studies. SERS enhancement can be maximized by controlling of plasmonic properties of the nanomaterials. In this study, a novel approach to fabricate tunable plasmonic 3D nanostructures based on combination of soft lithography and nanosphere lithography is studied. Spherical latex particles having different diameters are uniformly deposited on glass slides with convective assembly method. The experimental parameters for the convective assembly are optimized by changing of latex spheres concentration, stage velocity and latex particles volume placed between to two glass slides that staying with a certain angle to each other. Afterwards, polydimethylsiloxane (PDMS) elastomer is poured on the deposited latex particles and cured to obtain nanovoids on the PDMS surfaces. The diameter and depth of the nanovoids on the PDMS surface are controlled by the size of the latex particles. Finally, fabricated nanovoid template on the PDMS surfaces are filled with the silver coating to obtain plasmonic 3D nanostructures. Characterization of the fabricated surfaces is performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). SERS performance of fabricated 3D plasmonic nanostructures will be evaluated using Raman reporter molecules.

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.

Crystal structure analysis of a bacterial aryl acylamidase belonging to the amidase signature enzyme family

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

Lee, Saeyoung; Park, Eun-Hye; Ko, Hyeok-Jin

2015-11-13

The atomic structure of a bacterial aryl acylamidase (EC 3.5.1.13; AAA) is reported and structural features are investigated to better understand the catalytic profile of this enzyme. Structures of AAA were determined in its native form and in complex with the analgesic acetanilide, p-acetaminophenol, at 1.70 Å and 1.73 Å resolutions, respectively. The overall structural fold of AAA was identified as an α/β fold class, exhibiting an open twisted β-sheet core surrounded by α-helices. The asymmetric unit contains one AAA molecule and the monomeric form is functionally active. The core structure enclosing the signature sequence region, including the canonical Ser-cisSer-Lys catalytic triad,more » is conserved in all members of the Amidase Signature enzyme family. The structure of AAA in a complex with its ligand reveals a unique organization in the substrate-binding pocket. The binding pocket consists of two loops (loop1 and loop2) in the amidase signature sequence and one helix (α10) in the non-amidase signature sequence. We identified two residues (Tyr{sup 136} and Thr{sup 330}) that interact with the ligand via water molecules, and a hydrogen-bonding network that explains the catalytic affinity over various aryl acyl compounds. The optimum activity of AAA at pH > 10 suggests that the reaction mechanism employs Lys{sup 84} as the catalytic base to polarize the Ser{sup 187} nucleophile in the catalytic triad. - Highlights: • We determined the first structure of a bacterial aryl acylamidase (EC 3.5.1.13). • Structure revealed spatially distinct architecture of the substrate-binding pocket. • Hydrogen-bonding with Tyr{sup 136} and Thr{sup 330} mediates ligand-binding and substrate.« less

Fabrication of a novel transparent SERS substrate comprised of Ag-nanoparticle arrays and its application in rapid detection of ractopamine on meat

USDA-ARS?s Scientific Manuscript database

Surface-enhanced Raman spectroscopy (SERS) is an emerging analytical tool that boasts the feature of high detection sensitivity and molecular fingerprint specificity attracting increased attention and showing promise in applications including detecting residues of veterinary drugs. In practice, spec...

Checkpoint kinase 1-induced phosphorylation of O-linked β-N-acetylglucosamine transferase regulates the intermediate filament network during cytokinesis.

PubMed

Li, Zhe; Li, Xueyan; Nai, Shanshan; Geng, Qizhi; Liao, Ji; Xu, Xingzhi; Li, Jing

2017-12-01

Checkpoint kinase 1 (Chk1) is a kinase instrumental for orchestrating DNA replication, DNA damage checkpoints, the spindle assembly checkpoint, and cytokinesis. Despite Chk1's pivotal role in multiple cellular processes, many of its substrates remain elusive. Here, we identified O- linked β- N -acetylglucosamine ( O -GlcNAc)-transferase (OGT) as one of Chk1's substrates. We found that Chk1 interacts with and phosphorylates OGT at Ser-20, which not only stabilizes OGT, but also is required for cytokinesis. Phospho-specific antibodies of OGT-pSer-20 exhibited specific signals at the midbody of the cell, consistent with midbody localization of OGT as reported previously. Moreover, phospho-deficient OGT (S20A) cells attenuated cellular O -GlcNAcylation levels and also reduced phosphorylation of Ser-71 in the cytoskeletal protein vimentin, a modification critical for severing vimentin filament during cytokinesis. Consequently, elongated vimentin bridges were observed in cells depleted of OGT via an si OGT- based approach. Lastly, expression of plasmids resistant to si OGT efficiently rescued the vimentin bridge phenotype, but the OGT-S20A rescue plasmids did not. Our results suggest a Chk1-OGT-vimentin pathway that regulates the intermediate filament network during cytokinesis. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Rapid Biochemical Mixture Screening by Three-Dimensional Patterned Multifunctional Substrate with Ultra-Thin Layer Chromatography (UTLC) and Surface Enhanced Raman Scattering (SERS).

PubMed

Lee, Bi-Shen; Lin, Pi-Chen; Lin, Ding-Zheng; Yen, Ta-Jen

2018-01-11

We present a three-dimensional patterned (3DP) multifunctional substrate with the functions of ultra-thin layer chromatography (UTLC) and surface enhanced Raman scattering (SERS), which simultaneously enables mixture separation, target localization and label-free detection. This multifunctional substrate is comprised of a 3DP silicon nanowires array (3DP-SiNWA), decorated with silver nano-dendrites (AgNDs) atop. The 3DP-SiNWA is fabricated by a facile photolithographic process and low-cost metal assisted chemical etching (MaCE) process. Then, the AgNDs are decorated onto 3DP-SiNWA by a wet chemical reduction process, obtaining 3DP-AgNDs@SiNWA multifunctional substrates. With various patterns designed on the substrates, the signal intensity could be maximized by the excellent confinement and concentrated effects of patterns. By using this 3DP-AgNDs@SiNWA substrate to scrutinize the mixture of two visible dyes, the individual target could be recognized and further boosted the Raman signal of target 15.42 times comparing to the un-patterned AgNDs@SiNWA substrate. Therefore, such a three-dimensional patterned multifunctional substrate empowers rapid mixture screening, and can be readily employed in practical applications for biochemical assays, food safety and other fields.

Design of hybrid two-dimensional and three-dimensional nanostructured arrays for electronic and sensing applications

NASA Astrophysics Data System (ADS)

Ko, Hyunhyub

This dissertation presents the design of organic/inorganic hybrid 2D and 3D nanostructured arrays via controlled assembly of nanoscale building blocks. Two representative nanoscale building blocks such as carbon nanotubes (one-dimension) and metal nanoparticles (zero-dimension) are the core materials for the study of solution-based assembly of nanostructured arrays. The electrical, mechanical, and optical properties of the assembled nanostructure arrays have been investigated for future device applications. We successfully demonstrated the prospective use of assembled nanostructure arrays for electronic and sensing applications by designing flexible carbon nanotube nanomembranes as mechanical sensors, highly-oriented carbon nanotubes arrays for thin-film transistors, and gold nanoparticle arrays for SERS chemical sensors. In first section, we fabricated highly ordered carbon nanotube (CNT) arrays by tilted drop-casting or dip-coating of CNT solution on silicon substrates functionalized with micropatterned self-assembled monolayers. We further exploited the electronic performance of thin-film transistors based on highly-oriented, densely packed CNT micropatterns and showed that the carrier mobility is largely improved compared to randomly oriented CNTs. The prospective use of Raman-active CNTs for potential mechanical sensors has been investigated by studying the mechano-optical properties of flexible carbon nanotube nanomembranes, which contain freely-suspended carbon nanotube array encapsulated into ultrathin (<50 nm) layer-by-layer (LbL) polymer multilayers. In second section, we fabricated 3D nano-canal arrays of porous alumina membranes decorated with gold nanoparticles for prospective SERS sensors. We showed extraordinary SERS enhancement and suggested that the high performance is associated with the combined effects of Raman-active hot spots of nanoparticle aggregates and the optical waveguide properties of nano-canals. We demonstrated the ability of this SERS substrate for trace level sensing of nitroaromatic explosives by detecting down to 100 zeptogram (˜330 molecules) of DNT.

Morphologically manipulated Ag/ZnO nanostructures as surface enhanced Raman scattering probes for explosives detection

NASA Astrophysics Data System (ADS)

Shaik, Ummar Pasha; Hamad, Syed; Ahamad Mohiddon, Md.; Soma, Venugopal Rao; Ghanashyam Krishna, M.

2016-03-01

The detection of secondary explosive molecules (e.g., ANTA, FOX-7, and CL-20) using Ag decorated ZnO nanostructures as surface enhanced Raman scattering (SERS) probes is demonstrated. ZnO nanostructures were grown on borosilicate glass substrates by rapid thermal oxidation of metallic Zn films at 500 °C. The oxide nanostructures, including nanosheets and nanowires, emerged over the surface of the Zn film leaving behind the metal residue. We demonstrate that SERS measurements with concentrations as low as 10 μM, of the three explosive molecules ANTA, FOX-7, and CL-20 over ZnO/Ag nanostructures, resulted in enhancement factors of ˜107, ˜107, and ˜104, respectively. These measurements validate the high sensitivity of detection of explosive molecules using Ag decorated ZnO nanostructures as SERS substrates. The Zn metal residue and conditions of annealing play an important role in determining the detection sensitivity.

Naturally inspired SERS substrates fabricated by photocatalytically depositing silver nanoparticles on cicada wings

PubMed Central

2014-01-01

Densely stacked Ag nanoparticles with an average diameter of 199 nm were effectively deposited on TiO2-coated cicada wings (Ag/TiO2-coated wings) from a water-ethanol solution of AgNO3 using ultraviolet light irradiation at room temperature. It was seen that the surfaces of bare cicada wings contained nanopillar array structures. In the optical absorption spectra of the Ag/TiO2-coated wings, the absorption peak due to the localized surface plasmon resonance (LSPR) of Ag nanoparticles was observed at 440 nm. Strong Surface-enhanced Raman scattering (SERS) signals of Rhodamine 6G adsorbed on the Ag/TiO2-coated wings were clearly observed using the 514.5-nm line of an Ar+ laser. The Ag/TiO2-coated wings can be a promising candidate for naturally inspired SERS substrates. PMID:24959110

Naturally inspired SERS substrates fabricated by photocatalytically depositing silver nanoparticles on cicada wings

NASA Astrophysics Data System (ADS)

Tanahashi, Ichiro; Harada, Yoshiyuki

2014-06-01

Densely stacked Ag nanoparticles with an average diameter of 199 nm were effectively deposited on TiO2-coated cicada wings (Ag/TiO2-coated wings) from a water-ethanol solution of AgNO3 using ultraviolet light irradiation at room temperature. It was seen that the surfaces of bare cicada wings contained nanopillar array structures. In the optical absorption spectra of the Ag/TiO2-coated wings, the absorption peak due to the localized surface plasmon resonance (LSPR) of Ag nanoparticles was observed at 440 nm. Strong Surface-enhanced Raman scattering (SERS) signals of Rhodamine 6G adsorbed on the Ag/TiO2-coated wings were clearly observed using the 514.5-nm line of an Ar+ laser. The Ag/TiO2-coated wings can be a promising candidate for naturally inspired SERS substrates.

Tuning the SERS Response with Ag-Au Nanoparticle-Embedded Polymer Thin Film Substrates.

PubMed

Rao, V Kesava; Radhakrishnan, T P

2015-06-17

Development of facile routes to the fabrication of thin film substrates with tunable surface enhanced Raman scattering (SERS) efficiency and identification of the optimal conditions for maximizing the enhancement factor (EF) are significant in terms of both fundamental and application aspects of SERS. In the present work, polymer thin films with embedded bimetallic nanoparticles of Ag-Au are fabricated by a simple two-stage protocol. Ag nanoparticles are formed in the first stage, by the in situ reduction of silver nitrate by the poly(vinyl alcohol) (PVA) film through mild thermal annealing, without any additional reducing agent. In the second stage, aqueous solutions of chloroauric acid spread on the Ag-PVA thin film under ambient conditions, lead to the galvanic displacement of Ag by Au in situ inside the film, and the formation of Ag-Au particles. Evolution of the morphology of the bimetallic nanoparticles into hollow cage structures and the distribution of Au on the nanoparticles are revealed through electron microscopy and energy dispersive X-ray spectroscopy. The localized surface plasmon resonance (LSPR) extinction of the nanocomposite thin film evolves with the Ag-Au composition; theoretical simulation of the extinction spectra provides insight into the observed trends. The Ag-Au-PVA thin films are found to be efficient substrates for SERS. The EF follows the variation of the LSPR extinction vis-à-vis the excitation laser wavelength, but with an offset, and the maximum SERS effect is obtained at very low Au content; experiments with Rhodamine 6G showed EFs on the order of 10(8) and a limit of detection of 0.6 pmol. The present study describes a facile and simple fabrication of a nanocomposite thin film that can be conveniently deployed in SERS investigations, and the utility of the bimetallic system to tune and maximize the EF.

Determination of trichloroethylene by using self-referenced SERS and gold-core/silver-shell nanoparticles.

PubMed

Yu, Zhao; Smith, Michael E; Zhang, Jinnan; Zhou, Yan; Zhang, Peng

2018-06-18

A surface-enhanced Raman scattering (SERS) method has been developed to determine the concentration of trichloroethylene (TCE) in environmental water. Au-core/Ag-shell nanoparticles containing 4-mercaptophenylboronic acid (4-MPBA) between the core and shell are used as the SERS substrate. 4-MPBA serves as an internal reference with a Raman shift at 534 cm -1 . TCE reacts with 4-mercaptopyridine (4-MPy) in a so-called Fujiwara reaction. With the presence of TCE in water, the consumption of 4-MPy results in a change in the intensity of its Raman signal at 1220 cm -1 . The ratio of the Raman shift at 1220 cm -1 and 534 cm -1 decreases linearly in the 0.2 to 1.0 μM TCE concentration range, and the detection limit of TCE is as low as 8 ppb (60 nM). The method has been successfully applied to the determination of TCE in spiked lake water. Graphical abstract Gold-core/silver-shell nanoparticles with internal reference embedded have been fabracated to improve the quantitative measurement of SERS. These nanoparticles as SERS substrates, are used to indirectly quantify the concentration of trichloroethylene (a typical halogenated organic compound) by the consumption of 4-mercaptopyridine through the Fujiwara reaction.

Polyethylenimine-assisted seed-mediated synthesis of gold nanoparticles for surface-enhanced Raman scattering studies

NASA Astrophysics Data System (ADS)

Philip, Anish; Ankudze, Bright; Pakkanen, Tuula T.

2018-06-01

Large-sized gold nanoparticles (AuNPs) were synthesized with a new polyethylenimine - assisted seed - mediated method for surface-enhanced Raman scattering (SERS) studies. The size and polydispersity of gold nanoparticles are controlled in the growth step with the amounts of polyethylenimine (PEI) and seeds. Influence of three silicon oxide supports having different surface morphologies, namely halloysite (Hal) nanotubes, glass plates and inverse opal films of SiO2, on the performance of gold nanoparticles in Raman scattering of a 4-aminothiophenol (4-ATP) analyte was investigated. Electrostatic interaction between positively charged polyethylenimine-capped AuNPs and negatively charged surfaces of silicon oxide supports was utilized in fabrication of the SERS substrates using deposition and infiltration methods. The Au-photonic crystal of the three SERS substrate groups is the most active one as it showed the highest analytical enhancement factor (AEF) and the lowest detection limit of 1x10-8 M for 4-ATP. Coupling of the optical properties of photonic crystals with the plasmonic properties of AuNPs provided Au-photonic crystals with the high SERS activity. The AuNPs clusters formed both in the photonic crystal and on the glass plate are capable of forming more hot spots as compared to sparsely distributed AuNPs on Hal nanotubes and thereby increasing the SERS enhancement.

Regulation of AKT Phosphorylation at Ser473 and Thr308 by Endoplasmic Reticulum Stress Modulates Substrate Specificity in a Severity Dependent Manner

PubMed Central

Yung, Hong Wa

2011-01-01

Endoplasmic reticulum (ER) stress is a common factor in the pathophysiology of diverse human diseases that are characterised by contrasting cellular behaviours, from proliferation in cancer to apoptosis in neurodegenerative disorders. Coincidently, dysregulation of AKT/PKB activity, which is the central regulator of cell growth, proliferation and survival, is often associated with the same diseases. Here, we demonstrate that ER stress modulates AKT substrate specificity in a severity-dependent manner, as shown by phospho-specific antibodies against known AKT targets. ER stress also reduces both total and phosphorylated AKT in a severity-dependent manner, without affecting activity of the upstream kinase PDK1. Normalisation to total AKT revealed that under ER stress phosphorylation of Thr308 is suppressed while that of Ser473 is increased. ER stress induces GRP78, and siRNA-mediated knock-down of GRP78 enhances phosphorylation at Ser473 by 3.6 fold, but not at Thr308. Substrate specificity is again altered. An in-situ proximity ligation assay revealed a physical interaction between GRP78 and AKT at the plasma membrane of cells following induction of ER stress. Staining was weak in cells with normal nuclear morphology but stronger in those displaying rounded, condensed nuclei. Co-immunoprecipitation of GRP78 and P-AKT(Ser473) confirmed the immuno-complex consists of non-phosphorylated AKT (Ser473 and Thr308). The interaction is likely specific as AKT did not bind to all molecular chaperones, and GRP78 did not bind to p70 S6 kinase. These findings provide one mechanistic explanation for how ER stress contributes to human pathologies demonstrating contrasting cell fates via modulation of AKT signalling. PMID:21445305

Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone.

PubMed

Zheng, Ying; Chen, Zhuo; Zheng, Chengbin; Lee, Yong-Ill; Hou, Xiandeng; Wu, Li; Tian, Yunfei

2016-08-01

A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5mgL(-1) or 0.09mM (3σ). The relative standard deviation (RSD) for 80mgL(-1) acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

Classifying low-grade and high-grade bladder cancer using label-free serum surface-enhanced Raman spectroscopy and support vector machine

NASA Astrophysics Data System (ADS)

Zhang, Yanjiao; Lai, Xiaoping; Zeng, Qiuyao; Li, Linfang; Lin, Lin; Li, Shaoxin; Liu, Zhiming; Su, Chengkang; Qi, Minni; Guo, Zhouyi

2018-03-01

This study aims to classify low-grade and high-grade bladder cancer (BC) patients using serum surface-enhanced Raman scattering (SERS) spectra and support vector machine (SVM) algorithms. Serum SERS spectra are acquired from 88 serum samples with silver nanoparticles as the SERS-active substrate. Diagnostic accuracies of 96.4% and 95.4% are obtained when differentiating the serum SERS spectra of all BC patients versus normal subjects and low-grade versus high-grade BC patients, respectively, with optimal SVM classifier models. This study demonstrates that the serum SERS technique combined with SVM has great potential to noninvasively detect and classify high-grade and low-grade BC patients.

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

Chen, Limiao, E-mail: chenlimiao@csu.edu.cn; Jing, Qifeng; Chen, Jun

Silver nanostructures with dendritic, flower-like and irregular morphologies were controllably deposited on a silicon substrate in an aqueous hydrogen fluoride solution at room temperature. The morphology of the Ag nanostructures changed from dendritic to urchin-like, flowerlike and pinecone-like with increasing the concentration of polyvinyl pyrrolidone (MW = 55,000) from 2 to 10 mM. The Ag nanostructures were characterized by transmission electron microscopy, high-resolution transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray, and X-ray diffraction. Through a series of time-dependent morphological evolution studies, the growth processes of Ag nanostructures have been systematically investigated and the corresponding growth mechanisms have been discussed.more » In addition, the morphology-dependent surface-enhanced Raman scattering of as-synthesized Ag nanostructures were investigated. The results indicated that flower-like Ag nanostructure had the highest activity than the other Ag nanostructures for Rhodamine 6G probe molecules. Highlights: • A simple method was developed to prepare dendritic and flower-like Ag nanostructures. • The flower-like Ag nanoparticles exhibit highest SERS activity. • The SERS substrate based on flower-like Ag particles can be used to detect melamine.« less

SERS as a bioassay platform: fundamentals, design, and applications

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

Porter, M.; Lipert, R.; Siperko, L.

2008-03-18

Bioanalytical science is experiencing a period of unprecedented growth. Drivers behind this growth include the need to detect markers central to human and veterinary diagnostics at ever-lower levels and greater speeds. A set of parallel arguments applies to pathogens with respect to bioterrorism prevention and food and water safety. This tutorial review outlines our recent explorations on the use of surface enhanced Raman scattering (SERS) for detection of proteins, viruses, and microorganisms in heterogeneous immunoassays. It will detail the design and fabrication of the assay platform, including the capture substrate and nanoparticle-based labels. The latter, which is the cornerstone ofmore » our strategy, relies on the construction of gold nanoparticles modified with both an intrinsically strong Raman scatterer and an antibody. This labelling motif, referred to as extrinsic Raman labels (ERLs), takes advantage of the well-established signal enhancement of scatterers when coated on nanometre-sized gold particles, whereas the antibody imparts antigenic specificity. We will also examine the role of plasmon coupling between the ERLs and capture substrate, and challenges related to particle stability, nonspecific adsorption, and assay speed.« less

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.

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.

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.

Highly Sensitive and Selective In-Situ SERS Detection of Pb(2+), Hg(2+), and Cd(2+) Using Nanoporous Membrane Functionalized with CNTs.

PubMed

Shaban, Mohamed; Galaly, A R

2016-05-04

Porous Anodic Alumina (PAA) membrane was functionalized with CoFe2O4 nanoparticles and used as a substrate for the growing of very long helical-structured Carbon Nanotubes (CNTs) with a diameter less than 20 nm. The structures and morphologies of the fabricated nanostructures were characterized by field emission- scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), and Raman spectroscopy. By uploading the CNTs on PAA, the characteristic Raman peaks of CNTs and PAA showed 4 and 3 times enhancement, respectively, which leads to more sensitive Surface-Enhanced Raman Spectroscopy (SERS) substrates. For comparison, PAA and CNTs/PAA arrays were used as SERS substrates for the detection of Hg(2+), Cd(2+), and Pb(2+). The proposed sensor demonstrated high sensitivity and selectivity between these heavy metal ions. CNTs/PAA sensor showed excellent selectivity toward Pb(2+) over other metal ions, where the enhancement factor is decreased from ~17 for Pb(2+) to ~12 for Hg(2+) and to ~4 for Cd(2+). Therefore, the proposed CNTs/PAA sensor can be used as a powerful tool for the determination of heavy metal ions in aqueous solutions.

Highly Sensitive and Selective In-Situ SERS Detection of Pb2+, Hg2+, and Cd2+ Using Nanoporous Membrane Functionalized with CNTs

PubMed Central

Shaban, Mohamed; Galaly, A. R.

2016-01-01

Porous Anodic Alumina (PAA) membrane was functionalized with CoFe2O4 nanoparticles and used as a substrate for the growing of very long helical-structured Carbon Nanotubes (CNTs) with a diameter less than 20 nm. The structures and morphologies of the fabricated nanostructures were characterized by field emission- scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), and Raman spectroscopy. By uploading the CNTs on PAA, the characteristic Raman peaks of CNTs and PAA showed 4 and 3 times enhancement, respectively, which leads to more sensitive Surface-Enhanced Raman Spectroscopy (SERS) substrates. For comparison, PAA and CNTs/PAA arrays were used as SERS substrates for the detection of Hg2+, Cd2+, and Pb2+. The proposed sensor demonstrated high sensitivity and selectivity between these heavy metal ions. CNTs/PAA sensor showed excellent selectivity toward Pb2+ over other metal ions, where the enhancement factor is decreased from ~17 for Pb2+ to ~12 for Hg2+ and to ~4 for Cd2+. Therefore, the proposed CNTs/PAA sensor can be used as a powerful tool for the determination of heavy metal ions in aqueous solutions. PMID:27143512

Characterization and Potential Application of Next Generation Commercial Surface Enhanced Raman Scattering Substrates

DTIC Science & Technology

2011-11-01

were evaluated. For these experiments, an aliquot of the common bacillus spore B. coagulans was drop-dried onto the SERS substrate active surface...the Klarite surface. Spectra for bacillus spore B. coagulans on different substrate types. 3.5 Energetic Sample Evaluation Hazard detection...substrate types (a–f). Notice the dramatic difference in size between the spore and the active areas on the Klarite surface. Spectra for bacillus

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.

Gold nanoparticles paper as a SERS bio-diagnostic platform.

PubMed

Ngo, Ying Hui; Then, Whui Lyn; Shen, Wei; Garnier, Gil

2013-11-01

Bioactive papers are usually challenged by four major limitations: sensitivity, selectivity, simplicity and strength (4S). Gold nanoparticles (AuNPs) treated paper has previously been demonstrated as a Surface Enhanced Raman Scattering (SERS) active substrate, capable of addressing the 4S issues. In this study, AuNPs on paper substrate were functionalized by a series of biomolecules to develop a generic SERS platform for antibody-antigen detection. The functionalization steps were performed by taking advantage of the high affinity association between Streptomyces avidinii-derived protein, streptavidin, and biotin. Streptavidin was firstly bound onto the AuNPs treated paper using biotinylated-thiol. Subsequently, desired biotinylated-antibody was bound onto the streptavidin. SERS spectra of each functionalization step were obtained to ensure specific adsorption of the bio-molecules. The binding interaction of the antibody with its specific antigen was detected using SERS. Shifts of Raman band associated with α-helix and β-sheet structures indicated structural modification of the antibody upon interaction with its antigen. Predominant tryptophan and tyrosine residue bands were also detected, confirming the presence of antigen. Reproducible spectral features were quantified as AuNP papers were subjected to different concentrations of antigen; the spectra intensity increased as a function of the antigen concentration. The retention of AuNPs on paper remained constant after all the consecutive washing and functionalization steps. The feasibility of AuNPs paper as a low-cost and generic SERS platform for bio-diagnostic applications was demonstrated. Crown Copyright © 2013. Published by Elsevier Inc. All rights reserved.

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.

Headspace-Sampling Paper-Based Analytical Device for Colorimetric/Surface-Enhanced Raman Scattering Dual Sensing of Sulfur Dioxide in Wine.

PubMed

Li, Dan; Duan, Huazhen; Ma, Yadan; Deng, Wei

2018-05-01

This study demonstrates a novel strategy for colorimetric/surface-enhanced Raman scattering (SERS) dual-mode sensing of sulfur dioxide (SO 2 ) by coupling headspace sampling (HS) with paper-based analytical device (PAD). The smart and multifunctional PAD is fabricated with a vacuum filtration method in which 4-mercaptopyridine (Mpy)-modified gold nanorods (GNRs)-reduced graphene oxide (rGO) hybrids (rGO/MPy-GNRs), anhydrous methanol, and starch-iodine complex are immobilized into cellulose-based filter papers. The resultant PAD exhibits a deep-blue color with a strong absorption peak at 600 nm due to the formation of an intermolecular charge-transfer complex between starch and iodine. However, the addition of SO 2 induces the Karl Fischer reaction, resulting in the decrease of color and increase of SERS signals. Therefore, the PAD can be used not only as a naked-eye indicator of SO 2 changed from blue to colorless but also as a highly sensitive SERS substrates because of the SO 2 -triggered conversion of Mpy to pyridine methyl sulfate on the GNRs. A distinguishable change in the color was observed at a SO 2 concentration of 5 μM by the naked eye, and a detection limit as low as 1.45 μM was obtained by virtue of UV-vis spectroscopy. The PAD-based SERS method is effective over a wide range of concentrations (1 μM to 2000 μM) for SO 2 , and the detection limit for SO 2 is found to be 1 μM. The HS-PAD based colorimetric/SERS method is applied for the determination of SO 2 in wine, and the detection results match well with those obtained from the traditional Monier-Williams method. This study not only offers a new method for on-site monitoring of SO 2 but also provides a new strategy for designing of paper-based sensing platform for a wide range of field-test applications.

Specific primary sequence requirements for Aurora B kinase-mediated phosphorylation and subcellular localization of TMAP during mitosis.

PubMed

Kim, Hyun-Jun; Kwon, Hye-Rim; Bae, Chang-Dae; Park, Joobae; Hong, Kyung U

2010-05-15

During mitosis, regulation of protein structures and functions by phosphorylation plays critical roles in orchestrating a series of complex events essential for the cell division process. Tumor-associated microtubule-associated protein (TMAP), also known as cytoskeleton-associated protein 2 (CKAP2), is a novel player in spindle assembly and chromosome segregation. We have previously reported that TMAP is phosphorylated at multiple residues specifically during mitosis. However, the mechanisms and functional importance of phosphorylation at most of the sites identified are currently unknown. Here, we report that TMAP is a novel substrate of the Aurora B kinase. Ser627 of TMAP was specifically phosphorylated by Aurora B both in vitro and in vivo. Ser627 and neighboring conserved residues were strictly required for efficient phosphorylation of TMAP by Aurora B, as even minor amino acid substitutions of the phosphorylation motif significantly diminished the efficiency of the substrate phosphorylation. Nearly all mutations at the phosphorylation motif had dramatic effects on the subcellular localization of TMAP. Instead of being localized to the chromosome region during late mitosis, the mutants remained associated with microtubules and centrosomes throughout mitosis. However, the changes in the subcellular localization of these mutants could not be completely explained by the phosphorylation status on Ser627. Our findings suggest that the motif surrounding Ser627 ((625) RRSRRL (630)) is a critical part of a functionally important sequence motif which not only governs the kinase-substrate recognition, but also regulates the subcellular localization of TMAP during mitosis.

Bio-inspired in situ growth of monolayer silver nanoparticles on graphene oxide paper as multifunctional substrate

NASA Astrophysics Data System (ADS)

Li, Shi-Kuo; Yan, You-Xian; Wang, Jin-Long; Yu, Shu-Hong

2013-11-01

In this study, we report a facile bio-inspired method for large-scale preparation of highly dispersed Ag nanoparticles (NPs) on the surface of flexible reduced graphene oxide (rGO) paper with using dopamine (DA) both as a reductant and a surface modifier. Through the self-polymerization of dopamine, free-standing GO paper can be simultaneously reduced and modified with following in situ growth of monolayer Ag NPs on such a substrate. The spherical Ag NPs with an average diameter of 80 nm have a narrow size distribution and tunable cover density. Such a flexible rGO/Ag hybrid paper presents enhanced antibacterial activity against E. coli and a high active and sensitive SERS response toward Rhodamine 6G (R6G) molecules. The detection signals can be obtained while the R6G concentration is as low as to 10-8 M. This work provides a simple strategy for large-scale fabrication of monolayer Ag NPs on flexible rGO paper as a portable antibacterial substrate and a potential SERS substrate for molecular detection applications.In this study, we report a facile bio-inspired method for large-scale preparation of highly dispersed Ag nanoparticles (NPs) on the surface of flexible reduced graphene oxide (rGO) paper with using dopamine (DA) both as a reductant and a surface modifier. Through the self-polymerization of dopamine, free-standing GO paper can be simultaneously reduced and modified with following in situ growth of monolayer Ag NPs on such a substrate. The spherical Ag NPs with an average diameter of 80 nm have a narrow size distribution and tunable cover density. Such a flexible rGO/Ag hybrid paper presents enhanced antibacterial activity against E. coli and a high active and sensitive SERS response toward Rhodamine 6G (R6G) molecules. The detection signals can be obtained while the R6G concentration is as low as to 10-8 M. This work provides a simple strategy for large-scale fabrication of monolayer Ag NPs on flexible rGO paper as a portable antibacterial substrate and a potential SERS substrate for molecular detection applications. Electronic supplementary information (ESI) available: Preparation of GO aqueous colloid solution; XPS spectra of GO paper and PDA modified rGO paper; SEM images of rGO/Ag hybrid paper after immersed in mercaptoethanol solution or in high alkaline solution; photograph and SEM image of pure rGO paper after reaction with AgNO3 solution. SEM image and TEM graph of the pre-synthesized Ag NPs and their SEM images incubated with PDA modified rGO paper; SERS spectra of R6G (1.0 × 10-4 M) molecules before and after cleaning with concentrated hydrochloric acid liquid taken on rGO/Ag hybrid paper obtained by a reaction with 1.0 M AgNO3 solution; SERS spectra of R6G (1.0 × 10-4 M) molecules with different reusable cycles taken on rGO/Ag hybrid paper obtained by a reaction with 1.0 M AgNO3 solution; comparison between different kinds of substrates with the detection limit toward R6G. See DOI: 10.1039/c3nr03857b

The Effect of Dielectric Constants on Noble Metal/Semiconductor SERS Enhancement: FDTD Simulation and Experiment Validation of Ag/Ge and Ag/Si Substrates

PubMed Central

Wang, Tao; Zhang, Zhaoshun; Liao, Fan; Cai, Qian; Li, Yanqing; Lee, Shuit-Tong; Shao, Mingwang

2014-01-01

The finite-difference time-domain (FDTD) method was employed to simulate the electric field distribution for noble metal (Au or Ag)/semiconductor (Ge or Si) substrates. The simulation showed that noble metal/Ge had stronger SERS enhancement than noble metal/Si, which was mainly attributed to the different dielectric constants of semiconductors. In order to verify the simulation, Ag nanoparticles with the diameter of ca. 40 nm were grown on Ge or Si wafer (Ag/Ge or Ag/Si) and employed as surface-enhanced Raman scattering substrates to detect analytes in solution. The experiment demonstrated that both the two substrates exhibited excellent performance in the low concentration detection of Rhodamine 6G. Besides, the enhancement factor (1.3 × 109) and relative standard deviation values (less than 11%) of Ag/Ge substrate were both better than those of Ag/Si (2.9 × 107 and less than 15%, respectively), which was consistent with the FDTD simulation. Moreover, Ag nanoparticles were grown in-situ on Ge substrate, which kept the nanoparticles from aggregation in the detection. To data, Ag/Ge substrates showed the best performance for their sensitivity and uniformity among the noble metal/semiconductor ones. PMID:24514430

The effect of dielectric constants on noble metal/semiconductor SERS enhancement: FDTD simulation and experiment validation of Ag/Ge and Ag/Si substrates.

PubMed

Wang, Tao; Zhang, Zhaoshun; Liao, Fan; Cai, Qian; Li, Yanqing; Lee, Shuit-Tong; Shao, Mingwang

2014-02-11

The finite-difference time-domain (FDTD) method was employed to simulate the electric field distribution for noble metal (Au or Ag)/semiconductor (Ge or Si) substrates. The simulation showed that noble metal/Ge had stronger SERS enhancement than noble metal/Si, which was mainly attributed to the different dielectric constants of semiconductors. In order to verify the simulation, Ag nanoparticles with the diameter of ca. 40 nm were grown on Ge or Si wafer (Ag/Ge or Ag/Si) and employed as surface-enhanced Raman scattering substrates to detect analytes in solution. The experiment demonstrated that both the two substrates exhibited excellent performance in the low concentration detection of Rhodamine 6G. Besides, the enhancement factor (1.3 × 10(9)) and relative standard deviation values (less than 11%) of Ag/Ge substrate were both better than those of Ag/Si (2.9 × 10(7) and less than 15%, respectively), which was consistent with the FDTD simulation. Moreover, Ag nanoparticles were grown in-situ on Ge substrate, which kept the nanoparticles from aggregation in the detection. To data, Ag/Ge substrates showed the best performance for their sensitivity and uniformity among the noble metal/semiconductor ones.

Rapid Detection of Pathogenic Bacteria from Fresh Produce by Filtration and Surface-Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Xiaomeng; Han, Caiqin; Chen, Jing; Huang, Yao-Wen; Zhao, Yiping

2016-04-01

The detection of Salmonella Poona from cantaloupe cubes and E. coli O157:H7 from lettuce has been explored by using a filtration method and surface-enhanced Raman spectroscopy (SERS) based on vancomycin-functionalized silver nanorod array substrates. It is found that with a two-step filtration process, the limit of detection (LOD) of Salmonella Poona from cantaloupe cubes can be as low as 100 CFU/mL in less than 4 h, whereas the chlorophyll in the lettuce causes severe SERS spectral interference. To improve the LOD of lettuce, a three-step filtration method with a hydrophobic filter is proposed. The hydrophobic filter can effectively eliminate the interferences from chlorophyll and achieve a LOD of 1000 CFU/mL detection of E. coli O157:H7 from lettuce samples within 5 h. With the low LODs and rapid detection time, the SERS biosensing platform has demonstrated its potential as a rapid, simple, and inexpensive means for pathogenic bacteria detection from fresh produce.

Nanosphere Lithography on Fiber: Towards Engineered Lab-On-Fiber SERS Optrodes

PubMed Central

Quero, Giuseppe; Zito, Gianluigi; Cusano, Andrea

2018-01-01

In this paper we report on the engineering of repeatable surface enhanced Raman scattering (SERS) optical fiber sensor devices (optrodes), as realized through nanosphere lithography. The Lab-on-Fiber SERS optrode consists of polystyrene nanospheres in a close-packed arrays configuration covered by a thin film of gold on the optical fiber tip. The SERS surfaces were fabricated by using a nanosphere lithography approach that is already demonstrated as able to produce highly repeatable patterns on the fiber tip. In order to engineer and optimize the SERS probes, we first evaluated and compared the SERS performances in terms of Enhancement Factor (EF) pertaining to different patterns with different nanosphere diameters and gold thicknesses. To this aim, the EF of SERS surfaces with a pitch of 500, 750 and 1000 nm, and gold films of 20, 30 and 40 nm have been retrieved, adopting the SERS signal of a monolayer of biphenyl-4-thiol (BPT) as a reliable benchmark. The analysis allowed us to identify of the most promising SERS platform: for the samples with nanospheres diameter of 500 nm and gold thickness of 30 nm, we measured values of EF of 4 × 105, which is comparable with state-of-the-art SERS EF achievable with highly performing colloidal gold nanoparticles. The reproducibility of the SERS enhancement was thoroughly evaluated. In particular, the SERS intensity revealed intra-sample (i.e., between different spatial regions of a selected substrate) and inter-sample (i.e., between regions of different substrates) repeatability, with a relative standard deviation lower than 9 and 15%, respectively. Finally, in order to determine the most suitable optical fiber probe, in terms of excitation/collection efficiency and Raman background, we selected several commercially available optical fibers and tested them with a BPT solution used as benchmark. A fiber probe with a pure silica core of 200 µm diameter and high numerical aperture (i.e., 0.5) was found to be the most promising fiber platform, providing the best trade-off between high excitation/collection efficiency and low background. This work, thus, poses the basis for realizing reproducible and engineered Lab-on-Fiber SERS optrodes for in-situ trace detection directed toward highly advanced in vivo sensing. PMID:29495322

Deciphering the Arginine-Binding Preferences at the Substrate-Binding Groove of Ser/Thr Kinases by Computational Surface Mapping

PubMed Central

Ben-Shimon, Avraham; Niv, Masha Y.

2011-01-01

Protein kinases are key signaling enzymes that catalyze the transfer of γ-phosphate from an ATP molecule to a phospho-accepting residue in the substrate. Unraveling the molecular features that govern the preference of kinases for particular residues flanking the phosphoacceptor is important for understanding kinase specificities toward their substrates and for designing substrate-like peptidic inhibitors. We applied ANCHORSmap, a new fragment-based computational approach for mapping amino acid side chains on protein surfaces, to predict and characterize the preference of kinases toward Arginine binding. We focus on positions P−2 and P−5, commonly occupied by Arginine (Arg) in substrates of basophilic Ser/Thr kinases. The method accurately identified all the P−2/P−5 Arg binding sites previously determined by X-ray crystallography and produced Arg preferences that corresponded to those experimentally found by peptide arrays. The predicted Arg-binding positions and their associated pockets were analyzed in terms of shape, physicochemical properties, amino acid composition, and in-silico mutagenesis, providing structural rationalization for previously unexplained trends in kinase preferences toward Arg moieties. This methodology sheds light on several kinases that were described in the literature as having non-trivial preferences for Arg, and provides some surprising departures from the prevailing views regarding residues that determine kinase specificity toward Arg. In particular, we found that the preference for a P−5 Arg is not necessarily governed by the 170/230 acidic pair, as was previously assumed, but by several different pairs of acidic residues, selected from positions 133, 169, and 230 (PKA numbering). The acidic residue at position 230 serves as a pivotal element in recognizing Arg from both the P−2 and P−5 positions. PMID:22125489

cis-Proline-mediated Ser(P)[superscript 5] Dephosphorylation by the RNA Polymerase II C-terminal Domain Phosphatase Ssu72

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

Werner-Allen, Jon W.; Lee, Chul-Jin; Liu, Pengda

2012-05-16

RNA polymerase II coordinates co-transcriptional events by recruiting distinct sets of nuclear factors to specific stages of transcription via changes of phosphorylation patterns along its C-terminal domain (CTD). Although it has become increasingly clear that proline isomerization also helps regulate CTD-associated processes, the molecular basis of its role is unknown. Here, we report the structure of the Ser(P){sup 5} CTD phosphatase Ssu72 in complex with substrate, revealing a remarkable CTD conformation with the Ser(P){sup 5}-Pro{sup 6} motif in the cis configuration. We show that the cis-Ser(P){sup 5}-Pro{sup 6} isomer is the minor population in solution and that Ess1-catalyzed cis-trans-proline isomerizationmore » facilitates rapid dephosphorylation by Ssu72, providing an explanation for recently discovered in vivo connections between these enzymes and a revised model for CTD-mediated small nuclear RNA termination. This work presents the first structural evidence of a cis-proline-specific enzyme and an unexpected mechanism of isomer-based regulation of phosphorylation, with broad implications for CTD biology« less

Enhancement factor statistics of surface enhanced Raman scattering in multiscale heterostructures of nanoparticles.

PubMed

Zito, Gianluigi; Rusciano, Giulia; Sasso, Antonio

2016-08-07

Suitable metal nanostructures may induce surface-enhanced Raman scattering (SERS) enhancement factors (EFs) large-enough to reach single-molecule sensitivity. However, the gap hot-spot EF probability density function (PDF) has the character of a long-tail distribution, which dramatically mines the reproducibility of SERS experiments. Herein, we carry out electrodynamic calculations based on a 3D finite element method of two plasmonic nanostructures, combined with Monte Carlo simulations of the EF statistics under different external conditions. We compare the PDF produced by a homodimer of nanoparticles with that provided by a self-similar trimer. We show that the PDF is sensitive to the spatial distribution of near-field enhancement specifically supported by the nanostructure geometry. Breaking the symmetry of the plasmonic system is responsible for inducing particular modulations of the PDF tail resembling a multiple Poisson distribution. We also study the influence that molecular diffusion towards the hottest hot-spot, or selective hot-spot targeting, might have on the EF PDF. Our results quantitatively assess the possibility of designing the response of a SERS substrate so as to contain the intrinsic EF PDF variance and significantly improving, in principle, the reproducibility of SERS experiments.

Single Bacterium Detection Using Sers

NASA Astrophysics Data System (ADS)

Gonchukov, S. A.; Baikova, T. V.; Alushin, M. V.; Svistunova, T. S.; Minaeva, S. A.; Ionin, A. A.; Kudryashov, S. I.; Saraeva, I. N.; Zayarny, D. A.

2016-02-01

This work is devoted to the study of a single Staphylococcus aureus bacterium detection using surface-enhanced Raman spectroscopy (SERS) and resonant Raman spectroscopy (RS). It was shown that SERS allows increasing sensitivity of predominantly low frequency lines connected with the vibrations of Amide, Proteins and DNA. At the same time the lines of carotenoids inherent to this kind of bacterium are well-detected due to the resonance Raman scattering mechanism. The reproducibility and stability of Raman spectra strongly depend on the characteristics of nanostructured substrate, and molecular structure and size of the tested biological object.

SERS spectra of pyridine adsorbed on nickel film prepared by magnetron sputtering

NASA Astrophysics Data System (ADS)

Li, Daoyong; Ouyang, Yu; Chen, Li; Cao, Weiran; Shi, Shaohua

2011-02-01

As a repeating well and cheaper enhancement substrate, the nickel film was fabricated with magnetron sputtering coating instrument. Surface enhanced Raman spectra (SERS) of pyridine adsorbed on this nickel film are compared with the experimental values of gaseous pyridine, the theoretical value of pyridine solution listed in other literatures and our method is better than electro-chemical etching electrode method for large scale preparation. The enhancement factor of the nickel film is calculated and the result indicates that magnetron sputtering coating technology is feasible for obtaining good SERS active surface.

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.

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.

Graphene Dendrimer-stabilized silver nanoparticles for detection of methimazole using Surface-enhanced Raman scattering with computational assignment

NASA Astrophysics Data System (ADS)

Saleh, Tawfik A.; Al-Shalalfeh, Mutasem M.; Al-Saadi, Abdulaziz A.

2016-08-01

Graphene functionalized with polyamidoamine dendrimer, decorated with silver nanoparticles (G-D-Ag), was synthesized and evaluated as a substrate with surface-enhanced Raman scattering (SERS) for methimazole (MTZ) detection. Sodium borohydride was used as a reducing agent to cultivate silver nanoparticles on the dendrimer. The obtained G-D-Ag was characterized by using UV-vis spectroscopy, scanning electron microscope (SEM), high-resolution transmission electron microscope (TEM), Fourier-transformed infrared (FT-IR) and Raman spectroscopy. The SEM image indicated the successful formation of the G-D-Ag. The behavior of MTZ on the G-D-Ag as a reliable and robust substrate was investigated by SERS, which indicated mostly a chemical interaction between G-D-Ag and MTZ. The bands of the MTZ normal spectra at 1538, 1463, 1342, 1278, 1156, 1092, 1016, 600, 525 and 410 cm-1 were enhanced due to the SERS effect. Correlations between the logarithmical scale of MTZ concentrations and SERS signal intensities were established, and a low detection limit of 1.43 × 10-12 M was successfully obtained. The density functional theory (DFT) approach was utilized to provide reliable assignment of the key Raman bands.

Facile preparation of dendritic Ag-Pd bimetallic nanostructures on the surface of Cu foil for application as a SERS-substrate

NASA Astrophysics Data System (ADS)

Yi, Zao; Tan, Xiulan; Niu, Gao; Xu, Xibin; Li, Xibo; Ye, Xin; Luo, Jiangshan; Luo, Binchi; Wu, Weidong; Tang, Yongjian; Yi, Yougen

2012-05-01

Dendritic Ag-Pd bimetallic nanostructures have been synthesized on the surface of Cu foil via a multi-stage galvanic replacement reaction (MGRR) of Ag dendrites in a Na2PdCl4 solution. After five stages of replacement reaction, one obtained structures with protruding Ag-Pd flakes; these will mature into many porous structures with a few Ag atoms that are left over dendrites. The dendritic Ag-Pd bimetallic nanostructures were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), selected area electron diffraction (SAED) and X-ray photoelectron spectroscopy (XPS). The morphology of the products strongly depended on the stage of galvanic replacement reaction and reaction temperature. The morphology and composition-dependent surface-enhanced Raman scattering (SERS) of the as-synthesized Ag-Pd bimetallic nanostructures were investigated. The effectiveness of these dendritic Ag-Pd bimetallic nanostructures on the surface of Cu foil as substrates toward SERS detection was evaluated by using rhodamine 6G (R6G) as a probe molecule. The results indicate that as-synthesized dendritic Ag-Pd bimetallic nanostructures are good candidates for SERS spectroscopy.

Graphene Dendrimer-stabilized silver nanoparticles for detection of methimazole using Surface-enhanced Raman scattering with computational assignment

PubMed Central

Saleh, Tawfik A.; Al-Shalalfeh, Mutasem M.; Al-Saadi, Abdulaziz A.

2016-01-01

Graphene functionalized with polyamidoamine dendrimer, decorated with silver nanoparticles (G-D-Ag), was synthesized and evaluated as a substrate with surface-enhanced Raman scattering (SERS) for methimazole (MTZ) detection. Sodium borohydride was used as a reducing agent to cultivate silver nanoparticles on the dendrimer. The obtained G-D-Ag was characterized by using UV-vis spectroscopy, scanning electron microscope (SEM), high-resolution transmission electron microscope (TEM), Fourier-transformed infrared (FT-IR) and Raman spectroscopy. The SEM image indicated the successful formation of the G-D-Ag. The behavior of MTZ on the G-D-Ag as a reliable and robust substrate was investigated by SERS, which indicated mostly a chemical interaction between G-D-Ag and MTZ. The bands of the MTZ normal spectra at 1538, 1463, 1342, 1278, 1156, 1092, 1016, 600, 525 and 410 cm−1 were enhanced due to the SERS effect. Correlations between the logarithmical scale of MTZ concentrations and SERS signal intensities were established, and a low detection limit of 1.43 × 10−12 M was successfully obtained. The density functional theory (DFT) approach was utilized to provide reliable assignment of the key Raman bands. PMID:27572919

Molecular structure of EmbR, a response element of Ser/Thr kinase signaling in Mycobacterium tuberculosis

PubMed Central

Alderwick, Luke J.; Molle, Virginie; Kremer, Laurent; Cozzone, Alain J.; Dafforn, Timothy R.; Besra, Gurdyal S.; Fütterer, Klaus

2006-01-01

Ser/Thr phosphorylation has emerged as a critical regulatory mechanism in a number of bacteria, including Mycobacterium tuberculosis. This problematic pathogen encodes 11 eukaryotic-like Ser/Thr kinases, yet few substrates or signaling targets have been characterized. Here, we report the structure of EmbR (2.0 Å), a putative transcriptional regulator of key arabinosyltransferases (EmbC, -A, and -B), and an endogenous substrate of the Ser/Thr-kinase PknH. EmbR presents a unique domain architecture: the N-terminal winged-helix DNA-binding domain forms an extensive interface with the all-helical central bacterial transcriptional activation domain and is positioned adjacent to the regulatory C-terminal forkhead-associated (FHA) domain, which mediates binding to a Thr-phosphorylated site in PknH. The structure in complex with a phospho-peptide (1.9 Å) reveals a conserved mode of phospho-threonine recognition by the FHA domain and evidence for specific recognition of the cognate kinase. The present structures suggest hypotheses as to how EmbR might propagate the phospho-relay signal from its cognate kinase, while serving as a template for the structurally uncharacterized Streptomyces antibiotic regulatory protein family of transcription factors. PMID:16477027

Synergistic Allosteric Mechanism of Fructose-1,6-bisphosphate and Serine for Pyruvate Kinase M2 via Dynamics Fluctuation Network Analysis.

PubMed

Yang, Jingxu; Liu, Hao; Liu, Xiaorui; Gu, Chengbo; Luo, Ray; Chen, Hai-Feng

2016-06-27

Pyruvate kinase M2 (PKM2) plays a key role in tumor metabolism and regulates the rate-limiting final step of glycolysis. In tumor cells, there are two allosteric effectors for PKM2: fructose-1,6-bisphosphate (FBP) and serine. However, the relationship between FBP and serine for allosteric regulation of PKM2 is unknown. Here we constructed residue/residue fluctuation correlation network based on all-atom molecular dynamics simulations to reveal the regulation mechanism. The results suggest that the correlation network in bound PKM2 is distinctly different from that in the free state, FBP/PKM2, or Ser/PKM2. The community network analysis indicates that the information can freely transfer from the allosteric sites of FBP and serine to the substrate site in bound PKM2, while there exists a bottleneck for information transfer in the network of the free state. Furthermore, the binding free energy between the substrate and PKM2 for bound PKM2 is significantly lower than either of FBP/PKM2 or Ser/PKM2. Thus, a hypothesis of "synergistic allosteric mechanism" is proposed for the allosteric regulation of FBP and serine. This hypothesis was further confirmed by the perturbational and mutational analyses of community networks and binding free energies. Finally, two possible synergistic allosteric pathways of FBP-K433-T459-R461-A109-V71-R73-MG2-OXL and Ser-I47-C49-R73-MG2-OXL were identified based on the shortest path algorithm and were confirmed by the network perturbation analysis. Interestingly, no similar pathways could be found in the free state. The process targeting on the allosteric pathways can better regulate the glycolysis of PKM2 and significantly inhibit the progression of tumor.

Raptor binds the SAIN (Shc and IRS-1 NPXY binding) domain of insulin receptor substrate-1 (IRS-1) and regulates the phosphorylation of IRS-1 at Ser-636/639 by mTOR.

PubMed

Tzatsos, Alexandros

2009-08-21

In normal physiological states mTOR phosphorylates and activates Akt. However, under diabetic-mimicking conditions mTOR inhibits phosphatidylinositol (PI) 3-kinase/Akt signaling by phosphorylating insulin receptor substrate-1 (IRS-1) at Ser-636/639. The molecular basis for the differential effect of mTOR signaling on Akt is poorly understood. Here, it has been shown that knockdown of mTOR, Raptor, and mLST8, but not Rictor and mSin1, suppresses insulin-stimulated phosphorylation of IRS-1 at Ser-636/639 and stabilizes IRS-1 after long term insulin stimulation. This phosphorylation depends on the PI 3-kinase/PDK1 axis but is Akt-independent. At the molecular level, Raptor binds the SAIN (Shc and IRS-1 NPXY binding) domain of IRS-1 and regulates the phosphorylation of IRS-1 at Ser-636/639 by mTOR. IRS-1 lacking the SAIN domain does not interact with Raptor, is not phosphorylated at Ser-636/639, and favorably interacts with PI 3-kinase. Overall, these data provide new insights in the molecular mechanisms by which mTORC1 inhibits PI 3-kinase/Akt signaling at the level of IRS-1 and suggest that mTOR signaling toward Akt is scaffold-dependent.

Detection of chemical residues in food oil via surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Sun, Kexi; Huang, Qing

2016-05-01

Highly ordered hexagonally patterned Ag-nanorod (Ag-NR) arrays for surface-enhanced Raman scattering (SERS) detection of unhealthy chemical residues in food oil was reported, which was obtained by sputtering Ag on the alumina nanotip arrays stuck out of conical-pore anodic aluminum oxide (AAO) templates. SERS measurements demonstrate that the as-fabricated large-scale Ag-nanostructures can serve as highly sensitive and reproducible SERS substrates for detection of trace amount of chemicals in oil with the lower detection limits of 2×10-6 M for thiram and 10-7 M for rhodamine B, showing the potential of application of SERS in rapid trace detection of pesticide residues and illegal additives in food oils.

Bimetallic 3D nanostar dimers in ring cavities: recyclable and robust surface-enhanced Raman scattering substrates for signal detection from few molecules.

PubMed

Gopalakrishnan, Anisha; Chirumamilla, Manohar; De Angelis, Francesco; Toma, Andrea; Zaccaria, Remo Proietti; Krahne, Roman

2014-08-26

Top-down fabrication of electron-beam lithography (EBL)-defined metallic nanostructures is a successful route to obtain extremely high electromagnetic field enhancement via plasmonic effects in well-defined regions. To this aim, various geometries have been introduced such as disks, triangles, dimers, rings, self-similar lenses, and more. In particular, metallic dimers are highly efficient for surface-enhanced Raman spectroscopy (SERS), and their decoupling from the substrate in a three-dimensional design has proven to further improve their performance. However, the large fabrication time and cost has hindered EBL-defined structures from playing a role in practical applications. Here we present three-dimensional nanostar dimer devices that can be recycled via maskless metal etching and deposition processes, due to conservation of the nanostructure pattern in the 3D geometry of the underlying Si substrate. Furthermore, our 3D-nanostar-dimer-in-ring structures (3D-NSDiRs) incorporate several advantageous aspects for SERS by enhancing the performance of plasmonic dimers via an external ring cavity, by efficient decoupling from the substrate through an elevated 3D design, and by bimetallic AuAg layers that exploit the increased performance of Ag while maintaining the biocompatibility of Au. We demonstrate SERS detection on rhodamine and adenine at extremely low density up to the limit of few molecules and analyze the field enhancement of the 3D-NSDiRs with respect to the exciting wavelength and metal composition.

Label-free SERS study of galvanic replacement reaction on silver nanorod surface and its application to detect trace mercury ion

PubMed Central

Wang, Yaohui; Wen, Guiqing; Ye, Lingling; Liang, Aihui; Jiang, Zhiliang

2016-01-01

It is significant to explore a rapid and highly sensitive galvanic replacement reaction (GRR) surface enhanced Raman scattering (SERS) method for detection of trace mercury ions. This article was reported a new GRR SERS analytical platform for detecting Hg(II) with label-free molecular probe Victoria blue B (VBB). In HAc-NaCl-silver nanorod (AgNR) substrate, the molecular probe VBB exhibited a strong SERS peak at 1609 cm−1. Upon addition of Hg(II), the GRR occurred between the AgNR and Hg(II), and formed a weak SERS activity of Hg2Cl2 that deposited on the AgNR surfaces to decrease the SERS intensity at 1609 cm−1. The decreased SERS intensity was linear to Hg(II) concentration in the range of 1.25–125 nmol/L, with a detection limit of 0.2 nmol/L. The GRR was studied by SERS, transmission electron microscopy and other techniques, and the GRR mechanism was discussed. PMID:26792071

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.

A rapid detection method of Escherichia coli by surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Tao, Feifei; Peng, Yankun; Xu, Tianfeng

2015-05-01

Conventional microbiological detection and enumeration methods are time-consuming, labor-intensive, and giving retrospective information. The objectives of the present work are to study the capability of surface enhanced Raman scattering (SERS) to detect Escherichia coli (E. coli) using the presented silver colloidal substrate. The obtained results showed that the adaptive iteratively reweighed Penalized Least Squares (airPLS) algorithm could effectively remove the fluorescent background from original Raman spectra, and Raman characteristic peaks of 558, 682, 726, 1128, 1210 and 1328 cm-1 could be observed stably in the baseline corrected SERS spectra of all studied bacterial concentrations. The detection limit of SERS could be determined to be as low as 0.73 log CFU/ml for E. coli with the prepared silver colloidal substrate. The quantitative prediction results using the intensity values of characteristic peaks were not good, with the correlation coefficients of calibration set and cross validation set of 0.99 and 0.64, respectively.