Gold@silver bimetal nanoparticles/pyramidal silicon 3D substrate with high reproducibility for high-performance SERS

NASA Astrophysics Data System (ADS)

Zhang, Chao; Jiang, Shou Zhen; Yang, Cheng; Li, Chong Hui; Huo, Yan Yan; Liu, Xiao Yun; Liu, Ai Hua; Wei, Qin; Gao, Sai Sai; Gao, Xing Guo; Man, Bao Yuan

2016-05-01

A novel and efficient surface enhanced Raman scattering (SERS) substrate has been presented based on Gold@silver/pyramidal silicon 3D substrate (Au@Ag/3D-Si). By combining the SERS activity of Ag, the chemical stability of Au and the large field enhancement of 3D-Si, the Au@Ag/3D-Si substrate possesses perfect sensitivity, homogeneity, reproducibility and chemical stability. Using R6G as probe molecule, the SERS results imply that the Au@Ag/3D-Si substrate is superior to the 3D-Si, Ag/3D-Si and Au/3D-Si substrate. We also confirmed these excellent behaviors in theory via a commercial COMSOL software. The corresponding experimental and theoretical results indicate that our proposed Au@Ag/3D-Si substrate is expected to develop new opportunities for label-free SERS detections in biological sensors, biomedical diagnostics and food safety.

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.

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

Superhydrophobic Ag nanostructures on polyaniline membranes with strong SERS enhancement.

PubMed

Liu, Weiyu; Miao, Peng; Xiong, Lu; Du, Yunchen; Han, Xijiang; Xu, Ping

2014-11-07

We demonstrate here a facile fabrication of n-dodecyl mercaptan-modified superhydrophobic Ag nanostructures on polyaniline membranes for molecular detection based on SERS technique, which combines the superhydrophobic condensation effect and the high enhancement factor. It is calculated that the as-fabricated superhydrophobic substrate can exhibit a 21-fold stronger molecular condensation, and thus further amplifies the SERS signal to achieve more sensitive detection. The detection limit of the target molecule, methylene blue (MB), on this superhydrophobic substrate can be 1 order of magnitude higher than that on the hydrophilic substrate. With high reproducibility, the feasibility of using this SERS-active superhydrophobic substrate for quantitative molecular detection is explored. A partial least squares (PLS) model was established for the quantification of MB by SERS, with correlation coefficient R(2) = 95.1% and root-mean-squared error of prediction (RMSEP) = 0.226. We believe this superhydrophobic SERS substrate can be widely used in trace analysis due to its facile fabrication, high signal reproducibility and promising SERS performance.

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.

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.

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.

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

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

NASA Astrophysics Data System (ADS)

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

2013-10-01

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

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.

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.

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

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

Fast assembling microarrays of superparamagnetic Fe3O4@Au nanoparticle clusters as reproducible substrates for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Ye, Min; Wei, Zewen; Hu, Fei; Wang, Jianxin; Ge, Guanglu; Hu, Zhiyuan; Shao, Mingwang; Lee, Shuit-Tong; Liu, Jian

2015-08-01

It is currently a very active research area to develop new types of substrates which integrate various nanomaterials for surface-enhanced Raman scattering (SERS) techniques. Here we report a unique approach to prepare SERS substrates with reproducible performance. It features silicon mold-assisted magnetic assembling of superparamagnetic Fe3O4@Au nanoparticle clusters (NCs) into arrayed microstructures on a wafer scale. This approach enables the fabrication of both silicon-based and hydrogel-based substrates in a sequential manner. We have demonstrated that strong SERS signals can be harvested from these substrates due to an efficient coupling effect between Fe3O4@Au NCs, with enhancement factors >106. These substrates have been confirmed to provide reproducible SERS signals, with low variations in different locations or batches of samples. We investigate the spatial distributions of electromagnetic field enhancement around Fe3O4@Au NCs assemblies using finite-difference-time-domain (FDTD) simulations. The procedure to prepare the substrates is straightforward and fast. The silicon mold can be easily cleaned out and refilled with Fe3O4@Au NCs assisted by a magnet, therefore being re-useable for many cycles. Our approach has integrated microarray technologies and provided a platform for thousands of independently addressable SERS detection, in order to meet the requirements of a rapid, robust, and high throughput performance.It is currently a very active research area to develop new types of substrates which integrate various nanomaterials for surface-enhanced Raman scattering (SERS) techniques. Here we report a unique approach to prepare SERS substrates with reproducible performance. It features silicon mold-assisted magnetic assembling of superparamagnetic Fe3O4@Au nanoparticle clusters (NCs) into arrayed microstructures on a wafer scale. This approach enables the fabrication of both silicon-based and hydrogel-based substrates in a sequential manner. We have demonstrated that strong SERS signals can be harvested from these substrates due to an efficient coupling effect between Fe3O4@Au NCs, with enhancement factors >106. These substrates have been confirmed to provide reproducible SERS signals, with low variations in different locations or batches of samples. We investigate the spatial distributions of electromagnetic field enhancement around Fe3O4@Au NCs assemblies using finite-difference-time-domain (FDTD) simulations. The procedure to prepare the substrates is straightforward and fast. The silicon mold can be easily cleaned out and refilled with Fe3O4@Au NCs assisted by a magnet, therefore being re-useable for many cycles. Our approach has integrated microarray technologies and provided a platform for thousands of independently addressable SERS detection, in order to meet the requirements of a rapid, robust, and high throughput performance. Electronic supplementary information (ESI) available: XRD, reflection spectra, zeta potential, TEM images, evaluations of reproducibility, EDS, tables of EF and RSD values of different substrates. See DOI: 10.1039/c5nr02491a

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.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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.

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.

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.

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.

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.

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.

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.

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).

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

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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

USDA-ARS?s Scientific Manuscript database

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

Surface enhanced Raman 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.

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.

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.

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.

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.

Reassessing SERS enhancement factors: using thermodynamics to drive substrate design.

PubMed

Guicheteau, J A; Tripathi, A; Emmons, E D; Christesen, S D; Fountain, Augustus W

2017-12-04

Over the past 40 years fundamental and application research into Surface-Enhanced Raman Scattering (SERS) has been explored by academia, industry, and government laboratories. To date however, SERS has achieved little commercial success as an analytical technique. Researchers are tackling a variety of paths to help break through the commercial barrier by addressing the reproducibility in both the SERS substrates and SERS signals as well as continuing to explore the underlying mechanisms. To this end, investigators use a variety of methodologies, typically studying strongly binding analytes such as aromatic thiols and azarenes, and report SERS enhancement factor calculations. However a drawback of the traditional SERS enhancement factor calculation is that it does not yield enough information to understand substrate reproducibility, application potential with another analyte, or the driving factors behind the molecule-metal interaction. Our work at the US Army Edgewood Chemical Biological Center has focused on these questions and we have shown that thermodynamic principles play a key role in the SERS response and are an essential factor in future designs of substrates and applications. This work will discuss the advantages and disadvantages of various experimental techniques used to report SERS enhancement with planar SERS substrates and present our alternative SERS enhancement value. We will report on three types of analysis scenarios that all yield different information concerning the effectiveness of the SERS substrate, practical application of the substrate, and finally the thermodynamic properties of the substrate. We believe that through this work a greater understanding for designing substrates will be achieved, one that is based on both thermodynamic and plasmonic properties as opposed to just plasmonic properties. This new understanding and potential change in substrate design will enable more applications for SERS based methodologies including targeting molecules that are traditionally not easily detected with SERS due to the perceived weak molecule-metal interaction of substrates.

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

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

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.

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%.

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

Roles of s3 site residues of nattokinase on its activity and substrate specificity.

PubMed

Wu, Shuming; Feng, Chi; Zhong, Jin; Huan, Liandong

2007-09-01

Nattokinase (Subtilisin NAT, NK) is a bacterial serine protease with high fibrinolytic activity. To probe their roles on protease activity and substrate specificity, three residues of S3 site (Gly(100), Ser(101) and Leu(126)) were mutated by site-directed mutagenesis. Kinetics parameters of 20 mutants were measured using tetrapeptides as substrates, and their fibrinolytic activities were determined by fibrin plate method. Results of mutation analysis showed that Gly(100) and Ser(101) had reverse steric and electrostatic effects. Residues with bulky or positively charged side chains at position 100 decreased the substrate binding and catalytic activity drastically, while residues with the same characters at position 101 could obviously enhance protease and fibrinolytic activity of NK. Mutation of Leu(126) might impair the structure of the active cleft and drastically decreased the activity of NK. Kinetics studies of the mutants showed that S3 residues were crucial to keep protease activity while they moderately affected substrate specificity of NK. The present study provided some original insight into the P3-S3 interaction in NK and other subtilisins, as well as showed successful protein engineering cases to improve NK as a potential therapeutic agent.

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

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.

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

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.

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...

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.

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.

Rational design of Raman-labeled nanoparticles for a dual-modality, light scattering immunoassay on a polystyrene substrate.

PubMed

Israelsen, Nathan D; Wooley, Donald; Hanson, Cynthia; Vargis, Elizabeth

2016-01-01

Surface-enhanced Raman scattering (SERS) is a powerful light scattering technique that can be used for sensitive immunoassay development and cell labeling. A major obstacle to using SERS is the complexity of fabricating SERS probes since they require nanoscale characterization and optical uniformity. The light scattering response of SERS probes may also be modulated by the substrate used for SERS analysis. A typical SERS substrate such as quartz can be expensive. Polystyrene is a cheaper substrate option but can decrease the SERS response due to interfering Raman emission peaks and high background fluorescence. The goal of this research is to develop an optimized process for fabricating Raman-labeled nanoparticles for a SERS-based immunoassay on a polystyrene substrate. We have developed a method for fabricating SERS nanoparticle probes for use in a light scattering immunoassay on a polystyrene substrate. The light scattering profile of both spherical gold nanoparticle and gold nanorod SERS probes were characterized using Raman spectroscopy and optical absorbance spectroscopy. The effects of substrate interference and autofluorescence were reduced by selecting a Raman reporter with a strong light scattering response in a spectral region where interfering substrate emission peaks are minimized. Both spherical gold nanoparticles and gold nanorods SERS probes used in the immunoassay were detected at labeling concentrations in the low pM range. This analytical sensitivity falls within the typical dynamic range for direct labeling of cell-surface biomarkers using SERS probes. SERS nanoparticle probes were fabricated to produce a strong light scattering signal despite substrate interference. The optical extinction and inelastic light scattering of these probes was detected by optical absorbance spectroscopy and Raman spectroscopy, respectively. This immunoassay demonstrates the feasibility of analyzing strongly enhanced Raman signals on polystyrene, which is an inexpensive yet non-ideal Raman substrate. The assay sensitivity, which is in the low pM range, suggests that these SERS probe particles could be used for Raman labeling of cell or tissue samples in a polystyrene tissue culture plate. With continued development, this approach could be used for direct labeling of multiple cell surface biomarkers on strongly interfering substrate platforms.

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.

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.

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.

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

G protein-coupled receptors (GPCRs) That Signal via Protein Kinase A (PKA) Cross-talk at Insulin Receptor Substrate 1 (IRS1) to Activate the phosphatidylinositol 3-kinase (PI3K)/AKT Pathway.

PubMed

Law, Nathan C; White, Morris F; Hunzicker-Dunn, Mary E

2016-12-30

G protein-coupled receptors (GPCRs) activate PI3K/v-AKT thymoma viral oncoprotein (AKT) to regulate many cellular functions that promote cell survival, proliferation, and growth. However, the mechanism by which GPCRs activate PI3K/AKT remains poorly understood. We used ovarian preantral granulosa cells (GCs) to elucidate the mechanism by which the GPCR agonist FSH via PKA activates the PI3K/AKT cascade. Insulin-like growth factor 1 (IGF1) is secreted in an autocrine/paracrine manner by GCs and activates the IGF1 receptor (IGF1R) but, in the absence of FSH, fails to stimulate YXXM phosphorylation of IRS1 (insulin receptor substrate 1) required for PI3K/AKT activation. We show that PKA directly phosphorylates the protein phosphatase 1 (PP1) regulatory subunit myosin phosphatase targeting subunit 1 (MYPT1) to activate PP1 associated with the IGF1R-IRS1 complex. Activated PP1 is sufficient to dephosphorylate at least four IRS1 Ser residues, Ser 318 , Ser 346 , Ser 612 , and Ser 789 , and promotes IRS1 YXXM phosphorylation by the IGF1R to activate the PI3K/AKT cascade. Additional experiments indicate that this mechanism also occurs in breast cancer, thyroid, and preovulatory granulosa cells, suggesting that the PKA-dependent dephosphorylation of IRS1 Ser/Thr residues is a conserved mechanism by which GPCRs signal to activate the PI3K/AKT pathway downstream of the IGF1R. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

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.

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.

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.

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

Chemically attached gold nanoparticle-carbon nanotube hybrids for highly sensitive SERS substrate

NASA Astrophysics Data System (ADS)

Beqa, Lule; Singh, Anant Kumar; Fan, Zheng; Senapati, Dulal; Ray, Paresh Chandra

2011-08-01

Surface-enhanced Raman spectroscopy (SERS) has been shown as one of the most powerful analytical tool with high sensitivity. In this manuscript, we report the chemical design of SERS substrate, based on gold nanoparticles of different shapes-decorated with carbon nanotube with an enhancement factor of 7.5 × 1010. Shape dependent result shows that popcorn shape gold nanoparticle decorated SWCNT is the best choice for SERS substrate due to the existence of 'lightning rod effect' through several sharp edges or corners. Our results provide a good approach to develop highly sensitive SERS substrates and can help to improve the fundamental understanding of SERS phenomena.

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.

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.

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.

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.

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%.

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.

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.

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 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

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

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.

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

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..

Paper-based SERS swab for rapid trace detection on real-world surfaces.

PubMed

Lee, Chang H; Tian, Limei; Singamaneni, Srikanth

2010-12-01

One of the important but often overlooked considerations in the design of surface-enhanced Raman scattering (SERS) substrates for trace detection is the efficiency of sample collection. Conventional designs based on rigid substrates such as silicon, alumina, and glass resist conformal contact with the surface under investigation, making the sample collection inefficient. We demonstrate a novel SERS substrate based on common filter paper adsorbed with gold nanorods, which allows conformal contact with real-world surfaces, thus dramatically enhancing the sample collection efficiency compared to conventional rigid substrates. We demonstrate the detection of trace amounts of analyte (140 pg spread over 4 cm2) by simply swabbing the surface under investigation with the novel SERS substrate. The hierarchical fibrous structure of paper serves as a 3D vasculature for easy uptake and transport of the analytes to the electromagnetic hot spots in the paper. Simple yet highly efficient and cost-effective SERS substrate demonstrated here brings SERS-based trace detection closer to real-world applications.

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

Paper based Flexible and Conformal SERS Substrate for Rapid Trace Detection on Real-world Surfaces

NASA Astrophysics Data System (ADS)

Singamaneni, Srikanth; Lee, Chang; Tian, Limei

2011-03-01

One of the important but often overlooked considerations in the design of surface enhanced Raman scattering (SERS) substrates for trace detection is the efficiency of sample collection. Conventional designs based on rigid substrates such as silicon, alumina, and glass resist conformal contact with the surface under investigation, making the sample collection inefficient. We demonstrate a novel SERS substrate based on common filter paper adsorbed with gold nanorods, which allows conformal contact with real-world surfaces, thus dramatically enhancing the sample collection efficiency compared to conventional rigid substrates. We demonstrate the detection of trace amounts of analyte (140 pg spread over 4 cm2) by simply swabbing the surface under investigation with the novel SERS substrate. The hierarchical fibrous structure of paper serves as a 3D vasculature for easy uptake and transport of the analytes to the electromagnetic hot spots in the paper. Simple yet highly efficient and cost effective SERS substrate demonstrated here brings SERS based trace detection closer to real-world applications. We acknowledge the financial support from Center for Materials Innovation at Washington University.

Bioenabled SERS Substrates for Food Safety and Drinking Water Monitoring.

PubMed

Yang, Jing; Rorrer, Gregory L; Wang, Alan X

2015-04-20

We present low-cost bioenabled surface-enhanced Raman scattering (SERS) substrates that can be massively produced in sustainable and eco-friendly methods with significant commercial potentials for the detection of food contamination and drinking water pollution. The sensors are based on diatom frustules with integrated plasmonic nanoparticles. The ultra-high sensitivity of the SERS substrates comes from the coupling between the diatom frustules and Ag nanoparticles to achieve dramatically increased local optical field to enhance the light-matter interactions for SERS sensing. We successfully applied the bioenabled SERS substrates to detect melamine in milk and aromatic compounds in water with sensitivity down to 1μg/L.

Bioenabled SERS substrates for food safety and drinking water monitoring

NASA Astrophysics Data System (ADS)

Yang, Jing; Rorrer, Gregory L.; Wang, Alan X.

2015-05-01

We present low-cost bioenabled surface-enhanced Raman scattering (SERS) substrates that can be massively produced in sustainable and eco-friendly methods with significant commercial potentials for the detection of food contamination and drinking water pollution. The sensors are based on diatom frustules with integrated plasmonic nanoparticles. The ultra-high sensitivity of the SERS substrates comes from the coupling between the diatom frustules and Ag nanoparticles to achieve dramatically increased local optical field to enhance the light-matter interactions for SERS sensing. We successfully applied the bioenabled SERS substrates to detect melamine in milk and aromatic compounds in water with sensitivity down to 1μg/L.

Bioenabled SERS Substrates for Food Safety and Drinking Water Monitoring

PubMed Central

Yang, Jing; Rorrer, Gregory L.; Wang, Alan X.

2016-01-01

We present low-cost bioenabled surface-enhanced Raman scattering (SERS) substrates that can be massively produced in sustainable and eco-friendly methods with significant commercial potentials for the detection of food contamination and drinking water pollution. The sensors are based on diatom frustules with integrated plasmonic nanoparticles. The ultra-high sensitivity of the SERS substrates comes from the coupling between the diatom frustules and Ag nanoparticles to achieve dramatically increased local optical field to enhance the light-matter interactions for SERS sensing. We successfully applied the bioenabled SERS substrates to detect melamine in milk and aromatic compounds in water with sensitivity down to 1μg/L. PMID:26900205

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.

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.

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.

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.

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.

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.

Mutation of katG in a clinical isolate of Mycobacterium tuberculosis: effects on catalase-peroxidase for isoniazid activation.

PubMed

Purkan; Ihsanawati; Natalia, D; Syah, Y M; Retnoningrum, D S; Kusuma, H S

2016-01-01

Mutations in katG gene are often associated with isoniazid (INH) resistance in Mycobacterium tuberculosis strain. This research was perfomed to identify the katG mutation in clinical isolate (L8) that is resistant to INH at 1 μg/ml. In addition to characterize the catalase-peroxidase of KatG L8 and perform the ab initio structural study of the protein to get a more complete understanding in drug activation and the resistan­ce mechanism. The katG gene was cloned and expressed in Escherichia coli, then followed by characterization of catalase-peroxidase of KatG. The structure modelling was performed to know a basis of alterations in enzyme activity. A substitution of A713G that correspond to Asn238Ser replacement was found in the L8 katG. The Asn238Ser modification leads to a decline in the activity of catalase-peroxidase and INH oxidation of the L8 KatG protein. The catalytic efficiency (Kcat/KM) of mutant KatGAsn238Ser respectively decreases to 41 and 52% for catalase and peroxidase. The mutant KatGAsn238Ser also shows a decrease of 62% in INH oxidation if compared to a wild type KatG (KatGwt). The mutant Asn238Ser might cause instability in the substrate binding­ site of KatG, because of removal of a salt bridge connecting the amine group of Asn238 to the carbo­xyl group of Glu233, which presents in KatGwt. The lost of the salt bridge in the substrate binding site in mutant KatGAsn238Ser created changes unfavorable for enzyme activities, which in turn emerge as INH resistan­ce in the L8 isolate of M. tuberculosis.

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.

Role of ser-237 in the substrate specificity of the carbapenem-hydrolyzing class A beta-lactamase Sme-1.

PubMed

Sougakoff, W; Naas, T; Nordmann, P; Collatz, E; Jarlier, V

1999-08-17

The role of the serine residue found at position 237 in the carbapenemase Sme-1 has been investigated by constructing a mutant in which Ser-237 was replaced by an alanine. The S237A mutant showed a catalytic behavior against penicillins and aztreonam very similar to that of Sme-1. By contrast, S237A was characterized by a reduced catalytic efficiency against cephems, such as cephalothin and cephaloridine. In addition, the weak activity of Sme-1 against the cephamycin cefoxitin was hardly detectable with the mutant enzyme. Finally, the Ser-237-->Ala mutation resulted in a marked decrease in catalytic activity against imipenem, showing that Ser-237 contributes to the carbapenemase activity of the class A beta-lactamase Sme-1.

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.

Detection of volatile organic compounds by surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

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

2012-06-01

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

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.

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.

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

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.

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

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.

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.

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.

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.

[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.

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.

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.

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

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.

Role of the conserved amino acids of the 'SDN' loop (Ser130, Asp131 and Asn132) in a class A beta-lactamase studied by site-directed mutagenesis.

PubMed

Jacob, F; Joris, B; Lepage, S; Dusart, J; Frère, J M

1990-10-15

Ser130, Asp131 and Asn132 ('SDN') are highly conserved residues in class A beta-lactamases forming one wall of the active-site cavity. All three residues of the SDN loop in Streptomyces albus G beta-lactamase were modified by site-directed mutagenesis. The mutant proteins were expressed in Streptomyces lividans, purified from culture supernatants and their kinetic parameters were determined for several substrates. Ser130 was substituted by Asn, Ala and Gly. The first modification yielded an almost totally inactive protein, whereas the smaller-side-chain mutants (A and G) retained some activity, but were less stable than the wild-type enzyme. Ser130 might thus be involved in maintaining the structure of the active-site cavity. Mutations of Asp131 into Glu and Gly proved to be highly detrimental to enzyme stability, reflecting significant structural perturbations. Mutation of Asn132 into Ala resulted in a dramatically decreased enzymic activity (more than 100-fold) especially toward cephalosporin substrates, kcat. being the most affected parameter, which would indicate a role of Asn132 in transition-state stabilization rather than in ground-state binding. Comparison of the N132A and the previously described N132S mutant enzymes underline the importance of an H-bond-forming residue at position 132 for the catalytic process.

Parkin-catalyzed Ubiquitin-Ester Transfer Is Triggered by PINK1-dependent Phosphorylation*

PubMed Central

Iguchi, Masahiro; Kujuro, Yuki; Okatsu, Kei; Koyano, Fumika; Kosako, Hidetaka; Kimura, Mayumi; Suzuki, Norihiro; Uchiyama, Shinichiro; Tanaka, Keiji; Matsuda, Noriyuki

2013-01-01

PINK1 and PARKIN are causal genes for autosomal recessive familial Parkinsonism. PINK1 is a mitochondrial Ser/Thr kinase, whereas Parkin functions as an E3 ubiquitin ligase. Under steady-state conditions, Parkin localizes to the cytoplasm where its E3 activity is repressed. A decrease in mitochondrial membrane potential triggers Parkin E3 activity and recruits it to depolarized mitochondria for ubiquitylation of mitochondrial substrates. The molecular basis for how the E3 activity of Parkin is re-established by mitochondrial damage has yet to be determined. Here we provide in vitro biochemical evidence for ubiquitin-thioester formation on Cys-431 of recombinant Parkin. We also report that Parkin forms a ubiquitin-ester following a decrease in mitochondrial membrane potential in cells, and that this event is essential for substrate ubiquitylation. Importantly, the Parkin RING2 domain acts as a transthiolation or acyl-transferring domain rather than an E2-recruiting domain. Furthermore, formation of the ubiquitin-ester depends on PINK1 phosphorylation of Parkin Ser-65. A phosphorylation-deficient mutation completely inhibited formation of the Parkin ubiquitin-ester intermediate, whereas phosphorylation mimics, such as Ser to Glu substitution, enabled partial formation of the intermediate irrespective of Ser-65 phosphorylation. We propose that PINK1-dependent phosphorylation of Parkin leads to the ubiquitin-ester transfer reaction of the RING2 domain, and that this is an essential step in Parkin activation. PMID:23754282

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

The allosteric activator ATP induces a substrate-dependent alteration of the quaternary structure of a mutant aspartate transcarbamoylase impaired in active site closure.

PubMed Central

Baker, D. P.; Fetler, L.; Vachette, P.; Kantrowitz, E. R.

1996-01-01

Aspartate transcarbamoylase from Escherichia coli shows homotropic cooperativity for aspartate as well as heterotropic regulation by nucleotides. Structurally, it consists of two trimeric catalytic subunits and three dimeric regulatory subunits, each chain being comprised of two domains. Glu-50 and Ser-171 are involved in stabilizing the closed conformation of the catalytic chain. Replacement of Glu-50 or Ser-171 by Ala in the holoenzyme has been shown previously to result in marked decreases in the maximal observed specific activity, homotropic cooperativity, and affinity for aspartate (Dembowski NJ, Newton CJ, Kantrowitz ER, 1990, Biochemistry 29:3716-3723; Newton CJ, Kantrowitz ER, 1990, Biochemistry 29:1444-1451). We have constructed a double mutant enzyme combining both mutations. The resulting Glu-50/ser-171-->Ala enzyme is 9-fold less active than the Ser-171-->Ala enzyme, 69-fold less active than the Glu-50-->Ala enzyme, and shows 1.3-fold and 1.6-fold increases in the [S]0.5Asp as compared to the Ser-171-->Ala and Glu-50-->Ala enzymes, respectively. However, the double mutant enzyme exhibits some enhancement of homotropic cooperativity with respect to aspartate, relative to the single mutant enzymes. At subsaturating concentrations of aspartate, the Glu-50/Ser-171 -->Ala enzyme is activated less by ATP than either the Glu-50-->Ala or Ser-171-->Ala enzyme, whereas CTP inhibition is intermediate between that of the two single mutants. As opposed to the wild-type enzyme, the Glu-50/Ser-171 -->Ala enzyme is activated by ATP and inhibited by CTP at saturating concentrations of aspartate. Structural analysis of the Ser-171-->Ala and Glu-50/Ser-171-->Ala enzymes by solution X-ray scattering indicates that both mutants exist in the same T quaternary structure as the wild-type enzyme in the absence of ligands, and in the same R quaternary structure in the presence of saturating N-(phosphonoacetyl)-L-aspartate. However, saturating concentrations of carbamoyl phosphate and succinate are unable to convert a significant fraction of either mutant enzyme population to the R quaternary structure, as has been observed previously for the Glu-50-->Ala enzyme. The curves for both the Ser-171-->Ala and Glu-50/Ser-171-->Ala enzymes obtained in the presence of substoichiometric amounts of PALA are linear combinations of the two extreme T and R states. The structural consequences of nucleotide binding to these two enzymes were also investigated. Most surprisingly, the direction and amplitude of the effect of ATP upon the double mutant enzyme were shown to vary depending upon the substrate analogue used. PMID:8931146

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

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.

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.

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.

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

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

Periodic silver nanocluster arrays over large-area silica nanosphere template as highly sensitive SERS substrate

NASA Astrophysics Data System (ADS)

Hou, Xu; Wang, Qi; Mao, Guoming; Liu, Hao; Yu, Rongdi; Ren, Xiaomin

2018-04-01

Periodic Ag nanocluster arrays for surface enhanced Raman spectroscopy (SERS) were fabricated through magnetron sputtering Ag over a large-area monolayer template which is based on silica (SiO2) nanospheres. High-density nanogaps between the adjacent Ag nanoclusters acted as "hot-spots", making a dominant contribution to the high-performance SERS detection. Moreover, the nanospheres and Ag nanoclusters effectively increased the surface roughness and also enlarged the surface area of as-obtained SERS substrate, which resulted in a further enhancement in Raman signals. As-prepared SERS substrates showed very high sensitivity with the enhancement factor (EF) value of 4.1 × 1012 for Rhodamine 6G (R6G), allowing the corresponding detection limit as low as 10-16 M. Additionally, SERS signal of melamine was still strong even though its concentration was lowered to 10-7 M. Our results show that preparing highly sensitive SERS substrate with periodic Ag nanoclusters over SiO2 nanosphere template is a convenient and promising pathway for chemical and biologic sensing.

Surface-enhanced Raman 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.

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.

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

Synthesis and activity of histidine-containing catalytic peptide dendrimers.

PubMed

Delort, Estelle; Nguyen-Trung, Nhat-Quang; Darbre, Tamis; Reymond, Jean-Louis

2006-06-09

Peptide dendrimers built by iteration of the diamino acid dendron Dap-His-Ser (His = histidine, Ser = Serine, Dap = diamino propionic acid) display a strong positive dendritic effect for the catalytic hydrolysis of 8-acyloxypyrene 1,3,6-trisulfonates, which proceeds with enzyme-like kinetics in aqueous medium (Delort, E.; Darbre, T.; Reymond, J.-L. J. Am. Chem. Soc. 2004, 126, 15642-3). Thirty-two mutants of the original third generation dendrimer A3 ((Ac-His-Ser)8(Dap-His-Ser)4(Dap-His-Ser)2Dap-His-Ser-NH2) were prepared by manual synthesis or by automated synthesis with use of a Chemspeed PSW1100 peptide synthesizer. Dendrimer catalysis was specific for 8-acyloxypyrene 1,3,6-trisulfonates, and there was no activity with other types of esters. While dendrimers with hydrophobic residues at the core and histidine residues at the surface only showed weak activity, exchanging serine residues in dendrimer A3 against alanine (A3A), beta-alanine (A3B), or threonine (A3C) improved catalytic efficiency. Substrate binding was correlated with the total number of histidines per dendrimer, with an average of three histidines per substrate binding site. The catalytic rate constant kcat depended on the placement of histidines within the dendrimers and the nature of the other amino acid residues. The fastest catalyst was the threonine mutant A3C ((Ac-His-Thr)8(Dap-His-Thr)4(Dap-His-Thr)2Dap-His-Thr-NH2), with kcat = 1.3 min(-1), kcat/k(uncat) = 90'000, KM = 160 microM for 8-bytyryloxypyrene 1,3,6-trisulfonate, corresponding to a rate acceleration of 18'000 per catalytic site and a 5-fold improvement over the original sequence A3.

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.

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.

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.

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.

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.

SERS detection of R6G based on a novel graphene oxide/silver nanoparticles/silicon pyramid arrays structure.

PubMed

Zhang, C; Jiang, S Z; Huo, Y Y; Liu, A H; Xu, S C; Liu, X Y; Sun, Z C; Xu, Y Y; Li, Z; Man, B Y

2015-09-21

We present a novel surface-enhanced Raman scattering (SERS) substrate based on graphene oxide/silver nanoparticles/silicon pyramid arrays structure (GO/Ag/PSi). The SERS behaviors are discussed and compared by the detection of R6G. Based on the contrast experiments with PSi, GO/PSi, Ag/PSi and GO/AgA/PSi as SERS substrate, the perfect bio-compatibility, good homogeneity and chemical stability were confirmed. We also calculated the electric field distributions using Finite-difference time-domain (FDTD) analysis to further understand the GO/Ag/PSi structure as a perfect SERS platform. These experimental and theoretical results imply that the GO/Ag/PSi with regular pyramids array is expected to be an effective substrate for label-free sensitive SERS detections in areas of medicine, food safety and biotechnology.

Protein phosphatase 2Cm is a critical regulator of branched-chain amino acid catabolism in mice and cultured cells.

PubMed

Lu, Gang; Sun, Haipeng; She, Pengxiang; Youn, Ji-Youn; Warburton, Sarah; Ping, Peipei; Vondriska, Thomas M; Cai, Hua; Lynch, Christopher J; Wang, Yibin

2009-06-01

The branched-chain amino acids (BCAA) are essential amino acids required for protein homeostasis, energy balance, and nutrient signaling. In individuals with deficiencies in BCAA, these amino acids can be preserved through inhibition of the branched-chain-alpha-ketoacid dehydrogenase (BCKD) complex, the rate-limiting step in their metabolism. BCKD is inhibited by phosphorylation of its E1alpha subunit at Ser293, which is catalyzed by BCKD kinase. During BCAA excess, phosphorylated Ser293 (pSer293) becomes dephosphorylated through the concerted inhibition of BCKD kinase and the activity of an unknown intramitochondrial phosphatase. Using unbiased, proteomic approaches, we have found that a mitochondrial-targeted phosphatase, PP2Cm, specifically binds the BCKD complex and induces dephosphorylation of Ser293 in the presence of BCKD substrates. Loss of PP2Cm completely abolished substrate-induced E1alpha dephosphorylation both in vitro and in vivo. PP2Cm-deficient mice exhibited BCAA catabolic defects and a metabolic phenotype similar to the intermittent or intermediate types of human maple syrup urine disease (MSUD), a hereditary disorder caused by defects in BCKD activity. These results indicate that PP2Cm is the endogenous BCKD phosphatase required for nutrient-mediated regulation of BCKD activity and suggest that defects in PP2Cm may be responsible for a subset of human MSUD.

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.

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

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

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.

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.

The crystal structure of MCAT from Mycobacterium tuberculosis reveals three new catalytic models.

PubMed

Li, Zexuan; Huang, Yishu; Ge, Jing; Fan, Hang; Zhou, Xiaohong; Li, Shentao; Bartlam, Mark; Wang, Honghai; Rao, Zihe

2007-08-24

The malonyl coenzyme A (CoA)-acyl carrier protein (ACP) transacylase (MCAT) plays a key role in cell wall biosynthesis in Mycobacterium tuberculosis and other bacteria. The M. tuberculosis MCAT (MtMCAT) is encoded by the FabD gene and catalyzes the transacylation of malonate from malonyl-CoA to holo-ACP. Malonyl-ACP is the substrate in fatty acid biosynthesis and is a by-product of the transacylation reaction. This ability for fatty acid biosynthesis enables M. tuberculosis to survive in hostile environments, and thus understanding the mechanism of biosynthesis is important for the design of new anti-tuberculosis drugs. The 2.3 A crystal structure of MtMCAT reported here shows that its catalytic mechanism differs from those of ScMCAT and EcMCAT, whose structures have previously been determined. In MtMCAT, the C(beta)-O(gamma) bond of Ser91 turns upwards, resulting in a different orientation and thus an overall change of the active pocket compared to other known MCAT enzymes. We identify three new nucleophilic attack chains from the MtMCAT structure: His90-Ser91, Asn155-Wat6-Ser91 and Asn155-His90-Ser91. Enzyme activity assays show that His90A, Asn155A and His90A-Asn155A mutants all have substantially reduced MCAT activity, indicating that M. tuberculosis MCAT supports a unique means of proton transfer. Furthermore, His194 cannot form part of a His-Ser catalytic dyad and only stabilizes the substrate. This new discovery should provide a deeper insight into the catalytic mechanisms of MCATs.

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.

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.

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

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.

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

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.

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.

Pharmacophore, QSAR, and binding mode studies of substrates of human cytochrome P450 2D6 (CYP2D6) using molecular docking and virtual mutations and an application to chinese herbal medicine screening.

PubMed

Mo, Sui-Lin; Liu, Wei-Feng; Li, Chun-Guang; Zhou, Zhi-Wei; Luo, Hai-Bin; Chew, Helen; Liang, Jun; Zhou, Shu-Feng

2012-07-01

The highly polymorphic human cytochrome P450 2D6 (CYP2D6) metabolizes about 25% of currently used drugs. In this study, we have explored the interaction of a large number of substrates (n = 120) with wild-type and mutated CYP2D6 by molecular docking using the CDOCKER module. Before we conducted the molecular docking and virtual mutations, the pharmacophore and QSAR models of CYP2D6 substrates were developed and validated. Finally, we explored the interaction of a traditional Chinese herbal formula, Fangjifuling decoction, with CYP2D6 by virtual screening. The optimized pharmacophore model derived from 20 substrates of CYP2D6 contained two hydrophobic features and one hydrogen bond acceptor feature, giving a relevance ratio of 76% when a validation set of substrates were tested. However, our QSAR models gave poor prediction of the binding affinity of substrates. Our docking study demonstrated that 117 out of 120 substrates could be docked into the active site of CYP2D6. Forty one out of 117 substrates (35.04%) formed hydrogen bonds with various active site residues of CYP2D6 and 53 (45.30%) substrates formed a strong π-π interaction with Phe120 (53/54), with only carvedilol showing π-π interaction with Phe483. The active site residues involving hydrogen bond formation with substrates included Leu213, Lys214, Glu216, Ser217, Gln244, Asp301, Ser304, Ala305, Phe483, and Phe484. Furthermore, the CDOCKER algorithm was further applied to study the impact of mutations of 28 active site residues (mostly non-conserved) of CYP2D6 on substrate binding modes using five probe substrates including bufuralol, debrisoquine, dextromethorphan, sparteine, and tramadol. All mutations of the residues examined altered the hydrogen bond formation and/or aromatic interactions, depending on the probe used in molecular docking. Apparent changes of the binding modes have been observed with the Glu216Asp and Asp301Glu mutants. Overall, 60 compounds out of 130 from Fangjifuling decoction matched our pharmacophore model for CYP2D6 substrates. Fifty four out of these 60 compounds could be docked into the active site of CYP2D6 and 24 of 54 compounds formed hydrogen bonds with Glu216, Asp301, Ser304, and Ala305 in CYP2D6. These results have provided further insights into the factors that determining the binding modes of substrates to CYP2D6. Screening of high-affinity ligands for CYP2D6 from herbal formula using computational models is a useful approach to identify potential herb-drug interactions.

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.

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.

Synthesis of silver/silver chloride/graphene oxide composite and its surface-enhanced Raman scattering activity and self-cleaning property

NASA Astrophysics Data System (ADS)

Zhao, Nan; Fei, Xiao; Cheng, Xiaonong; Yang, Juan

2017-09-01

Recently, silver nanoparticles decorated with graphene and graphene oxide (GO) sheets can be employed as surface-enhanced Raman scattering (SERS) substrates. However, their SERS activity on macromolecular compound detection is all one-time process. In order to solve this issue and decrease the cost of routine SERS detection, silver/silver chloride (Ag/AgCl) with photocatalytic activity under visible light was introduced. In this study, a novel, simple and clean approach is carried out for synthesis of the Ag/AgCl/GO composite. The Ag/AgCl colloidal solution is obtained by hydrothermal method and then mixed with GO solution to obtain the Ag/AgCl/GO composite using a facile electrostatic self-assembly method. Results showed that the Ag/AgCl/GO composite has the optimized SERS activity to Rhodamine 6G molecules with the maximum enhancement factor value of 3.8×107. Furthermore, the Ag/AgCl particles with high efficient and stable photocatalytic activity under visible light lead to an outstanding self-cleaning property of the Ag/AgCl/GO composite.

The synthesis of biocompatible and SERS-active gold nanoparticles using chitosan.

PubMed

Potara, Monica; Maniu, Dana; Astilean, Simion

2009-08-05

In this study we present a clean, nontoxic, environmentally friendly synthesis procedure to generate a large variety of gold nanoparticles (GNPs) by using chitosan, a biocompatible, biodegradable, natural polymer, as reducing and stabilizing agent. The formation of gold-chitosan nanocomposites was characterized by UV-vis absorption spectroscopy, transmission electron microscopy (TEM), x-ray diffraction (XRD) and Raman spectroscopy. The results show that the reaction temperature plays a crucial role in controlling the size, shape and crystalline structure of GNPs. In addition, it is demonstrated that chitosan can perform as a scaffold for the assembly of GNPs, which were successfully applied as substrate for surface-enhanced Raman scattering (SERS). To test the SERS activity, a relevant biological molecule--tryptophan--was adopted as the analyte.

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.

Surface modification of nanoporous alumina layers by deposition of Ag nanoparticles. Effect of alumina pore diameter on the morphology of silver deposit and its influence on SERS activity

NASA Astrophysics Data System (ADS)

Pisarek, Marcin; Nowakowski, Robert; Kudelski, Andrzej; Holdynski, Marcin; Roguska, Agata; Janik-Czachor, Maria; Kurowska-Tabor, Elżbieta; Sulka, Grzegorz D.

2015-12-01

Self-organized Al2O3 nanoporous/nanotubular (Al2O3-NP) oxide layers decorated with silver nanoparticles (Ag-NPs) exhibiting specific properties may serve as attractive SERS substrates for investigating the interactions between an adsorbate and adsorbent, or as stable platforms for detecting various organic compounds. This article presents the influence of the size of the alumina nanopores with a deposit of silver nanoparticles obtained by the magnetron sputtering technique on the morphology of silver film. Moreover, the effect of pore diameter on the intensity of SERS spectra in Ag-NPs/Al2O3-NP/Al composites has also been estimated. For such investigations we used pyridine as a probe molecule, since it has a large cross-section for Raman scattering. To characterize the morphology of the composite oxide layer Ag-NPs/Al2O3-NP/Al, before and after deposition of Ag-NPs by PVD methods (Physical Vapor Deposition), we used scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface analytical technique of surface-enhanced Raman spectroscopy (SERS) was used to investigate the surface activity of the composite. The results obtained show that, for a carefully controlled amount of Ag (0.020 mg/cm2 - deposited on the top of alumina nanopores whose average size varies from ∼86 nm up to ∼320 nm) in the composites investigated, pore size significantly affects SERS enhancement. We obtained distinctly higher intensities of SERS spectra for substrates with an Ag-NPs deposit having a larger diameter of the alumina nanopores. AFM results suggest that both the lateral and perpendicular distribution of Ag-NPs within and on the top of the largest pores is responsible for the highest SERS activity of the resulting Ag-NPs/Al2O3-NP/Al composite layer, since it produces a variety of cavities and slits which function as resonators for the adsorbed molecules. The Ag-NPs/MeOx-NP/Me composite layers obtained ensure a good reproducibility of the SERS measurements.

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.

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.

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.

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.

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.

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.

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.

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.

Biosynthesis of pteridines. Reaction mechanism of GTP cyclohydrolase I.

PubMed

Rebelo, Jorge; Auerbach, Günter; Bader, Gerd; Bracher, Andreas; Nar, Herbert; Hösl, Cornelia; Schramek, Nicholas; Kaiser, Johannes; Bacher, Adelbert; Huber, Robert; Fischer, Markus

2003-02-14

GTP cyclohydrolase I catalyses the hydrolytic release of formate from GTP followed by cyclization to dihydroneopterin triphosphate. The enzymes from bacteria and animals are homodecamers containing one zinc ion per subunit. Replacement of Cys110, Cys181, His112 or His113 of the enzyme from Escherichia coli by serine affords catalytically inactive mutant proteins with reduced capacity to bind zinc. These mutant proteins are unable to convert GTP or the committed reaction intermediate, 2-amino-5-formylamino-6-(beta-ribosylamino)-4(3H)-pyrimidinone 5'-triphosphate, to dihydroneopterin triphosphate. The crystal structures of GTP complexes of the His113Ser, His112Ser and Cys181Ser mutant proteins determined at resolutions of 2.5A, 2.8A and 3.2A, respectively, revealed the conformation of substrate GTP in the active site cavity. The carboxylic group of the highly conserved residue Glu152 anchors the substrate GTP, by hydrogen bonding to N-3 and to the position 2 amino group. Several basic amino acid residues interact with the triphosphate moiety of the substrate. The structure of the His112Ser mutant in complex with an undefined mixture of nucleotides determined at a resolution of 2.1A afforded additional details of the peptide folding. Comparison between the wild-type and mutant enzyme structures indicates that the catalytically active zinc ion is directly coordinated to Cys110, Cys181 and His113. Moreover, the zinc ion is complexed to a water molecule, which is in close hydrogen bond contact to His112. In close analogy to zinc proteases, the zinc-coordinated water molecule is suggested to attack C-8 of the substrate affording a zinc-bound 8R hydrate of GTP. Opening of the hydrated imidazole ring affords a formamide derivative, which remains coordinated to zinc. The subsequent hydrolysis of the formamide motif has an absolute requirement for zinc ion catalysis. The hydrolysis of the formamide bond shows close mechanistic similarity with peptide hydrolysis by zinc proteases.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

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.

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.

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.

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.

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.

Phosphorylation and mutations of Ser(16) in human phenylalanine hydroxylase. Kinetic and structural effects.

PubMed

Miranda, Frederico Faria; Teigen, Knut; Thórólfsson, Matthías; Svebak, Randi M; Knappskog, Per M; Flatmark, Torgeir; Martínez, Aurora

2002-10-25

Phosphorylation of phenylalanine hydroxylase (PAH) at Ser(16) by cyclic AMP-dependent protein kinase is a post-translational modification that increases its basal activity and facilitates its activation by the substrate l-Phe. So far there is no structural information on the flexible N-terminal tail (residues 1-18), including the phosphorylation site. To get further insight into the molecular basis for the effects of phosphorylation on the catalytic efficiency and enzyme stability, molecular modeling was performed using the crystal structure of the recombinant rat enzyme. The most probable conformation and orientation of the N-terminal tail thus obtained indicates that phosphorylation of Ser(16) induces a local conformational change as a result of an electrostatic interaction between the phosphate group and Arg(13) as well as a repulsion by Glu(280) in the loop at the entrance of the active site crevice structure. The modeled reorientation of the N-terminal tail residues (Met(1)-Leu(15)) on phosphorylation is in agreement with the observed conformational change and increased accessibility of the substrate to the active site, as indicated by circular dichroism spectroscopy and the enzyme kinetic data for the full-length phosphorylated and nonphosphorylated human PAH. To further validate the model we have prepared and characterized mutants substituting Ser(16) with a negatively charged residue and found that S16E largely mimics the effects of phosphorylation of human PAH. Both the phosphorylated enzyme and the mutants with acidic side chains instead of Ser(16) revealed an increased resistance toward limited tryptic proteolysis and, as indicated by circular dichroism spectroscopy, an increased content of alpha-helical structure. In agreement with the modeled structure, the formation of an Arg(13) to Ser(16) phosphate salt bridge and the conformational change of the N-terminal tail also explain the higher stability toward limited tryptic proteolysis of the phosphorylated enzyme. The results obtained with the mutant R13A and E381A further support the model proposed for the molecular mechanism for the activation of the enzyme by phosphorylation.

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.

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.

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

Alkaline phosphatase labeled SERS active sandwich immunoassay for detection of Escherichia coli

NASA Astrophysics Data System (ADS)

Bozkurt, Akif Goktug; Buyukgoz, Guluzar Gorkem; Soforoglu, Mehmet; Tamer, Ugur; Suludere, Zekiye; Boyaci, Ismail Hakki

2018-04-01

In this study, a sandwich immunoassay method utilizing enzymatic activity of alkaline phosphatase (ALP) on 5-bromo-4-chloro-3-indolyl phosphate (BCIP) for Escherichia coli (E. coli) detection was developed using surface enhanced Raman spectroscopy (SERS). For this purpose, spherical magnetic gold coated core-shell nanoparticles (MNPs-Au) and rod shape gold nanoparticles (Au-NRs) were synthesized and modified for immunomagnetic separation (IMS) of E. coli from the solution. In order to specify the developed method to ALP activity, Au-NRs were labeled with this enzyme. After successful construction of the immunoassay, BCIP substrate was added to produce the SERS-active product; 5-bromo-4-chloro-3-indole (BCI). A good linearity (R2 = 0.992) was established between the specific SERS intensity of BCI at 600 cm- 1 and logarithmic E. coli concentration in the range of 1.7 × 101-1.7 × 106 cfu mL- 1. LOD and LOQ values were also calculated and found to be 10 cfu mL- 1 and 30 cfu mL- 1, respectively.

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.

Multifunctional paper strip based on GO-veiled Ag nanoparticles with highly SERS sensitive and deliverable properties for high-performance molecular detection.

PubMed

Yang, Cheng; Xu, Yuanyuan; Wang, Minghong; Li, Tianming; Huo, Yanyan; Yang, Chuanxi; Man, Baoyuan

2018-04-16

The development of paper-based SERS substrates that can allow multi-component detection in real-word scenarios is of great value for applications in molecule detection under complex conditions. Here, a multifunctional SERS-based paper sensing substrate has been developed through the uniform patterning of high-density arrays of GO-isolated Ag nanoparticles on the hydrophilic porous cellulose paper strip (GO@AgNP@paper). Wet-chemical synthesis was used to provide the cover of SERS hot spots on any part of the paper, not just limited surface deposition. In virtue of the inherent ability of paper to deliver analytes by the capillary force, the detection ability of the GO@AgNP@paper substrate was greatly promoted, allowing as low as 10 -19 M R6G detection from microliter-volume (50 μL) samples. For the components with different polarity, the paper substrate can be used as an all-in-one machine to achieve the integration of separation and high-sensitive detection for ultralow mixture components, which improves the practical application value of SERS-based paper devices.

Sensing of p53 and EGFR Biomarkers Using High Efficiency SERS Substrates

PubMed Central

Owens, Peter; Phillipson, Nigel; Perumal, Jayakumar; O’Connor, Gerard M.; Olivo, Malini

2015-01-01

In this paper we describe a method for the determination of protein concentration using Surface Enhanced Raman Resonance Scattering (SERRS) immunoassays. We use two different Raman active linkers, 4-aminothiophenol and 6-mercaptopurine, to bind to a high sensitivity SERS substrate and investigate the influence of varying concentrations of p53 and EGFR on the Raman spectra. Perturbations in the spectra are due to the influence of protein–antibody binding on Raman linker molecules and are attributed to small changes in localised mechanical stress, which are enhanced by SERRS. These influences are greatest for peaks due to the C-S functional group and the Full Width Half Maximum (FWHM) was found to be inversely proportional to protein concentration. PMID:26516922

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.

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.

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.

In situ Silver Spot Preparation and on-Plate Surface-Enhanced Raman Scattering Detection in Thin Layer Chromatography Separation

NASA Astrophysics Data System (ADS)

Herman, K.; Mircescu, N. E.; Szabo, L.; Leopold, L. F.; Chiş, V.; Leopold, N.

2013-05-01

An improved approach for surface-enhanced Raman scattering (SERS) detection of mixture constituents after thin layer chromatography (TLC) separation is presented. A SERS active silver substrate was prepared under open air conditions, directly on the thin silica film by photo-reduction of silver nitrate, allowing the detection of binary mixtures of cresyl violet, bixine, crystal violet, and Cu(II) complex of 4-(2-pyridylazo)resorcinol. The recorded SERS spectrum provides a unique spectral fingerprint for each molecule; therefore the use of analyte standards is avoided, thus rendering the presented procedure advantageous compared to the conventional detection methodology in TLC.

Rapid Detection of Melamine in Tap Water and Milk Using Conjugated "One-Step" Molecularly Imprinted Polymers-Surface Enhanced Raman Spectroscopic Sensor.

PubMed

Hu, Yaxi; Lu, Xiaonan

2016-05-01

An innovative "one-step" sensor conjugating molecularly imprinted polymers and surface enhanced Raman spectroscopic-active substrate (MIPs-SERS) was investigated for simultaneous extraction and determination of melamine in tap water and milk. This sensor was fabricated by integrating silver nanoparticles (AgNPs) with MIPs synthesized by bulk polymerization of melamine (template), methacrylic acid (functional monomer), ethylene glycol dimethacrylate (cross-linking agent), and 2,2'-azobisisobutyronitrile (initiator). Static and kinetic adsorption tests validated the specific affinity of MIPs-AgNPs to melamine and the rapid adsorption equilibration rate. Principal component analysis segregated SERS spectral features of tap water and milk samples with different melamine concentrations. Partial least squares regression models correlated melamine concentrations in tap water and skim milk with SERS spectral features. The limit of detection (LOD) and limit of quantification (LOQ) of melamine in tap water were determined as 0.0019 and 0.0064 mmol/L, while the LOD and LOQ were 0.0165 and 0.055 mmol/L for the determination of melamine in skim milk. However, this sensor is not ideal to quantify melamine in tap water and skim milk. By conjugating MIPs with SERS-active substrate (that is, AgNPs), reproducibility of SERS spectral features was increased, resulting in more accurate detection. The time required to determine melamine in tap water and milk were 6 and 25 min, respectively. The low LOD, LOQ, and rapid detection confirm the potential of applying this sensor for accurate and high-throughput detection of melamine in tap water and milk. © 2016 Institute of Food Technologists®

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.

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.

Ubiquitin phosphorylated at Ser57 hyper-activates parkin.

PubMed

George, Susanna; Wang, Sabrina M; Bi, Yumin; Treidlinger, Margot; Barber, Kathryn R; Shaw, Gary S; O'Donoghue, Patrick

2017-11-01

Malfunction of the ubiquitin (Ub) E3 ligase, parkin, leads to defects in mitophagy and protein quality control linked to Parkinson's disease. Parkin activity is stimulated by phosphorylation of Ub at Ser65 (pUb S65 ). Since the upstream kinase is only known for Ser65 (PINK1), the biochemical function of other phosphorylation sites on Ub remain largely unknown. We used fluorescently labelled and site-specifically phosphorylated Ub substrates to quantitatively relate the position and stoichiometry of Ub phosphorylation to parkin activation. Fluorescence measurements show that pUb S65 -stimulated parkin is 5-fold more active than auto-inhibited and un-stimulated parkin, which catalyzes a basal level of auto-ubiquitination. We consistently observed a low but detectable level of parkin activity with pUb S12 . Strikingly, pUb S57 hyper-activates parkin, and our data demonstrate that parkin is able to selectively synthesize poly-pUb S57 chains, even when 90% of the Ub in the reaction is un-phosphorylated. We further found that parkin ubiquitinates its physiological substrate Miro-1 with chains solely composed of pUb S65 and more efficiently with pUb S57 chains. Parkin hyper-activation by pUb S57 demonstrates the first PINK1-independent route to active parkin, revealing the roles of multiple ubiquitin phosphorylation sites in governing parkin stimulation and catalytic activity. This article is part of a Special Issue entitled "Biochemistry of Synthetic Biology - Recent Developments" Guest Editor: Dr. Ilka Heinemann and Dr. Patrick O'Donoghue. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

Combination of inverted pyramidal nanovoid with silver nanoparticles to obtain further enhancement and its detection for ricin

NASA Astrophysics Data System (ADS)

Wang, Meng; Wang, Bin; Wu, Shixuan; Guo, Tingke; Li, Haoyu; Guo, Zhaoqing; Wu, Junhua; Jia, Peiyuan; Wang, Yuxia; Xu, Xiaoxuan; Wang, Yufang; Zhang, Cunzhou

2015-02-01

We have obtained the surface-enhanced Raman scattering substrate by depositing silver nanoparticles on the surface of the inverted pyramidal nanovoid in order to improve the enhance effects. Experimental results showed that the combined substrate exhibited greater enhancement than the nanovoid substrate or nanoparticles. In order to test the SERS activity of the combined substrates, Rh6G and ricin toxin were used as Raman probes. Finite element method was employed to simulate electric field and induced charge distribution of the substrates, which have been used to explore the interaction between nanoparticles and nanovoid as well as mechanism of the great enhancement.

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.

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

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.

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.

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.

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.

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

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

Surface-enhanced Raman scattering active gold nanoparticle/nanohole arrays fabricated through electron beam lithography

NASA Astrophysics Data System (ADS)

Wu, Tsunghsueh; Lin, Yang-Wei

2018-03-01

Effective surface-enhanced Raman scattering (SERS)-active substrates from gold nanoparticle and gold nanohole arrays were successfully fabricated through electron beam lithography with precise computer-aided control of the unit size and intergap distance. Their SERS performance was evaluated using 4-mercaptobenzoic acid (4-MBA). These gold arrays yielded strong SERS signals under 785 nm laser excitation. The enhancement factors for 4-MBA molecules on the prepared gold nanoparticle and nanohole arrays maxed at 1.08 × 107 and 8.61 × 106, respectively. The observed increase in SERS enhancement was attributed to the localized surface plasmon resonance (LSPR) wavelength shifting toward the near-infrared regime when the gold nanohole diameter increased, in agreement with the theoretical prediction in this study. The contribution of LSPR to the Raman enhancement from nanohole arrays deposited on fluorine-doped tin oxide glass was elucidated by comparing SERS and transmission spectra. This simple fabrication procedure, which entails employing electron beam lithography and the controllability of the intergap distance, suggests highly promising uses of nanohole arrays as functional components in sensing and photonic devices.

Sodium Chloride Crystal-Induced SERS Platform for Controlled Highly Sensitive Detection of Illicit Drugs.

PubMed

Yu, Borong; Li, Pan; Zhou, Binbin; Tang, Xianghu; Li, Shaofei; Yang, Liangbao

2018-04-03

A sodium chloride crystal-driven spontaneous 'hot spot' structure was demonstrated as a SERS-active platform, to get reproducible SERS signals, and eliminate the need for mapping large areas, in comparison with solution phase testing. During the process of solvent evaporation, the crystals produced induced silver aggregates to assemble around themselves. The micro-scale crystals can also act as a template to obtain an optical position, such that the assembled hot area is conveniently located during SERS measurements. More importantly, the chloride ions added in colloids can also replace the citrate and on the surface of the silver sol, and further decrease the background interference. High quality SERS spectra from heroin, methamphetamine (MAMP), and cocaine have been obtained on the crystal-driven hot spot structure with high sensitivity and credible reproducibility. This approach can not only bring the nanoparticles to form plasmonic hot spots in a controlled way, and thus provide high sensitivity, but also potentially be explored as an active substrate for label-free detection of other illicit drugs or additives. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

SERS spectral study of HAuCl4-cysteine nanocatalytic reaction and its application for detection of heparin sodium with label-free VB4r molecular probe

NASA Astrophysics Data System (ADS)

Wang, Xiaoliang; Jiang, Caina; Qin, Yanna; Peng, Yutao; Wen, Guiqing; Liang, Aihui; Jiang, Zhiliang

2017-04-01

In the presence of nanocatalyst, L-cysteine reduce HAuCl4 rapidly to form gold nanoparticles (AuNP), and a quick nanocatalytic preparation procedure was established for Au/AuNP sol with highly active surface enhanced Raman scattering (SERS) effect and good stability. The nanoreaction was also studied by absorption, resonance Rayleigh scattering (RRS), transmission electron microscopy (TEM) and energy spectra. In the selected conditions, the analyte heparin sodium (HS) could react with victoria blue 4 R (VB4r) to form associated complexes which have very weak SERS effect to make the SERS signals decrease. The SERS signals at 1617 cm-1 reduced linearly with HS concentration increasing. Upon addition of FeCl3, it hydrolyzed to form stable Fe(OH)3 sol platform that carried SERS active Au/AuNPs to enhance the sensitivity. Accordingly, we established a SERS quantitative analysis method in the sol substrate of Fe(OH)3-Au/AuNPs, with a linear range of 0.5-75 ng/mL HS and a detection limit of 0.2 ng/mL. HS in real samples was determined, with a relative standard deviation of 2.65-7.63% and a recovery of 99.3-101%.

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.

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

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.

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

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.

Surface-enhanced Raman spectroscopy on litographically constructed microelectrodes

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

Zhelyaskov, V.R.; Milne, E.T.; Weldon, M.K.

1995-12-31

A novel silicon substrate microelectrode array has been demonstrated to function as a surface-enhanced Raman Spectroscopy (SERS) microelectrode. SERS from adenosine and pyridine down to 10 mM concentration on silver coated iridium and gold microelectrode arrays have been observed with excitation at 532 nm and 633 nm correspondingly. Ag/AgCl reference electrode and platinum or integrated on the microelectrode iridium counter electrodes were used. Owing to the small area of the activated sites on the microelectrode (10 mm x 15 mm) the SERS signal exhibited a strong laser power dependence. The optimal laser power on the activated site was shown tomore » be in the order of x 100 mW. Good quality SERS spectra were recorded with exposure times of 10s and less. The small size of the electrodes makes them promising for studies in confined spaces. This includes potential applications as capillary electrophoreses detectors and probes of chemistry of biological organisms. A work on detection of lipids adhered to self-organized monolayers (SAM)s of alkanethiols on the activated microelectrodes is in progress.« less

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.

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.

SPAK kinase is a substrate and target of PKCθ in T-cell receptor-induced AP-1 activation pathway

PubMed Central

Li, Yingqiu; Hu, Junru; Vita, Randi; Sun, Binggang; Tabata, Hiroki; Altman, Amnon

2004-01-01

Protein kinase C-θ (PKCθ) plays an important role in T-cell activation via stimulation of AP-1 and NF-κB. Here we report the isolation of SPAK, a Ste20-related upstream mitogen-activated protein kinase (MAPK), as a PKCθ-interacting kinase. SPAK interacted with PKCθ (but not with PKCα) via its 99 COOH-terminal residues. TCR/CD28 costimulation enhanced this association and stimulated the catalytic activity of SPAK. Recombinant SPAK was phosphorylated on Ser-311 in its kinase domain by PKCθ, but not by PKCα. The magnitude and duration of TCR/CD28-induced endogenous SPAK activation were markedly impaired in PKCθ-deficient T cells. Transfected SPAK synergized with constitutively active PKCθ to activate AP-1, but not NF-κB. This synergistic activity, as well as the receptor-induced SPAK activation, required the PKCθ-interacting region of SPAK, and Ser-311 mutation greatly reduced these activities of SPAK. Conversely, a SPAK-specific RNAi or a dominant-negative SPAK mutant inhibited PKCθ- and TCR/CD28-induced AP-1, but not NF-κB, activation. These results define SPAK as a substrate and target of PKCθ in a TCR/CD28-induced signaling pathway leading selectively to AP-1 (but not NF-κB) activation. PMID:14988727

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.

Dissecting the total transition state stabilization provided by amino acid side chains at orotidine 5'-monophosphate decarboxylase: a two-part substrate approach.

PubMed

Barnett, Shonoi A; Amyes, Tina L; Wood, Bryant M; Gerlt, John A; Richard, John P

2008-07-29

Kinetic analysis of decarboxylation catalyzed by S154A, Q215A, and S154A/Q215A mutant yeast orotidine 5'-monophosphate decarboxylases with orotidine 5'-monophosphate (OMP) and with a truncated nucleoside substrate (EO) activated by phosphite dianion shows (1) the side chain of Ser-154 stabilizes the transition state through interactions with the pyrimidine rings of OMP or EO, (2) the side chain of Gln-215 interacts with the phosphodianion group of OMP or with phosphite dianion, and (3) the interloop hydrogen bond between the side chains of Ser-154 and Gln-215 orients the amide side chain of Gln-215 to interact with the phosphodianion group of OMP or with phosphite dianion.

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.

SUMO chain formation relies on the amino-terminal region of SUMO-conjugating enzyme and has dedicated substrates in plants

PubMed Central

Tomanov, Konstantin; Nehlin, Lilian; Ziba, Ionida

2018-01-01

The small ubiquitin-related modifier (SUMO) conjugation apparatus usually attaches single SUMO moieties to its substrates, but SUMO chains have also been identified. To better define the biochemical requirements and characteristics of SUMO chain formation, mutations in surface-exposed Lys residues of Arabidopsis SUMO-conjugating enzyme (SCE) were tested for in vitro activity. Lys-to-Arg changes in the amino-terminal region of SCE allowed SUMO acceptance from SUMO-activating enzyme and supported substrate mono-sumoylation, but these mutations had significant effects on SUMO chain assembly. We found no indication that SUMO modification of SCE promotes chain formation. A substrate was identified that is modified by SUMO chain addition, showing that SCE can distinguish substrates for either mono-sumoylation or SUMO chain attachment. It is also shown that SCE with active site Cys mutated to Ser can accept SUMO to form an oxyester, but cannot transfer this SUMO moiety onto substrates, explaining a previously known dominant negative effect of this mutation. PMID:29133528

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.

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.

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.

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

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

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

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.

Rapid and sensitive detection of malachite green in aquaculture water by electrochemical preconcentration and surface-enhanced Raman scattering.

PubMed

Xu, Kai-Xuan; Guo, Mei-Hong; Huang, Yu-Ping; Li, Xiao-Dong; Sun, Jian-Jun

2018-04-01

A highly sensitive and rapid method of in-situ surface-enhanced Raman spectroscopy (SERS) combining with electrochemical preconcentration (EP) in detecting malachite green (MG) in aquaculture water was established. Ag nanoparticles (AgNPs) were synthesized and spread onto the surface of gold electrodes after centrifuging to produce SERS-active substrates. After optimizing the pH values, preconcentration potentials and times, in-situ EP-SERS detection was carried out. A sensitive and rapid analysis of the low-concentration MG was accomplished within 200s and the limit of detection was 2.4 × 10 -16 M. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface enhanced Raman spectroscopy (SERS) from a molecule adsorbed on a nanoscale silver particle cluster in a holographic plate

NASA Astrophysics Data System (ADS)

Jusinski, Leonard E.; Bahuguna, Ramen; Das, Amrita; Arya, Karamjeet

2006-02-01

Surface enhanced Raman spectroscopy has become a viable technique for the detection of single molecules. This highly sensitive technique is due to the very large (up to 14 orders in magnitude) enhancement in the Raman cross section when the molecule is adsorbed on a metal nanoparticle cluster. We report here SERS (Surface Enhanced Raman Spectroscopy) experiments performed by adsorbing analyte molecules on nanoscale silver particle clusters within the gelatin layer of commercially available holographic plates which have been developed and fixed. The Ag particles range in size between 5 - 30 nanometers (nm). Sample preparation was performed by immersing the prepared holographic plate in an analyte solution for a few minutes. We report here the production of SERS signals from Rhodamine 6G (R6G) molecules of nanomolar concentration. These measurements demonstrate a fast, low cost, reproducible technique of producing SERS substrates in a matter of minutes compared to the conventional procedure of preparing Ag clusters from colloidal solutions. SERS active colloidal solutions require up to a full day to prepare. In addition, the preparations of colloidal aggregates are not consistent in shape, contain additional interfering chemicals, and do not generate consistent SERS enhancement. Colloidal solutions require the addition of KCl or NaCl to increase the ionic strength to allow aggregation and cluster formation. We find no need to add KCl or NaCl to create SERS active clusters in the holographic gelatin matrix. These holographic plates, prepared using simple, conventional procedures, can be stored in an inert environment and preserve SERS activity after several weeks subsequent to preparation.

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.

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.

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.

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.

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.

Akt-RSK-S6-kinase Signaling Networks Activated by Oncogenic Receptor Tyrosine Kinases

PubMed Central

Moritz, Albrecht; Li, Yu; Guo, Ailan; Villén, Judit; Wang, Yi; MacNeill, Joan; Kornhauser, Jon; Sprott, Kam; Zhou, Jing; Possemato, Anthony; Ren, Jian Min; Hornbeck, Peter; Cantley, Lewis C.; Gygi, Steven P.; Rush, John; Comb, Michael J.

2011-01-01

Receptor tyrosine kinases (RTKs) activate pathways mediated by serine/threonine (Ser/Thr) kinases such as the PI3K (phosphatidylinositol 3-kinase)-Akt pathway, the Ras-MAPK (mitogen-activated protein kinase)-RSK pathway, and the mTOR (mammalian target of rapamycin)-p70 S6 pathway that control important aspects of cell growth, proliferation, and survival. The Akt, RSK, and p70 S6 family of protein kinases transmit signals by phosphorylating substrates on a RxRxxS/T motif. Here, we developed a large-scale proteomic approach to identify over 200 substrates of this kinase family in cancer cell lines driven by the c-Met, epidermal growth factor receptor (EGFR), or platelet-derived growth factor receptor a (PDGFRα) RTKs. We identified a subset of proteins with RxRxxS/T sites for which phosphorylation was decreased by RTKIs as well as by inhibitors of the PI3K, mTOR, and MAPK pathways and determined the effects of siRNA directed against these substrates on cell viability. We found that phosphorylation of the protein chaperone SGTA (small glutamine-rich tetratricopeptide repeat-containing protein alpha) at Ser305 is essential for PDGFRα stabilization and cell survival in PDGFRα-dependent cancer cells. Our approach provides a new view of RTK and Akt-RSK-S6 kinase signaling, revealing many previously unidentified Akt-RSK-S6 kinase substrates that merit further consideration as targets for combination therapy with RTKIs. PMID:20736484

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

Active site-directed double mutants of dihydrofolate reductase.

PubMed

Ercikan-Abali, E A; Mineishi, S; Tong, Y; Nakahara, S; Waltham, M C; Banerjee, D; Chen, W; Sadelain, M; Bertino, J R

1996-09-15

Variants of dihydrofolate reductase (DHFR), which confer resistance to antifolates, are used as dominant selectable markers in vitro and in vivo and may be useful in the context of gene therapy. To identify improved mutant human DHFRs with increased catalytic efficiency and decreased binding to methotrexate, we constructed by site-directed mutagenesis four variants with substitutions at both Leu22 and Phe31 (i.e., Phe22-Ser31, Tyr22-Ser31, Phe22-Gly31, and Tyr22-Gly31). Antifolate resistance has been observed previously when individual changes are made at these active-site residues. Substrate and antifolate binding properties of these "double" mutants revealed that each have greatly diminished affinity for antifolates (> 10,000-fold) yet only slightly reduced substrate affinity. Comparison of in vitro measured properties with those of single-residue variants indicates that double mutants are indeed significantly superior. This was verified for one of the double mutants that provided high-level methotrexate resistance following retrovirus-mediated gene transfer in NIH3T3 cells.

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.

Mechanism of Surface-Enhanced Raman Scattering Based on 3D Graphene-TiO2 Nanocomposites and Application to Real-Time Monitoring of Telomerase Activity in Differentiation of Stem Cells.

PubMed

Zheng, Tingting; Feng, Enduo; Wang, Zhiqiang; Gong, Xueqing; Tian, Yang

2017-10-25

With a burst development of new nanomaterials for plasmon-free surface-enhanced Raman scattering (SERS), the understanding of chemical mechanism (CM) and further applications have become more and more attractive. Herein, a novel SERS platform was specially designed through electrochemical deposition of graphene onto TiO 2 nanoarrays (EG-TiO 2 ). The developed EG-TiO 2 nanocomposite SERS platform possessed remarkable Raman activity using copper phthalocyanine (CuPc) as a probe molecule. X-ray photoelectron spectroscopy measurement revealed that the chemical bond Ti-O-C was formed at the interface between graphene and TiO 2 in EG-TiO 2 nanocomposites. Both experimental and theoretical results demonstrated that the obvious Raman enhancement was attributed to TiO 2 -induced Fermi level shift of graphene, resulting in effective charge transfer between EG-TiO 2 nanocomposites and molecules. Taking advantage of a marked Raman response of the CuPc molecule on the EG-TiO 2 nanocomposite surface as well as specific recognition of CuPc toward multiple telomeric G-quadruplex, EG-TiO 2 nanocomposites were tactfully employed as the SERS substrate for selective and ultrasensitive determination of telomerase activity, with a low detection limit down to 2.07 × 10 -16 IU. Interestingly, the self-cleaning characteristic of EG-TiO 2 nanocomposites under visible light irradiation successfully provided a recycling ability for this plasmon-free EG-TiO 2 substrate. The present SERS biosensor with high analytical performance, such as high selectivity and sensitivity, has been further explored to determine telomerase activity in stem cells as well as to count the cell numbers. More importantly, using this useful tool, it was discovered that telomerase activity plays an important role in the proliferation and differentiation from human mesenchymal stem cells to neural stem cells. This work has not only established an approach for gaining fundamental insights into the chemical mechanism (CM) of Raman enhancement but also has opened a new way in the investigation of long-term dynamics of stem cell differentiation and clinical drug screening.

Phosphorylation of the Yeast Choline Kinase by Protein Kinase C

PubMed Central

Choi, Mal-Gi; Kurnov, Vladlen; Kersting, Michael C.; Sreenivas, Avula; Carman, George M.

2005-01-01

The Saccharomyces cerevisiae CKI1-encoded choline kinase catalyzes the committed step in phosphatidylcholine synthesis via the Kennedy pathway. The enzyme is phosphorylated on multiple serine residues, and some of this phosphorylation is mediated by protein kinase A. In this work, we examined the hypothesis that choline kinase is also phosphorylated by protein kinase C. Using choline kinase as a substrate, protein kinase C activity was dose- and time-dependent, and dependent on the concentrations of choline kinase (Km = 27 μg/ml) and ATP (Km = 15 μM). This phosphorylation, which occurred on a serine residue, was accompanied by a 1.6-fold stimulation of choline kinase activity. The synthetic peptide SRSSS25QRRHS (Vmax/Km = 17.5 mM-1 μmol min-1 mg-1) that contains the protein kinase C motif for Ser25 was a substrate for protein kinase C. A Ser25 to Ala (S25A) mutation in choline kinase resulted in a 60% decrease in protein kinase C phosphorylation of the enzyme. Phosphopeptide mapping analysis of the S25A mutant enzyme confirmed that Ser25 was a protein kinase C target site. In vivo, the S25A mutation correlated with a decrease (55%) in phosphatidylcholine synthesis via the Kennedy pathway whereas an S25D phosphorylation site mimic correlated with an increase (44%) in phosphatidylcholine synthesis. Whereas the S25A (protein kinase C site) mutation did not affect the phosphorylation of choline kinase by protein kinase A, the S30A (protein kinase A site) mutation caused a 46% reduction in enzyme phosphorylation by protein kinase C. A choline kinase synthetic peptide (SQRRHS30LTRQ) containing Ser30 was a substrate (Vmax/Km = 3.0 mM−1 μmol min−1 mg−1) for protein kinase C. Comparison of phosphopeptide maps of the wild type and S30A mutant choline kinase enzymes phosphorylated by protein kinase C confirmed that Ser30 was also a target site for protein kinase C. PMID:15919656

Simulation of two-dimensional gratings for SERS-active substrate

NASA Astrophysics Data System (ADS)

Zou, Wenlong; Wu, Jianhong

2016-11-01

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

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.

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.

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.

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.

Phosphorylation of insulin receptor substrate-1 serine 307 correlates with JNK activity in atrophic skeletal muscle

NASA Technical Reports Server (NTRS)

Hilder, Thomas L.; Tou, Janet C L.; Grindeland, Richard E.; Wade, Charles E.; Graves, Lee M.

2003-01-01

c-Jun NH(2)-terminal kinase (JNK) has been shown to negatively regulate insulin signaling through serine phosphorylation of residue 307 within the insulin receptor substrate-1 (IRS-1) in adipose and liver tissue. Using a rat hindlimb suspension model for muscle disuse atrophy, we found that JNK activity was significantly elevated in atrophic soleus muscle and that IRS-1 was phosphorylated on Ser(307) prior to the degradation of the IRS-1 protein. Moreover, we observed a corresponding reduction in Akt activity, providing biochemical evidence for the development of insulin resistance in atrophic skeletal muscle.

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.

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.

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.

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.

Three dimensional structural studies of alpha-N-acetylgalactosaminidase (alpha-NAGA) in alpha-NAGA deficiency (Kanzaki disease): different gene mutations cause peculiar structural changes in alpha-NAGAs resulting in different substrate specificities and clinical phenotypes.

PubMed

Kanekura, Takuro; Sakuraba, Hitoshi; Matsuzawa, Fumiko; Aikawa, Seiichi; Doi, Hirofumi; Hirabayashi, Yoshio; Yoshii, Noriko; Fukushige, Tomoko; Kanzaki, Tamotsu

2005-01-01

Kanzaki disease (OMIM#104170) is attributable to a deficiency in alpha-N-acetylgalactosaminidase (alpha-NAGA; E.C.3.2.1.49), which hydrolyzes GalNAcalpha1-O-Ser/Thr. Missense mutations, R329W or R329Q were identified in two Japanese Kanzaki patients. Although they are on the same codon, the clinical manifestation was more severe in R329W because an amino acid substitution led to protein instability resulting in structural change, which is greater in R329W than in R329Q. To examine whether the different clinical phenotypes are attributable to the two mutations. Plasma alpha-NAGA activity and urinary excreted glycopeptides were measured and three-dimensional models of human alpha-NAGA and its complexes with GalNAcalpha1-O-Ser and GalNAcalpha1-O-Thr were constructed by homology modeling. Residual enzyme activity was significantly higher in the R329Q- than the R329W mutant (0.022+/-0.005 versus 0.005+/-0.001 nmol/h/ml: p<0.05); the urinary ratios of GalNAcalpha1-O-Ser:GalNAcalpha1-O-Thr were 2:10 and 8:10, respectively. GalNAcalpha1-O-Ser/Thr fit tightly in a narrow space of the active site pocket of alpha-NAGA. GalNAcalpha1-O-Thr requires a larger space to associate with alpha-NAGA because of the side chain (CH3) of the threonine residue. Our findings suggest that the association of alpha-NAGA with its substrates is strongly affected by the amino acid substitution at R329 and that the association with GalNAcalpha1-O-Thr is more highly susceptible to structural changes. The residual mutant enzyme in R329W could not associate with GalNAcalpha1-O-Thr and GalNAcalpha1-O-Ser. However, the residual mutant enzyme in R329Q catalyzed GalNAcalpha1-O-Ser to some extent. Therefore, the urinary ratio of GalNAcalpha1-O-Ser:GalNAcalpha1-O-Thr was lower and the clinical phenotype was milder in the R329Q mutation. Structural analysis revealed biochemical and phenotypic differences in these Kanzaki patients with the R329Q and R329W mutation.

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.

Controllable formation of high density SERS-active silver nanoprism layers on hybrid silica-APTES coatings

NASA Astrophysics Data System (ADS)

Pilipavicius, J.; Kaleinikaite, R.; Pucetaite, M.; Velicka, M.; Kareiva, A.; Beganskiene, A.

2016-07-01

In this work sol-gel process for preparation of the uniform hybrid silica-3-aminopropyltriethoxysilane (APTES) coatings on glass surface is presented from mechanistic point of view. The suggested synthetic approach is straightforward, scalable and provides the means to tune the amount of amino groups on the surface simply by changing concentration of APTES in the initial sol. Deposition rate of different size silver nanoprisms (AgNPRs) on hybrid silica coatings of various amounts of APTES were studied and their performance as SERS materials were probed. The acquired data shows that the deposition rate of AgNPRs can be tuned by changing the amount of APTES. The optimal amount of APTES was found to be crucial for successful AgNPRs assembly and subsequent uniformity of the final SERS substrate-too high APTES content may result in rapid non-stable aggregation and non-uniform assembly process. SERS study revealed that SERS enhancement is the strongest at moderate AgNPRs aggregation level whereas it significantly drops at high aggregation levels.

PINK1 autophosphorylation is required for ubiquitin recognition.

PubMed

Rasool, Shafqat; Soya, Naoto; Truong, Luc; Croteau, Nathalie; Lukacs, Gergely L; Trempe, Jean-François

2018-04-01

Mutations in PINK1 cause autosomal recessive Parkinson's disease (PD), a neurodegenerative movement disorder. PINK1 is a kinase that acts as a sensor of mitochondrial damage and initiates Parkin-mediated clearance of the damaged organelle. PINK1 phosphorylates Ser65 in both ubiquitin and the ubiquitin-like (Ubl) domain of Parkin, which stimulates its E3 ligase activity. Autophosphorylation of PINK1 is required for Parkin activation, but how this modulates the ubiquitin kinase activity is unclear. Here, we show that autophosphorylation of Tribolium castaneum PINK1 is required for substrate recognition. Using enzyme kinetics and NMR spectroscopy, we reveal that PINK1 binds the Parkin Ubl with a 10-fold higher affinity than ubiquitin via a conserved interface that is also implicated in RING1 and SH3 binding. The interaction requires phosphorylation at Ser205, an invariant PINK1 residue (Ser228 in human). Using mass spectrometry, we demonstrate that PINK1 rapidly autophosphorylates in trans at Ser205. Small-angle X-ray scattering and hydrogen-deuterium exchange experiments provide insights into the structure of the PINK1 catalytic domain. Our findings suggest that multiple PINK1 molecules autophosphorylate first prior to binding and phosphorylating ubiquitin and Parkin. © 2018 The Authors.

A study of the depth and size of concave cube Au nanoparticles as highly sensitive SERS probes

NASA Astrophysics Data System (ADS)

Romo-Herrera, J. M.; González, A. L.; Guerrini, L.; Castiello, F. R.; Alonso-Nuñez, G.; Contreras, O. E.; Alvarez-Puebla, R. A.

2016-03-01

High and uniform near fields are localized at the eight similar sharp corners of cubic gold nanoparticles. Moreover, by introducing concavity in the particle lateral planes, such field intensities can be further increased and tuned in the near infrared region without altering the overall size of the nanoparticles. Herein, we perform a thorough investigation of the morphological, crystallographic and plasmonic properties of concave gold nanocubes (GNCs) in the sub-70 nm size range, for their potential application as highly efficient SERS substrates in size-limiting cases. Theoretical calculations indicate that the highest increment of the near-field is located at the eight sharp tips and, interestingly, a medium near-field increment is also activated over the volume next to the concave surface. Remarkably, the plasmonic response of the concave cubic morphology showed great sensitivity to the concavity degree. Experimental SERS analysis nicely matches the outcome of the theoretical model, confirming that medium-sized concave GNCs (35 nm side length) possess the highest SERS activity upon excitation with a 633 nm laser, whereas larger 61 nm side concave GNCs dominate the optical response at 785 nm. Due to their size-intensity trade off, we envision that such small concave gold nanocubes can provide a highly active and efficient SERS platform for size-limiting applications, especially when near infrared excitations are required.High and uniform near fields are localized at the eight similar sharp corners of cubic gold nanoparticles. Moreover, by introducing concavity in the particle lateral planes, such field intensities can be further increased and tuned in the near infrared region without altering the overall size of the nanoparticles. Herein, we perform a thorough investigation of the morphological, crystallographic and plasmonic properties of concave gold nanocubes (GNCs) in the sub-70 nm size range, for their potential application as highly efficient SERS substrates in size-limiting cases. Theoretical calculations indicate that the highest increment of the near-field is located at the eight sharp tips and, interestingly, a medium near-field increment is also activated over the volume next to the concave surface. Remarkably, the plasmonic response of the concave cubic morphology showed great sensitivity to the concavity degree. Experimental SERS analysis nicely matches the outcome of the theoretical model, confirming that medium-sized concave GNCs (35 nm side length) possess the highest SERS activity upon excitation with a 633 nm laser, whereas larger 61 nm side concave GNCs dominate the optical response at 785 nm. Due to their size-intensity trade off, we envision that such small concave gold nanocubes can provide a highly active and efficient SERS platform for size-limiting applications, especially when near infrared excitations are required. Electronic supplementary information (ESI) available: Nanoparticle size distribution analysis (Fig. SI-1); extended TEM analysis on nanocubes morphology (Fig. SI-2, SI-3 and SI-4); comparison of GNCs size and concavity degree (Fig. SI-4); optical response calculations using the curved edges model (Fig. SI-5); simulated optical absorption spectra as a function of the concavity depth (Fig. SI-6); background SERS spectrum (Fig. SI-8) and details on the calculation of the SERS enhancement factors. See DOI: 10.1039/c6nr01155a

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.

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

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.

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.

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

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.

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

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

Proteolysis of HCF-1 by Ser/Thr glycosylation-incompetent O-GlcNAc transferase:UDP-GlcNAc complexes

PubMed Central

Kapuria, Vaibhav; Röhrig, Ute F.; Bhuiyan, Tanja; Borodkin, Vladimir S.; van Aalten, Daan M.F.; Zoete, Vincent; Herr, Winship

2016-01-01

In complex with the cosubstrate UDP-N-acetylglucosamine (UDP-GlcNAc), O-linked-GlcNAc transferase (OGT) catalyzes Ser/Thr O-GlcNAcylation of many cellular proteins and proteolysis of the transcriptional coregulator HCF-1. Such a dual glycosyltransferase–protease activity, which occurs in the same active site, is unprecedented and integrates both reversible and irreversible forms of protein post-translational modification within one enzyme. Although occurring within the same active site, we show here that glycosylation and proteolysis occur through separable mechanisms. OGT consists of tetratricopeptide repeat (TPR) and catalytic domains, which, together with UDP-GlcNAc, are required for both glycosylation and proteolysis. Nevertheless, a specific TPR domain contact with the HCF-1 substrate is critical for proteolysis but not Ser/Thr glycosylation. In contrast, key catalytic domain residues and even a UDP-GlcNAc oxygen important for Ser/Thr glycosylation are irrelevant for proteolysis. Thus, from a dual glycosyltransferase–protease, essentially single-activity enzymes can be engineered both in vitro and in vivo. Curiously, whereas OGT-mediated HCF-1 proteolysis is limited to vertebrate species, invertebrate OGTs can cleave human HCF-1. We present a model for the evolution of HCF-1 proteolysis by OGT. PMID:27056667

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.

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.

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 ...

The synergistic effect of nitrogen-doped titanium dioxide/mercaptobenzoic acid/silver nanocomplexes for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Feng, Jun; Bao, Wenyuan; Li, Lijun; Cheng, Hao; Huang, Wenyi; Kong, Hongxing; Li, Yanqing

2018-03-01

We synthesized titanium dioxide (TiO2) and nitrogen-doped TiO2 nanoparticles (N-TiO2 NPs) via a sol-hydrothermal method using ammonium chloride (NH4Cl) as the nitrogen (N) source. Furthermore, an N-TiO2/4-mercaptobenzoic acid (4-MBA)/silver (Ag) nanocomplex served as an active substrate for surface-enhanced Raman scattering (SERS) and was prepared by self-assembly. During SERS, the Raman signals of 4-MBA of the N-TiO2/MBA/Ag nanocomplexes exhibited higher intensity and sensitivity than pure TiO2/MBA/Ag, with 1% N doping in N-TiO2, producing the strongest Raman signals. We characterized the N-TiO2 hybrid materials by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and ultraviolet-visible diffuse reflectance spectra. N doping did not influence the phase of the TiO2 crystal. The doped N entered into the crystal lattice of the TiO2, replacing some oxygen (O) to form Ti-O-N or Ti-N-O linkage. The results indicated that an appropriate amount of N doping could enhance the SERS performance of the TiO2 SERS substrate via N substitution doping. These doping forms were beneficial to the molecular charge transfer (CT), and this resulted in improved SERS performance for N-doped TiO2 NPs. We attributed this improvement to the formation of N-doping energy levels that were beneficial to the process of TiO2 to MBA molecule CT. This work not only enriched the nonmetal-doped CT mechanism in SERS but also provided several reference values for practical applications. [Figure not available: see fulltext.

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

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.

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

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.

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.

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

Rapid and label-free screening and identification of Anthrax simulants by Surface Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Lai, Antonia; Almaviva, Salvatore; Spizzichino, Valeria; Palucci, Antonio; Addari, Lorella; Luciani, Domenico; Mengali, Sandro; Marquette, Christophe; Berthuy, Ophélie; Jankiewicz, Bartlomiej; Pierno, Luigi

2014-10-01

In the framework of RAMBO (Rapid-Air Monitoring particle against biological threats) project of the European Defense Agency (EDA), the feasibility of an unattended Surface Enhanced Raman Spectroscopy (SERS) sensor for biological threats detection was investigated. Its main goal concern Bacillus anthrax detection, both as vegetative cells and endospores. However since such bacteria are classified in Risk Group 3 (very dangerous microorganism), Bacillus thuringiensis and Bacillus atrophaeus were used as simulants. In order to bind selectively the target bacilli, Phages properly selected were immobilized on an active commercially available SERS substrate (functionalization). The Phages are a type of virus that infect selectively, by means of receptors, specific bacteria. Moreover they can resist on water or air environments without losing their binding capabilities. The sensing surface was characterized by standard micro-Raman equipments to assess the background Raman features. The Raman measurements have been carried out from 10X to 100X of magnification to differentiate between average and local features. Moreover the fast response was acquired by limiting the measure time at less than 1 minute. Samples of vegetative cells and endospores of Bacilli were randomly dispersed on the functionalized SERS substrates. The results obtained are promising: samples with and without bacilli could be distinguished one from the other. This is a step toward the use of SERS as an effective and fast technique for early warning of biological threats.

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.

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.

A Novel Angiotensin I-Converting Enzyme Mutation (S333W) Impairs N-Domain Enzymatic Cleavage of the Anti-Fibrotic Peptide, AcSDKP

PubMed Central

Danilov, Sergei M.; Wade, Michael S.; Schwager, Sylva L.; Douglas, Ross G.; Nesterovitch, Andrew B.; Popova, Isolda A.; Hogarth, Kyle D.; Bhardwaj, Nakul; Schwartz, David E.; Sturrock, Edward D.; Garcia, Joe G. N.

2014-01-01

Background Angiotensin I-converting enzyme (ACE) has two functional N- and C-domain active centers that display differences in the metabolism of biologically-active peptides including the hemoregulatory tetrapeptide, Ac-SDKP, hydrolysed preferentially by the N domain active center. Elevated Ac-SDKP concentrations are associated with reduced tissue fibrosis. Results We identified a patient of African descent exhibiting unusual blood ACE kinetics with reduced relative hydrolysis of two synthetic ACE substrates (ZPHL/HHL ratio) suggestive of the ACE N domain center inactivation. Inhibition of blood ACE activity by anti-catalytic mAbs and ACE inhibitors and conformational fingerprint of blood ACE suggested overall conformational changes in the ACE molecule and sequencing identified Ser333Trp substitution in the N domain of ACE. In silico analysis demonstrated S333W localized in the S1 pocket of the active site of the N domain with the bulky Trp adversely affecting binding of ACE substrates due to steric hindrance. Expression of mutant ACE (S333W) in CHO cells confirmed altered kinetic properties of mutant ACE and conformational changes in the N domain. Further, the S333W mutant displayed decreased ability (5-fold) to cleave the physiological substrate AcSDKP compared to wild-type ACE. Conclusions and Significance A novel Ser333Trp ACE mutation results in dramatic changes in ACE kinetic properties and lowered clearance of Ac-SDKP. Individuals with this mutation (likely with significantly increased levels of the hemoregulatory tetrapeptide in blood and tissues), may confer protection against fibrosis. PMID:24505347

Biochemical characterisation of the chlamydial MurF ligase, and possible sequence of the chlamydial peptidoglycan pentapeptide stem.

PubMed

Patin, Delphine; Bostock, Julieanne; Chopra, Ian; Mengin-Lecreulx, Dominique; Blanot, Didier

2012-06-01

Chlamydiaceae are obligate intracellular bacteria that do not synthesise detectable peptidoglycan although they possess an almost complete arsenal of genes encoding peptidoglycan biosynthetic activities. In this paper, the murF gene from Chlamydia trachomatis was shown to be capable of complementing a conditional Escherichia coli mutant impaired in UDP-MurNAc-tripeptide:D-Ala-D-Ala ligase activity. Recombinant MurF from C. trachomatis was overproduced and purified from E. coli. It exhibited ATP-dependent UDP-MurNAc-X-γ-D-Glu-meso-A(2)pm:D-Ala-D-Ala ligase activity in vitro. No significant difference of kinetic parameters was seen when X was L-Ala, L-Ser or Gly. The L-Lys-containing UDP-MurNAc-tripeptide was a poorer substrate as compared to the meso-A(2)pm-containing one. Based on the respective substrate specificities of the chlamydial MurC, MurE, MurF and Ddl enzymes, a sequence L-Ala/L-Ser/Gly-γ-D-Glu-meso-A(2)pm-D-Ala-D-Ala is expected for the chlamydial pentapeptide stem, with Gly at position 1 being less likely.

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

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

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).

Study on surface-enhanced Raman scattering efficiency of Ag core-Au shell bimetallic nanoparticles

NASA Astrophysics Data System (ADS)

Dong, Xiao; Gu, Huaimin; Kang, Jian; Yuan, Xiaojuan

2009-08-01

In this article, the relationship between the states of Ag core-Au shell (core-shell) nanoparticles (NP) and the intensity of Raman scattering of analytes dissolved in the water and adsorbed on the NP was studied. The core-shell NP were synthesised by coating Au layers over Ag seeds by the method of "seed-growth". To highlight the advantage of the core-shell NP, Ag colloid and Au colloid were chosen for contrasting. The analyte that were chosen for this testing were methylene blue (MB) for the reason that MB has very strong signal in surface-enhanced Raman scattering (SERS). The SERS activity of optimalizing states of Ag and Au colloids were compared with that of core-shell NP when MB was used as analyte. In this study, sodium chloride, sodium sulfate and sodium nitrate were used as aggregating agents for Ag, Au colloids and core-shell NP, because anions have a strong influence on the SERS efficiency and the stability of colloids. The results indicate that core-shell NP can obviously enhance the SERS of MB. The aim of this study is to prove that compared with the metal colloid, the core-shell NP is a high efficiency SERS active substrate.

Functionalization of nanostructured gold substrates with chiral chromophores for SERS applications: The case of 5-Aza[5]helicene.

PubMed

Zanchi, Chiara; Lucotti, Andrea; Cancogni, Damiano; Fontana, Francesca; Trusso, Sebastiano; Ossi, Paolo M; Tommasini, Matteo

2018-05-31

Nanostructured gold thin films can be fabricated by controlled pulsed laser deposition to get efficient sensors, with uniform morphology and optimized plasmon resonance, to be employed as plasmonic substrates in surface enhanced Raman scattering spectroscopy. By attaching 5-aza[5]helicen-6-yl-6-hexanethiol to such gold nanostructures, used in a previous work for label-free drug sensing with biomedical purposes, we successfully prepared functionalized substrates with remarkable surface enhanced Raman scattering activity. The long-term motivation is to develop probes for drug detection at low concentrations, where sensitivity to specific chiral targets is required. © 2018 Wiley Periodicals, Inc.

Domain wise docking analyses of the modular chitin binding protein CBP50 from Bacillus thuringiensis serovar konkukian S4.

PubMed

Sehar, Ujala; Mehmood, Muhammad Aamer; Hussain, Khadim; Nawaz, Salman; Nadeem, Shahid; Siddique, Muhammad Hussnain; Nadeem, Habibullah; Gull, Munazza; Ahmad, Niaz; Sohail, Iqra; Gill, Saba Shahid; Majeed, Summera

2013-01-01

This paper presents an in silico characterization of the chitin binding protein CBP50 from B. thuringiensis serovar konkukian S4 through homology modeling and molecular docking. The CBP50 has shown a modular structure containing an N-terminal CBM33 domain, two consecutive fibronectin-III (Fn-III) like domains and a C-terminal CBM5 domain. The protein presented a unique modular structure which could not be modeled using ordinary procedures. So, domain wise modeling using MODELLER and docking analyses using Autodock Vina were performed. The best conformation for each domain was selected using standard procedure. It was revealed that four amino acid residues Glu-71, Ser-74, Glu-76 and Gln-90 from N-terminal domain are involved in protein-substrate interaction. Similarly, amino acid residues Trp-20, Asn-21, Ser-23 and Val-30 of Fn-III like domains and Glu-15, Ala-17, Ser-18 and Leu-35 of C-terminal domain were involved in substrate binding. Site-directed mutagenesis of these proposed amino acid residues in future will elucidate the key amino acids involved in chitin binding activity of CBP50 protein.

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

PKI-587 and sorafenib targeting PI3K/AKT/mTOR and Ras/Raf/MAPK pathways synergistically inhibit HCC cell proliferation.

PubMed

Gedaly, Roberto; Angulo, Paul; Hundley, Jonathan; Daily, Michael F; Chen, Changguo; Evers, B Mark

2012-08-01

Deregulated Ras/Raf/MAPK and PI3K/AKT/mTOR signaling pathways are found in hepatocellular carcinoma (HCC). This study aimed to test the inhibitory effects of PKI-587 and sorafenib as single agents or in combination on HCC (Huh7 cell line) proliferation. (3)H-thymidine incorporation and MTT assay were used to assess Huh7 cell proliferation. Phosphorylation of the key enzymes in the Ras/Raf/MAPK and PI3K/AKT/mTOR pathways was detected by Western blot. We found that PKI-587 is a more potent PI3K/mTOR inhibitor than PI-103. Combination of PKI-587 and sorafenib was a more effective inhibitor of Huh7 proliferation than the combination of PI-103 and sorafenib. Combination of PKI-587 and sorafenib synergistically inhibited epidermal growth factor (EGF)-stimulated Huh7 proliferation compared with monodrug therapy. EGF increased phosphorylation of Ras/Raf downstream signaling proteins MEK and ERK; EGF-stimulated activation was inhibited by sorafenib. However, sorafenib, as a single agent, increased AKT (Ser473) phosphorylation. EGF-stimulated AKT (ser473) activation was inhibited by PKI-587. PKI-587 is a potent inhibitor of AKT (Ser473), mTOR (Ser2448), and S6K (Thr389) phosphorylation; in contrast, rapamycin stimulated mTOR complex 2 substrate AKT(Ser473) phosphorylation although it inhibited mTOR complex 1 substrate S6K phosphorylation. PKI-587, as a single agent, stimulated MEK and ERK phosphorylation. However, when PKI-587 and sorafenib were used in combination, they inhibited all the tested kinases in the Ras/Raf /MAPK and PI3K/AKT/mTOR pathways. The combination of PKI-587 and sorafenib has the advantage over monodrug therapy on inhibition of HCC cell proliferation by blocking both PI3K/AKT/mTOR and Ras/Raf/MAPK signaling pathways. Copyright © 2012 Elsevier Inc. All rights reserved.

Single-order, subwavelength resonant nanograting as a uniformly hot substrate for surface-enhanced Raman spectroscopy.

PubMed

Deng, Xuegong; Braun, Gary B; Liu, Sheng; Sciortino, Paul F; Koefer, Bob; Tombler, Thomas; Moskovits, Martin

2010-05-12

The surface-enhanced Raman spectroscopy (SERS) activity and the optical reflectance of a subwavelength gold nanograting fabricated entirely using top down technologies on silicon wafers are presented. The grating consists of 120 nm gold cladding on top of parallel silica nanowires constituting the grating's lines, with gaps between nanowires <10 nm wide at their narrowest point. The grating produces inordinately intense SERS and shows very strong polarization dependence. Reflectance measurements for the optimized grating indicate that (when p-polarization is used and at least one of the incident electric field components lies across the grating lines) the reflectance drops to <1% at resonance, indicating that essentially all of the radiant energy falling on the surface is coupled into the grating. The SERS intensity and the reflectance at resonance anticorrelate predicatively, suggesting that reflectance measurements can provide a nondestructive, wafer-level test of SERS efficacy. The SERS performance of the gratings is very uniform and reproducible. Extensive measurements on samples cut from both the same wafer and from different wafers, produce a SERS intensity distribution function that is similar to that obtained for ordinary Raman measurements carried out at multiple locations on a polished (100) silicon wafer.

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

PubMed

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

2015-05-08

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

Facile fabrication of silver nanoparticles with temperature-responsive sizes as highly active SERS substrates

NASA Astrophysics Data System (ADS)

Wu, Jing; Fang, Jinghuai; Cheng, Mingfei; Gong, Xiao

2016-12-01

In our work, large-scale silver NPs (nanoparticles) are successfully synthesized on zinc foils with controllable size by regulating the temperature of the displacement reaction. Our results show that when the temperature is 70 °C, the average size of silver NPs is approximately 88 nm in diameter, and they exhibit the strongest SERS activity. The gap between nanoparticles is simultaneously regulated as near as possible, which produces abundant "hot spots" and nanogaps. Crystal violet (CV) was used as probe molecules, and the SERS signals show that the values of relative standard deviation in the intensity of the main vibration modes are less than 10%, demonstrating excellent reproducibility of the silver NPs. Furthermore, the high surface-average enhancement factor of 3.86 × 107 is achieved even when the concentration of CV is 10-7 M, which is sufficient for single-molecule detection. We believe that this low cost and rapid route would get wide applications in chemical synthesis.

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.

Phosphorylation of a splice variant of collapsin response mediator protein 2 in the nucleus of tumour cells links cyclin dependent kinase-5 to oncogenesis.

PubMed

Grant, Nicola J; Coates, Philip J; Woods, Yvonne L; Bray, Susan E; Morrice, Nicholas A; Hastie, C James; Lamont, Douglas J; Carey, Francis A; Sutherland, Calum

2015-11-10

Cyclin-dependent protein kinase-5 (CDK5) is an unusual member of the CDK family as it is not cell cycle regulated. However many of its substrates have roles in cell growth and oncogenesis, raising the possibility that CDK5 modulation could have therapeutic benefit. In order to establish whether changes in CDK5 activity are associated with oncogenesis one could quantify phosphorylation of CDK5 targets in disease tissue in comparison to appropriate controls. However the identity of physiological and pathophysiological CDK5 substrates remains the subject of debate, making the choice of CDK5 activity biomarkers difficult. Here we use in vitro and in cell phosphorylation assays to identify novel features of CDK5 target sequence determinants that confer enhanced CDK5 selectivity, providing means to select substrate biomarkers of CDK5 activity with more confidence. We then characterize tools for the best CDK5 substrate we identified to monitor its phosphorylation in human tissue and use these to interrogate human tumour arrays. The close proximity of Arg/Lys amino acids and a proline two residues N-terminal to the phosphorylated residue both improve recognition of the substrate by CDK5. In contrast the presence of a proline two residues C-terminal to the target residue dramatically reduces phosphorylation rate. Serine-522 of Collapsin Response Mediator-2 (CRMP2) is a validated CDK5 substrate with many of these structural criteria. We generate and characterise phosphospecific antibodies to Ser522 and show that phosphorylation appears in human tumours (lung, breast, and lymphoma) in stark contrast to surrounding non-neoplastic tissue. In lung cancer the anti-phospho-Ser522 signal is positive in squamous cell carcinoma more frequently than adenocarcinoma. Finally we demonstrate that it is a specific and unusual splice variant of CRMP2 (CRMP2A) that is phosphorylated in tumour cells. For the first time this data associates altered CDK5 substrate phosphorylation with oncogenesis in some but not all tumour types, implicating altered CDK5 activity in aspects of pathogenesis. These data identify a novel oncogenic mechanism where CDK5 activation induces CRMP2A phosphorylation in the nuclei of tumour cells.

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.

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.

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.

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.

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.

Crystal structures of yellowtail ascites virus VP4 protease: trapping an internal cleavage site trans acyl-enzyme complex in a native Ser/Lys dyad active site.

PubMed

Chung, Ivy Yeuk Wah; Paetzel, Mark

2013-05-03

Yellowtail ascites virus (YAV) is an aquabirnavirus that causes ascites in yellowtail, a fish often used in sushi. Segment A of the YAV genome codes for a polyprotein (pVP2-VP4-VP3), where processing by its own VP4 protease yields the capsid protein precursor pVP2, the ribonucleoprotein-forming VP3, and free VP4. VP4 protease utilizes the rarely observed serine-lysine catalytic dyad mechanism. Here we have confirmed the existence of an internal cleavage site, preceding the VP4/VP3 cleavage site. The resulting C-terminally truncated enzyme (ending at Ala(716)) is active, as shown by a trans full-length VP4 cleavage assay and a fluorometric peptide cleavage assay. We present a crystal structure of a native active site YAV VP4 with the internal cleavage site trapped as trans product complexes and trans acyl-enzyme complexes. The acyl-enzyme complexes confirm directly the role of Ser(633) as the nucleophile. A crystal structure of the lysine general base mutant (K674A) reveals the acyl-enzyme and empty binding site states of VP4, which allows for the observation of structural changes upon substrate or product binding. These snapshots of three different stages in the VP4 protease reaction mechanism will aid in the design of anti-birnavirus compounds, provide insight into previous site-directed mutagenesis results, and contribute to understanding of the serine-lysine dyad protease mechanism. In addition, we have discovered that this protease contains a channel that leads from the enzyme surface (adjacent to the substrate binding groove) to the active site and the deacylating water.

Anticancer activities of emetine prodrugs that are proteolytically activated by the prostate specific antigen (PSA) and evaluation of in vivo toxicity of emetine derivatives.

PubMed

Akinboye, Emmanuel S; Rosen, Marc D; Bakare, Oladapo; Denmeade, Samuel R

2017-12-15

Emetine is a small molecule protein synthesis inhibitor that is toxic to all cell types and therefore suitable for complete killing of all types of heterogeneous cancer cells within a tumor. It becomes significantly inactive (non-toxic) when derivatized at its N-2' secondary amine. This provides a strategy for targeting emetine to cancerous tumor without killing normal cells. In this report, PSA activatable peptide prodrugs of emetine were synthesized. To overcome steric hindrances and enhance protease specific cleavage, a 2-stage prodrug activation process was needed to release emetine in cancer cells. In this 2-stage process, emetine prodrug intermediates are coupled to PSA peptide substrate (Ac-His-Ser-Ser-Lys-Leu-Gln) to obtain the full prodrug. Both prodrug intermediates 10 (Ala-Pro-PABC-Emetine) and 14 (Ser-Leu-PABC-Emetine) were evaluated for kinetics of hydrolysis to emetine and potency [Where PABC = p-aminobenzyloxycarbonyl]. While both intermediates quantitatively liberate emetine when incubated under appropriate conditions, upon coupling of PSA substrate to give the full prodrugs, only prodrug 16, the prodrug obtained from 14 was hydrolyzable by PSA. Cytotoxicity studies in PSA producing LNCaP and CWR22Rv1 confirm the activation of the prodrug by PSA with an IC 50 of 75 nM and 59 nM respectively. The cytotoxicity of 16 is significantly reduced in cell lines that do not produce PSA. Further, in vivo toxicity studies are done on these prodrugs and other derivatives of emetine. The results show the significance of conformational modulation in obtaining safe emetine prodrugs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfated Low Molecular Weight Lignins, Allosteric Inhibitors of Coagulation Proteinases via the Heparin Binding Site, Significantly Alter the Active Site of Thrombin and Factor Xa Compared to Heparin

PubMed Central

Henry, Brian L.; Desai, Umesh R.

2014-01-01

Sulfated low molecular weight lignins (LMWLs) have been found to bind in the heparin binding sites of coagulation proteinases. LMWLs represent a library of diverse non-carbohydrate, aromatic molecules which are structures different from heparin, but still potently inhibit thrombin and factor Xa. To better understand their mechanism of action, we studied the effects of three sulfated LMWLs (CDSO3, FDSO3, and SDSO3) on the active sites of thrombin and factor Xa. LMWLs were found to uniformly inhibit the catalytic activity of thrombin and factor Xa, regardless of the substrate used. Michaelis-Menten kinetic studies indicate that maximal velocity of hydrolysis of each chromogenic substrate decreases significantly in the presence of sulfated LMWLs, while the effect on Michaelis constant is dependent on the nature of the substrate. These studies indicate that LMWLs inhibit thrombin and factor Xa through allosteric disruption of the catalytic apparatus, specifically through the catalytic step. As opposed to heparin, LMWLs significantly alter the binding of the active site fluorescent ligand p-aminobenzamidine. LMWLs also had a greater effect on the molecular orientation of fluorescein-labeled His 57 than heparin. The molecular geometry surrounding the most important catalytic amino acid, Ser 195, was significantly altered by the binding of LMWLs while heparin had no measurable effect on Ser 195. These results further advance the concept of sulfated LMWLs as heparin mimics and will aid the design of anticoagulants based on their novel scaffold. PMID:25242245

Sulfated low molecular weight lignins, allosteric inhibitors of coagulation proteinases via the heparin binding site, significantly alter the active site of thrombin and factor xa compared to heparin.

PubMed

Henry, Brian L; Desai, Umesh R

2014-11-01

Sulfated low molecular weight lignins (LMWLs) have been found to bind in the heparin binding sites of coagulation proteinases. LMWLs represent a library of diverse non-carbohydrate, aromatic molecules which are structures different from heparin, but still potently inhibit thrombin and factor Xa. To better understand their mechanism of action, we studied the effects of three sulfated LMWLs (CDSO3, FDSO3, and SDSO3) on the active sites of thrombin and factor Xa. LMWLs were found to uniformly inhibit the catalytic activity of thrombin and factor Xa, regardless of the substrate used. Michaelis-Menten kinetic studies indicate that maximal velocity of hydrolysis of each chromogenic substrate decreases significantly in the presence of sulfated LMWLs, while the effect on Michaelis constant is dependent on the nature of the substrate. These studies indicate that LMWLs inhibit thrombin and factor Xa through allosteric disruption of the catalytic apparatus, specifically through the catalytic step. As opposed to heparin, LMWLs significantly alter the binding of the active site fluorescent ligand p-aminobenzamidine. LMWLs also had a greater effect on the molecular orientation of fluorescein-labeled His 57 than heparin. The molecular geometry surrounding the most important catalytic amino acid, Ser 195, was significantly altered by the binding of LMWLs while heparin had no measurable effect on Ser 195. These results further advance the concept of sulfated LMWLs as heparin mimics and will aid the design of anticoagulants based on their novel scaffold. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rough SERS substrate based on gold coated porous silicon layer prepared on the silicon backside surface

NASA Astrophysics Data System (ADS)

Dridi, H.; Haji, L.; Moadhen, A.

2017-04-01

We report in this paper a novel method to elaborate rough Surface Enhanced Raman Scattering (SERS) substrate. A single layer of porous silicon was formed on the silicon backside surface. Morphological characteristics of the porous silicon layer before and after gold deposition were influenced by the rough character (gold size). The reflectance measurements showed a dependence of the gold nano-grains size on the surface nature, through the Localized Surface Plasmon (LSP) band properties. SERS signal of Rhodamine 6G used as a model analyte, adsorbed on the rough porous silicon layer revealed a marked enhancement of its vibrational modes intensities.

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.

Scutellarin’s Cardiovascular Endothelium Protective Mechanism: Important Role of PKG-Iα

PubMed Central

Chen, Chen; Yang, Jian; Li, Jiaxun; Hu, Na; Li, Yang; Zhang, Dongmei; Guo, Tao; Liu, Xuan; Yang, Weimin

2015-01-01

Scutellarin (SCU), a flavonoid glycoside compound, has been successfully used in clinic for treatment of ischemic diseases in China. In this report, we checked the effects of SCU on endothelium dysfunction (ED) of coronary artery (CA) against myocardial ischemia reperfusion (MIR) injury in vivo. The involvement of PKG-Iα was further studied using cultured endothelial cells subjected to hypoxia reoxygenation (HR) injury in vitro. In rat MIR model, SCU (45 and 90 mg/kg, iv) significantly reduced ischemic size and restored the endothelium-dependent vasodilation of isolated CA rings. PKG inhibitor Rp-8-Br-cGMP (50 μg/kg, iv) could ameliorate the protective effects of SCU. Increase in phosphorylation of vasodilator-stimulated phosphoprotein (VASP), a main substrate of PKG, at Ser 239 was observed in both heart tissue and serum of SCU-treated animals. In cultured human cardiac microvascular endothelial cells (HCMECs), SCU (1 and 10 μM) dose-dependently protected cell viability and increased the mRNA and protein level of PKG-Iα against HR injury. The activity of PKG was also increased by SCU treatment. The activation of PKG–1α was then studied using targeted proteomic analysis (MRM-MS) checking the phosphorylation state of the autophosphorylation domain (aa42-94). Significant decrease in phosphorylation of PKG-Iα at Ser50, Ser72, Ser89 was induced by HR injury while SCU treatment significantly increased the phosphorylation of PKG-Iα, not only at Ser50, Ser72 and Ser89, but also at Ser44 and Thr58 (two novel phosphorylation domains). Our results demonstrate PKG-Iα might play an important role in the protective effects of SCU on ED against MIR injury. PMID:26440524

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.

Synthesis by picosecond laser ablation of ligand-free Ag and Au nanoparticles for SERS applications

NASA Astrophysics Data System (ADS)

Fazio, Enza; Spadaro, Salvatore; Santoro, Marco; Trusso, Sebastiano; Lucotti, Andrea.; Tommasini, Matteo.; Neri, Fortunato; Maria Ossi, Paolo

2018-01-01

The morphological and optical properties of noble metal nanoparticles prepared by picosecond laser generated plasmas in water were investigated. First, the ablation efficiency was maximized searching the optimal focusing conditions. The nanoparticle size, measured by Scanning Transmission Electron Microscopy, strongly depends on the laser fluence, keeping fixed the other deposition parameters such as the target to scanner objective distance and laser repetition frequency. STEM images indicate narrow gradients of NP sizes. Hence the optimization of ablation parameters favours a fine tuning of nanoparticles. UV-Visible spectroscopy helped to determine the appropriate laser wavelength to resonantly excite the localized surface plasmon to carry out Surface Enhanced Raman Scattering (SERS) measurements. The SERS activity of Ag and Au substrates, obtained spraying the colloids synthesized in water, was tested using crystal violet as a probe molecule. The good SERS performance, observed at excitation wavelength 785 nm, is attributed to aggregation phenomena of nanoparticles sprayed on the support.

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

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.

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®.

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.

mTORC1/2 and rapamycin in female Han:SPRD rats with polycystic kidney disease.

PubMed

Belibi, Franck; Ravichandran, Kameswaran; Zafar, Iram; He, Zhibin; Edelstein, Charles L

2011-01-01

Rapamycin slows disease progression in the male Han:SPRD (Cy/+) rat with polycystic kidney disease (PKD). The aim of this study was to determine the effect of rapamycin on PKD and the relative contributions of the proproliferative mammalian target of rapamycin complexes 1 and 2 (mTORC1 and mTORC2) in female Cy/+ rats. Female Cy/+ rats were treated with rapamycin from 4 to 12 wk of age. In vehicle-treated Cy/+ rats, kidney volume increased by 40% and cyst volume density (CVD) was 19%. Phosphorylated S6 (p-S6) ribosomal protein, a marker of mTORC1 activity, was increased in Cy/+ rats compared with normal littermate controls (+/+) and decreased by rapamycin. Despite activation of mTORC1 in female Cy/+ rats, rapamycin had no effect on kidney size, CVD, number of PCNA-positive cystic tubular cells, caspase-3 activity, or the number of terminal deoxynucleotidyl transferase dUTP-mediated nick-end label-positive apoptotic cells. To determine a reason for the lack of effect of rapamycin, we studied the mTORC2 signaling pathway. On immunoblot of kidney, phosphorylated (Ser473) Akt (p-Akt), a marker of mTORC2 activity, was increased in female Cy/+ rats treated with rapamycin. Phosphorylated (Ser657) PKCα, a substrate of mTORC2, was unaffected by rapamycin in females. In contrast, in male rats, where rapamycin significantly decreases PKD, p-Akt (Ser473) was decreased by rapamcyin. PKCα (Ser657) was increased in male Cy/+ rats but was unaffected by rapamycin. In summary, in female Cy/+ rats, rapamycin had no effect on PKD and proproliferative p-Akt (Ser473) activity was increased by rapamycin. There were differential effects of rapamycin on mTORC2 signaling in female vs. male Cy/+ rats.

Cube-like Fe3O4@SiO2@Au@Ag magnetic nanoparticles: a highly efficient SERS substrate for pesticide detection

NASA Astrophysics Data System (ADS)

Sun, Mei; Zhao, Aiwu; Wang, Dapeng; Wang, Jin; Chen, Ping; Sun, Henghui

2018-04-01

As a novel surface-enhanced Raman spectroscopic (SERS) nanocomposite, cube-like Fe3O4@SiO2@Au@Ag magnetic nanoparticles (NPs) were synthesized for the first time. Cube-like α-Fe2O3 NPs with uniform size were achieved by optimizing reaction temperature and time. Firstly, the cube-like Fe3O4@SiO2 with good dispersity was achieved by calcining α-Fe2O3@SiO2 NPs in hydrogen atmosphere at 360 °C for 2.5 h, followed by self-assembling a PEI shell via sonication. Furthermore, the Au@Ag particles were densely assembled on the Fe3O4@SiO2 NPs to form the Fe3O4@SiO2@Au@Ag composite structure via strong Ag-N interaction. The obtained nanocomposites exhibited an excellent SERS behavior, reflected by the low detection of limit (p-ATP) at the 5 × 10-14 M level. Moreover, these nanocubes were used for the detection of thiram, and the detection limit can reach 5 × 10-11 M. Meanwhile, the U.S. Environmental Protection Agency specifies that the residue in fruit must be lower than 7 ppm. Hence, the resulting substrate with high SERS activity has great practical potential applications in the rapid detection of chemical, biological, and environment pollutants with a simple portable Raman instrument at trace level.

Cube-like Fe3O4@SiO2@Au@Ag magnetic nanoparticles: a highly efficient SERS substrate for detection of pesticide.

PubMed

Sun, Mei; Zhao, Aiwu; Wang, Dapeng; Wang, Jin; Chen, Ping; Sun, Henghui

2018-02-09

As a novel SERS nanocomposities, cube-like Fe3O4@SiO2@Au@Ag magnetic nanoparticles have been synthesized for the first time. Cube-like α-Fe2O3 NPs with uniform size can be achieved by optimizing reaction temperature and time. Firstly, the cube-like Fe3O4@SiO2 with good dispersity were achieved by calcining α-Fe2O3@SiO2 NPs in hydrogen atmosphere at 360 °C for 2.5 h, followed by self-assembling PEI shell via sonication. Furthermore, the Au@Ag particles can be densely assembled on the Fe3O4@SiO2 NPs to form the Fe3O4@SiO2@Au@Ag composite structure via strong Ag-N interaction. The obtained nanocomposites exhibit an excellent surface-enhanced Raman (SERS) behavior, reflected from low detection of limit (p-ATP) at 5×10-14 M level. Moreover, these nanocubes are used for detection of thiram and the detection limit can reach up to 5×10-11 M, while the rule of U.S. Environmental Protection Agency specifies that the residue in fruit must be lower than 7 ppm. Hence, the resulting substrate with high SERS activity has great practical potential applications in rapid detection of chemical, biological and environment pollutants with a simple portable Raman instrument at trace level. © 2018 IOP Publishing Ltd.

Characterization of cortactin as an in vivo protein kinase D substrate: interdependence of sites and potentiation by Src.

PubMed

De Kimpe, Line; Janssens, Katrien; Derua, Rita; Armacki, Milena; Goicoechea, Silvia; Otey, Carol; Waelkens, Etienne; Vandoninck, Sandy; Vandenheede, Jackie R; Seufferlein, Thomas; Van Lint, Johan

2009-02-01

Protein Kinase D (PKD) has been implicated in the regulation of actin turnover at the leading edge, invasion and migration. In particular, a complex between cortactin, paxillin and PKD in the invadopodia of invasive breast cancer cells has been described earlier, but so far this complex remained ill defined. Here we have investigated the possible role of PKD as a cortactin kinase. Using a mass spectrometric approach, we found that PKD phosphorylates cortactin on Ser 298 in the 6th cortactin repeat region and on Ser 348, right before the helical-proline rich domain of cortactin. We developed phosphospecific antibodies against these phosphorylated sequences, and used them as tools to follow the in vivo phosphorylation of cortactin by PKD. Examination of cortactin phosphorylation kinetics revealed that Ser 298 serves as a priming site for subsequent phosphorylation of Ser 348. Src, a well-known cortactin kinase, strongly potentiated the in vivo PKD mediated cortactin phosphorylation. This Src effect is neither mediated by pre-phosphorylation of cortactin nor by activation of PKD by Src. Phosphorylation of cortactin by PKD does not affect its subcellular localization, nor does it affect its translocation to podosomes or membrane ruffles. Moreover, there was no effect of PKD mediated cortactin phosphorylation on EGF receptor degradation and LPA induced migration. Taken together, these data establish cortactin as a novel PKD substrate and reveal a novel connection between Src and PKD.

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

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

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.

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

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.

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.

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.

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).

Structural basis of the broad substrate tolerance of the antibody 7B9-catalyzed hydrolysis of p-nitrobenzyl esters.

PubMed

Miyamoto, Naoki; Yoshimura, Miho; Okubo, Yuji; Suzuki-Nagata, Kayo; Tsumuraya, Takeshi; Ito, Nobutoshi; Fujii, Ikuo

2018-05-01

Catalytic antibody 7B9, which was elicited against p-nitrobenzyl phosphonate transition-state analogue (TSA) 1, hydrolyzes a wide range of p-nitrobenzyl monoesters and thus shows broad substrate tolerance. To reveal the molecular basis of this substrate tolerance, the 7B9 Fab fragment complexed with p-nitrobenzyl ethylphosphonate 2 was crystallized and the three-dimensional structure was determined. The crystal structure showed that the strongly antigenic p-nitrobenzyl moiety occupied a relatively shallow antigen-combining site and therefore the alkyl moiety was located outside the pocket. These results support the observed broad substrate tolerance of 7B9 and help rationalize how 7B9 can catalyze various p-nitrobenzyl ester derivatives. The crystal structure also showed that three amino acid residues (Asn H33 , Ser H95 , and Arg L96 ) were placed in key positions to form hydrogen bonds with the phosphonate oxygens of the transitions-state analogue. In addition, the role of these amino acid residues was examined by site-directed mutagenesis to alanine: all mutants (Asn H33 Ala, Ser H95 Ala, and Arg L96 Ala) showed no detectable catalytic activity. Coupling the findings from our structural studies with these mutagenesis results clarified the structural basis of the observed broad substrate tolerance of antibody 7B9-catalyzed hydrolyses. Our findings provide new strategies for the generation of catalytic antibodies that accept a broad range of substrates, aiding their practical application in synthetic organic chemistry. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Crystal structure of the dopamine N-acetyltransferase–acetyl-CoA complex provides insights into the catalytic mechanism

PubMed Central

Cheng, Kuo-Chang; Liao, Jhen-Ni; Lyu, Ping-Chiang

2012-01-01

The daily cycle of melatonin biosynthesis in mammals is regulated by AANAT (arylalkylamine N-acetyltransferase; EC 2.3.1.87), making it an attractive target for therapeutic control of abnormal melatonin production in mood and sleep disorders. Drosophila melanogaster Dat (dopamine N-acetyltransferase) is an AANAT. Until the present study, no insect Dat structure had been solved, and, consequently, the structural basis for its acetyl-transfer activity was not well understood. We report in the present paper the high-resolution crystal structure for a D. melanogaster Dat–AcCoA (acetyl-CoA) complex obtained using one-edge (selenium) single-wavelength anomalous diffraction. A binding study using isothermal titration calorimetry suggested that the cofactor bound to Dat first before substrate. Examination of the complex structure and a substrate-docked model indicated that Dat contains a novel AANAT catalytic triad. Site-directed mutagenesis, kinetic studies and pH-rate profiles confirmed that Glu47, Ser182 and Ser186 were critical for catalysis. Collectively, the results of the present study suggest that Dat possesses a specialized active site structure dedicated to a catalytic mechanism. PMID:22716280

Adsorption of 6-mercaptopurine and 6-mercaptopurine riboside on silver colloid: a pH dependent surface enhanced Raman spectroscopy and density functional theory study. Part I. 6-Mercaptopurine

NASA Astrophysics Data System (ADS)

Szeghalmi, A. V.; Leopold, L.; Pînzaru, S.; Chis, V.; Silaghi-Dumitrescu, I.; Schmitt, M.; Popp, J.; Kiefer, W.

2005-02-01

Surface enhanced Raman spectroscopy (SERS) on silver colloid has been applied to characterize the interaction of 6-mercaptopurine (6MP), an active drug used in chemotherapy of acute lymphoblastic leukemia, with a model biological substrate at therapeutical concentrations and as function of the pH value. The adsorption active sites and molecular orientation on the metal surface have been determined on the basis of SERS 'surface selection rules' subsequent to a detailed vibrational analysis of the 6MP tautomeric forms. Therefore, DFT calculations (vibrational wavenumbers, Raman scattering activities, partial atomic charges) of the optimized tautomers and potential energy distribution calculations have been performed. Around neutral pH value reorientation of the molecule has been observed. Under basic conditions the 6MP molecule is probably adsorbed on the silver colloid through the N1 atom of the purine ring and possibly the S atom, and adopts a tilted orientation to the surface. A reduction in the number of adsorbed molecules under basic conditions is proposed, since the SERS spectrum recorded at 10-6 M concentration at neutral pH value resembles the SERS spectra obtained under basic conditions at 10-5 M concentration. At acidic pH values a stronger interaction through the N9 and N3 atoms is suggested with an end-on orientation.

Tuning plasmons layer-by-layer for quantitative colloidal sensing with surface-enhanced Raman spectroscopy.

PubMed

Anderson, William J; Nowinska, Kamila; Hutter, Tanya; Mahajan, Sumeet; Fischlechner, Martin

2018-04-19

Surface-enhanced Raman spectroscopy (SERS) is well known for its high sensitivity that emerges due to the plasmonic enhancement of electric fields typically on gold and silver nanostructures. However, difficulties associated with the preparation of nanostructured substrates with uniform and reproducible features limit reliability and quantitation using SERS measurements. In this work we use layer-by-layer (LbL) self-assembly to incorporate multiple functional building blocks of collaborative assemblies of nanoparticles on colloidal spheres to fabricate SERS sensors. Gold nanoparticles (AuNPs) are packaged in discrete layers, effectively 'freezing nano-gaps', on spherical colloidal cores to achieve multifunctionality and reproducible sensing. Coupling between layers tunes the plasmon resonance for optimum SERS signal generation to achieve a 10 nM limit of detection. Significantly, using the layer-by-layer construction, SERS-active AuNP layers are spaced out and thus optically isolated. This uniquely allows the creation of an internal standard within each colloidal sensor to enable highly reproducible self-calibrated sensing. By using 4-mercaptobenzoic acid (4-MBA) as the internal standard adenine concentrations are quantified to an accuracy of 92.6-99.5%. Our versatile approach paves the way for rationally designed yet quantitative colloidal SERS sensors and their use in a variety of sensing applications.

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.

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.

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.

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

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.

Assembly of potassium niobate nanosheets/silver oxide composite films with good SERS performance towards crystal violet detection

NASA Astrophysics Data System (ADS)

Zhu, Kun; Hong, Zhen; Kang, Shi-Zhao; Qin, Lixia; Li, Guodong; Li, Xiangqing

2018-04-01

The orderly potassium niobate nanosheets/silver oxide (Ag2O) composite films with uniform morphology were achieved by layer-by-layer self-assembly combined with ultraviolet light irradiation. The composition, structure and morphology of the potassium niobate nanosheets/Ag2O composite films were studied by XPS, XRD and SEM. Furthermore, the films were used as a SERS probe to detect crystal violet molecules. The results showed that the potassium niobate nanosheets/Ag2O composite films were an active substrate for fast and sensitive detection of crystal violet with low concentration. The limit of detection by the films can reach 1 × 10-6 mol L-1. Both electromagnetic enhancement and chemical enhancement contributed to the enhanced SERS in the (potassium niobate nanosheets/Ag2O)4 films. Moreover, it was found that the films were relatively stable under light irradiation or heat treatment in a certain range.

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.

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.

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† †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

Cordycepin-enriched WIB801C from Cordyceps militaris inhibits ADP-induced [Ca(2+)] i mobilization and fibrinogen binding via phosphorylation of IP 3R and VASP.

PubMed

Lee, Dong-Ha; Kwon, Hyuk-Woo; Kim, Hyun-Hong; Lim, Deok Hwi; Nam, Gi Suk; Shin, Jung-Hae; Kim, Yun-Yi; Kim, Jong-Lae; Lee, Jong-Jin; Kwon, Ho-Kyun; Park, Hwa-Jin

2015-01-01

In this study, we investigated the effect of cordycepin-enriched (CE)-WIB801C from Cordyceps militaris on ADP (20 µM)-stimulated platelet aggregation. CE-WIB801C dose-dependently inhibited ADP-induced platelet aggregation, and its IC50 value was 18.5 μg/mL. CE-WIB801C decreased TXA2 production, but did not inhibit the activities of COX-1 and thromboxane synthase (TXAS) in ADP-activated platelets, which suggests that the inhibition of TXA2 production by CE-WIB801C is not resulted from the direct inhibition of COX-1 and TXAS. CE-WIB801C inhibited ATP release and [Ca(2+)]i mobilization, and increased cAMP level and IP3RI (Ser(1756)) phosphorylation in ADP-activated platelets. cAMP-dependent protein kinase (A-kinase) inhibitor Rp-8-Br-cAMPS increased CE-WIB801C-inhibited [Ca(2+)]i mobilization, and strongly inhibited CE-WIB801C-increased IP3RI (Ser(1756)) phosphorylation. CE-WIB801C elevated the phosphorylation of VASP (Ser(157)), an A-kinase substrate, but inhibited fibrinogen binding to αIIb/β3. These results suggest that CE-WIB801C-elevated cAMP involved in IP3RI (Ser(1756)) phosphorylation to inhibit [Ca(2+)]i mobilization and, VASP (Ser(157)) phosphorylation to inhibit αIIb/β3 activation. Therefore, in this study, we demonstrate that CE-WIB801C may have a preventive or therapeutic potential for platelet aggregation-mediated diseases, such as thrombosis, myocardial infarction, atherosclerosis, and ischemic cerebrovascular disease.

Biosynthesis of Selenocysteine on Its tRNA in Eukaryotes

PubMed Central

Mix, Heiko; Zhang, Yan; Saira, Kazima; Glass, Richard S; Berry, Marla J; Gladyshev, Vadim N; Hatfield, Dolph L

2007-01-01

Selenocysteine (Sec) is cotranslationally inserted into protein in response to UGA codons and is the 21st amino acid in the genetic code. However, the means by which Sec is synthesized in eukaryotes is not known. Herein, comparative genomics and experimental analyses revealed that the mammalian Sec synthase (SecS) is the previously identified pyridoxal phosphate-containing protein known as the soluble liver antigen. SecS required selenophosphate and O-phosphoseryl-tRNA[Ser]Sec as substrates to generate selenocysteyl-tRNA[Ser]Sec. Moreover, it was found that Sec was synthesized on the tRNA scaffold from selenide, ATP, and serine using tRNA[Ser]Sec, seryl-tRNA synthetase, O-phosphoseryl-tRNA[Ser]Sec kinase, selenophosphate synthetase, and SecS. By identifying the pathway of Sec biosynthesis in mammals, this study not only functionally characterized SecS but also assigned the function of the O-phosphoseryl-tRNA[Ser]Sec kinase. In addition, we found that selenophosphate synthetase 2 could synthesize monoselenophosphate in vitro but selenophosphate synthetase 1 could not. Conservation of the overall pathway of Sec biosynthesis suggests that this pathway is also active in other eukaryotes and archaea that synthesize selenoproteins. PMID:17194211

Phosphorylation of hormone-sensitive lipase by protein kinase A in vitro promotes an increase in its hydrophobic surface area.

PubMed

Krintel, Christian; Mörgelin, Matthias; Logan, Derek T; Holm, Cecilia

2009-09-01

Hormone-sensitive lipase (EC 3.1.1.79; HSL) is a key enzyme in the mobilization of fatty acids from stored triacylglycerols. HSL activity is controlled by phosphorylation of at least four serines. In rat HSL, Ser563, Ser659 and Ser660 are phosphorylated by protein kinase A (PKA) in vitro as well as in vivo, and Ser660 and Ser659 have been shown to be the activity-controlling sites in vitro. The exact molecular events of PKA-mediated activation of HSL in vitro are yet to be determined, but increases in both Vmax and S0.5 seem to be involved, as recently shown for human HSL. In this study, the hydrophobic fluorescent probe 4,4'-dianilino-1,1'-binaphthyl-5,5'-disulfonic acid (bis-ANS) was found to inhibit the hydrolysis of triolein by purified recombinant rat adipocyte HSL, with a decrease in the effect of bis-ANS upon PKA phosphorylation of HSL. The interaction of HSL with bis-ANS was found to have a Kd of 1 microM in binding assays. Upon PKA phosphorylation, the interactions of HSL with both bis-ANS and the alternative probe SYPRO Orange were increased. By negative stain transmission electron microscopy, phosphorylated HSL was found to have a closer interaction with phospholipid vesicles than unphosphorylated HSL. Taken together, our results show that HSL increases its hydrophobic nature upon phosphorylation by PKA. This suggests that PKA phosphorylation induces a conformational change that increases the exposed hydrophobic surface and thereby facilitates binding of HSL to the lipid substrate.

Sphingolipid Long-Chain Base Synthesis in Plants (Characterization of Serine Palmitoyltransferase Activity in Squash Fruit Microsomes).

PubMed

Lynch, D. V.; Fairfield, S. R.

1993-12-01

The activity of serine palmitoyltransferase (palmitoyl-coenzyme A [CoA]:L-serine [Ser]-C-palmitoyltransferase [decarboxylating], EC 2.3.1.50), the enzyme catalyzing the first step in the synthesis of the long-chain base required for sphingolipid assembly, has been characterized in a plant system. Enzyme activity in a microsomal membrane fraction from summer squash fruit (Cucurbita pepo L. cv Early Prolific Straightneck) was assayed by monitoring the incorporation of L-[3H]Ser into the chloroform-soluble product, 3-ketosphinganine. Addition of NADPH to the assay system resulted in the conversion of 3-ketosphinganine to sphinganine. The apparent Km for Ser was approximately 1.8 mM. The enzyme exhibited a strong preference for palmitoyl-CoA, with optimal activity at a substrate concentration of 200 [mu]M. Pyridoxal 5[prime]-phosphate was required as a coenzyme. The pH optimum was 7.6, and the temperature optimum was 36 to 40[deg]C. Enzyme activity was greatest in the microsomal fraction obtained by differential centrifugation and was localized to the endoplasmic reticulum using marker enzymes. Two known mechanism-based inhibitors of the mammalian enzyme, L-cycloserine and [beta]-chloro-L-alanine, were effective inhibitors of enzyme activity in squash microsomes. Changes in enzyme activity with size (age) of squash fruit were observed. The results from this study suggest that the properties and catalytic mechanism of Ser palmitoyltransferase from squash are similar to those of the animal, fungal, and bacterial enzyme in most respects. The specific activity of the enzyme in squash microsomes ranged from 0.57 to 0.84 nmol min-1 mg-1 of protein, values 2- to 20-fold higher than those previously reported for preparations from animal tissues.

Raptor, a positive regulatory subunit of mTOR complex 1, is a novel phosphoprotein of the rDNA transcription machinery in nucleoli and chromosomal nucleolus organizer regions (NORs).

PubMed

Vazquez-Martin, Alejandro; Cufí, Sílvia; Oliveras-Ferraros, Cristina; Menendez, Javier A

2011-09-15

Raptor is the key scaffolding protein that recruits mTOR substrates to rapamycin-sensitive mTOR complex 1 (mTORC1), a molecular integrator of mitogenic and nutrient/energy environmental inputs into protein translation and cell growth. Although Raptor phosphorylation on various sites is pivotal in the regulation of mTORC1 activity, it remains to be elucidated whether site-specific phosphorylation differentially distributes Raptor to unique subcellular compartments. When exploring the spatiotemporal cell cycle dynamics of six different phospho (P)-Raptor isoforms (Thr ( 706) , Ser ( 722) , Ser ( 863) , Ser ( 792) and Ser ( 877) ), a number of remarkable events differentially defined a topological resetting of P-RaptorThr706 on interphasic and mitotic chromosomes. In interphase nuclei, P-Raptor (Thr706) co-localized with fibrillarin, a component of the nucleolar small nuclear ribonucleoprotein particle, as well as with RNA polymerase I, the enzyme that transcribes nucleolar rRNA. Upon Actinomycin D-induced nucleolar segregation and disaggregation, P-RaptorThr706 was excluded from the nucleolus to accumulate at discrete nucleoplasmic bodies. During mitosis, CDK1 inhibition-induced premature assembly of nucleoli relocated fibrillarin to the surrounding regions of chromosomal-associated P-Raptor (Thr706) , suggesting that a subpopulation of mitotic P-Raptor (Thr706) remained targeted at chromosomal loops of rDNA or nuclear organizer regions (NORs). At the end of mitosis and cytokinesis, when reassembly of incipient nucleoli begins upon NORs activation of rDNA transcription, fibrillarin spatially reorganized with P-Raptor (Thr706) to give rise to daughter nucleoli. Treatment with IGF1 exclusively hyperactivated nuclear P-Raptor (Ser706) and concomitantly promoted Ser ( 2481) autophosphorylation of mTOR, which monitors mTORC1-associated catalytic activity. Nucleolar- and NOR-associated P-Raptor (Ser706) may physically link mTORC1 signaling to ever-growing nucleolus plurifunctionality including ribosome biogenesis, cell stress sensor and cell cycle/aging control.

Contribution of cutinase serine 42 side chain to the stabilization of the oxyanion transition state.

PubMed

Nicolas, A; Egmond, M; Verrips, C T; de Vlieg, J; Longhi, S; Cambillau, C; Martinez, C

1996-01-16

Cutinase from the fungus Fusarium solani pisi is a lipolytic enzyme able to hydrolyze both aggregated and soluble substrates. It therefore provides a powerful tool for probing the mechanisms underlying lipid hydrolysis. Lipolytic enzymes have a catalytic machinery similar to those present in serine proteinases. It is characterized by the triad Ser, His, and Asp (Glu) residues, by an oxyanion binding site that stabilizes the transition state via hydrogen bonds with two main chain amide groups, and possibly by other determinants. It has been suggested on the basis of a covalently bond inhibitor that the cutinase oxyanion hole may consist not only of two main chain amide groups but also of the Ser42 O gamma side chain. Among the esterases and the serine and the cysteine proteases, only Streptomyces scabies esterase, subtilisin, and papain, respectively, have a side chain residue which is involved in the oxyanion hole formation. The position of the cutinase Ser42 side chain is structurally conserved in Rhizomucor miehei lipase with Ser82 O gamma, in Rhizopus delemar lipase with Thr83 O gamma 1, and in Candida antartica B lipase with Thr40 O gamma 1. To evaluate the increase in the tetrahedral intermediate stability provided by Ser42 O gamma, we mutated Ser42 into Ala. Furthermore, since the proper orientation of Ser42 O gamma is directed by Asn84, we mutated Asn84 into Ala, Leu, Asp, and Trp, respectively, to investigate the contribution of this indirect interaction to the stabilization of the oxyanion hole. The S42A mutation resulted in a drastic decrease in the activity (450-fold) without significantly perturbing the three-dimensional structure. The N84A and N84L mutations had milder kinetic effects and did not disrupt the structure of the active site, whereas the N84W and N84D mutations abolished the enzymatic activity due to drastic steric and electrostatic effects, respectively.

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.

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.

New Surface-Enhanced Raman Sensing Chip Designed for On-Site Detection of Active Ricin in Complex Matrices Based on Specific Depurination.

PubMed

Tang, Ji-Jun; Sun, Jie-Fang; Lui, Rui; Zhang, Zong-Mian; Liu, Jing-Fu; Xie, Jian-Wei

2016-01-27

Quick and accurate on-site detection of active ricin has very important realistic significance in view of national security and defense. In this paper, optimized single-stranded oligodeoxynucleotides named poly(21dA), which function as a depurination substrate of active ricin, were screened and chemically attached on gold nanoparticles (AuNPs, ∼100 nm) via the Au-S bond [poly(21dA)-AuNPs]. Subsequently, poly(21dA)-AuNPs were assembled on a dihydrogen lipoic-acid-modified Si wafer (SH-Si), thus forming the specific surface-enhanced Raman spectroscopy (SERS) chip [poly(21dA)-AuNPs@SH-Si] for depurination of active ricin. Under optimized conditions, active ricin could specifically hydrolyze multiple adenines from poly(21dA) on the chip. This depurination-induced composition change could be conveniently monitored by measuring the distinct attenuation of the SERS signature corresponding to adenine. To improve sensitivity of this method, a silver nanoshell was deposited on post-reacted poly(21dA)-AuNPs, which lowered the limit of detection to 8.9 ng mL(-1). The utility of this well-controlled SERS chip was successfully demonstrated in food and biological matrices spiked with different concentrations of active ricin, thus showing to be very promising assay for reliable and rapid on-site detection of active ricin.

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

Detoxification of gold nanorods by conjugation with thiolated poly(ethylene glycol) and their assessment as SERS-active carriers of Raman tags

NASA Astrophysics Data System (ADS)

Boca, Sanda C.; Astilean, Simion

2010-06-01

We present an effective, low cost protocol to reduce the toxicity of gold nanorods induced by the presence of cetyltrimethylammonium bromide (CTAB) on their lateral surface as a result of the synthesis process. Here, we use thiolated methoxy-poly(ethylene) glycol (mPEG-SH) polymer to displace most of the CTAB bilayer cap from the particle surface. The detoxification process, chemical and structural stability of as-prepared mPEG-SH-conjugated gold nanorods were characterized using a number of techniques including localized surface plasmon resonance (LSPR), transmission electron microscopy (TEM) and surface-enhanced Raman spectroscopy (SERS). In view of future applications as near-infrared (NIR) nanoheaters in localized photothermal therapy of cancer, we investigated the thermal behaviour of mPEG-SH-conjugated gold nanorods above room temperature. We found a critical temperature at around 40 °C at which the adsorbed polymer layer is susceptible to undergo conformational changes. Additionally, we believe that such plasmonic nanoprobes could act as SERS-active carriers of Raman tags for application in cellular imaging. In this sense we successfully tested them as effective SERS substrates at 785 nm laser line with p-aminothiophenol (pATP) as a tag molecule.

Crystal Structure and Substrate Specificity Modification of Acetyl Xylan Esterase from Aspergillus luchuensis.

PubMed

Komiya, Dai; Hori, Akane; Ishida, Takuya; Igarashi, Kiyohiko; Samejima, Masahiro; Koseki, Takuya; Fushinobu, Shinya

2017-10-15

Acetyl xylan esterase (AXE) catalyzes the hydrolysis of the acetyl bonds present in plant cell wall polysaccharides. Here, we determined the crystal structure of AXE from Aspergillus luchuensis ( Al AXEA), providing the three-dimensional structure of an enzyme in the Esterase_phb family. Al AXEA shares its core α/β-hydrolase fold structure with esterases in other families, but it has an extended central β-sheet at both its ends and an extra loop. Structural comparison with a ferulic acid esterase (FAE) from Aspergillus niger indicated that Al AXEA has a conserved catalytic machinery: a catalytic triad (Ser119, His259, and Asp202) and an oxyanion hole (Cys40 and Ser120). Near the catalytic triad of A lAXEA, two aromatic residues (Tyr39 and Trp160) form small pockets at both sides. Homology models of fungal FAEs in the same Esterase_phb family have wide pockets at the corresponding sites because they have residues with smaller side chains (Pro, Ser, and Gly). Mutants with site-directed mutations at Tyr39 showed a substrate specificity similar to that of the wild-type enzyme, whereas those with mutations at Trp160 acquired an expanded substrate specificity. Interestingly, the Trp160 mutants acquired weak but significant type B-like FAE activity. Moreover, the engineered enzymes exhibited ferulic acid-releasing activity from wheat arabinoxylan. IMPORTANCE Hemicelluloses in the plant cell wall are often decorated by acetyl and ferulic acid groups. Therefore, complete and efficient degradation of plant polysaccharides requires the enzymes for cleaving the side chains of the polymer. Since the Esterase_phb family contains a wide array of fungal FAEs and AXEs from fungi and bacteria, our study will provide a structural basis for the molecular mechanism of these industrially relevant enzymes in biopolymer degradation. The structure of the Esterase_phb family also provides information for bacterial polyhydroxyalkanoate depolymerases that are involved in biodegradation of thermoplastic polymers. Copyright © 2017 American Society for Microbiology.

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.

Molecular mechanisms underlying PINK1 and Parkin catalyzed ubiquitylation of substrates on damaged mitochondria.

PubMed

Koyano, Fumika; Matsuda, Noriyuki

2015-10-01

PINK1 and Parkin are gene products that cause genetic recessive Parkinsonism. PINK1 is a protein kinase and Parkin is a ubiquitin ligase (E3) that links ubiquitin to a substrate. Importantly, under steady state conditions, the enzymatic activity of Parkin is completely suppressed, but is activated when mitochondria become abnormal. In 2013 and 2014, biochemical and structure-function analyses revealed a number of critical mechanistic insights. First, Parkin is a self-inhibitory E3 that suppresses its E3 activity via intramolecular interactions. Second, in response to a decrease in mitochondrial membrane potential, PINK1 phosphorylates Ser65 in both the Parkin ubiquitin-like domain and ubiquitin itself. These phosphorylation events cooperate to relieve the Parkin autoinhibition. Third, activated Parkin forms a ubiquitin-thioester bond at Cys431 to produce a reaction intermediate that catalyzes ubiquitylation of substrates on damaged mitochondria. While the molecular mechanism regulating Parkin enzymatic activity has largely eluded clarification, a complete picture is now emerging. Copyright © 2015 Elsevier B.V. All rights reserved.

Active Site Mutations Change the Cleavage Specificity of Neprilysin

PubMed Central

Sexton, Travis; Hitchcook, Lisa J.; Rodgers, David W.; Bradley, Luke H.; Hersh, Louis B.

2012-01-01

Neprilysin (NEP), a member of the M13 subgroup of the zinc-dependent endopeptidase family is a membrane bound peptidase capable of cleaving a variety of physiological peptides. We have generated a series of neprilysin variants containing mutations at either one of two active site residues, Phe563 and Ser546. Among the mutants studied in detail we observed changes in their activity towards leucine5-enkephalin, insulin B chain, and amyloid β1–40. For example, NEPF563I displayed an increase in preference towards cleaving leucine5-enkephalin relative to insulin B chain, while mutant NEPS546E was less discriminating than neprilysin. Mutants NEPF563L and NEPS546E exhibit different cleavage site preferences than neprilysin with insulin B chain and amyloid ß1–40 as substrates. These data indicate that it is possible to alter the cleavage site specificity of neprilysin opening the way for the development of substrate specific or substrate exclusive forms of the enzyme with enhanced therapeutic potential. PMID:22384224

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.

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.

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.

The somatostatin analogue octreotide confers sensitivity to rapamycin treatment on pituitary tumor cells.

PubMed

Cerovac, Vesna; Monteserin-Garcia, Jose; Rubinfeld, Hadara; Buchfelder, Michael; Losa, Marco; Florio, Tullio; Paez-Pereda, Marcelo; Stalla, Günter K; Theodoropoulou, Marily

2010-01-15

Rapamycin and its analogues have significant antiproliferative action against a variety of tumors. However, sensitivity to rapamycin is reduced by Akt activation that results from the ablative effects of rapamycin on a p70 S6K-induced negative feedback loop that blunts phosphoinositide 3-kinase (PI3K)-mediated support for Akt activity. Thus, sensitivity to rapamycin might be increased by imposing an upstream blockade to the PI3K/Akt pathway. Here, we investigated this model using the somatostatin analogue octreotide as a tool to decrease levels of activated Ser(473)-phosphorylated Akt (pAkt-Ser(473)) in pituitary tumor cells that express somatostatin receptors. Octreotide increased levels of phosphorylated insulin receptor substrate-1 that were suppressed by rapamycin, subsequently decreasing levels of pAkt-Ser(473) through effects on phosphotyrosine phosphatase SHP-1. Octreotide potentiated the antiproliferative effects of rapamycin in immortalized pituitary tumor cells or human nonfunctioning pituitary adenoma cells in primary cell culture, sensitizing tumor cells even to low rapamycin concentrations. Combined treatment of octreotide and rapamycin triggered G(1) cell cycle arrest, decreasing E2F transcriptional activity and cyclin E levels by increasing levels of p27/Kip1. These findings show that adjuvant treatment with a somatostatin analogue can sensitize pituitary tumor cells to the antiproliferative effects of rapamycin.

Eukaryotic-like Ser/Thr Protein Kinases SpkC/F/K Are Involved in Phosphorylation of GroES in the Cyanobacterium Synechocystis

PubMed Central

Zorina, Anna; Stepanchenko, Natalia; Novikova, Galina V.; Sinetova, Maria; Panichkin, Vladimir B.; Moshkov, Igor E.; Zinchenko, Vladislav V.; Shestakov, Sergey V.; Suzuki, Iwane; Murata, Norio; Los, Dmitry A.

2011-01-01

Serine/threonine protein kinases (STPKs) are the major participants in intracellular signal transduction in eukaryotes, such as yeasts, fungi, plants, and animals. Genome sequences indicate that these kinases are also present in prokaryotes, such as cyanobacteria. However, their roles in signal transduction in prokaryotes remain poorly understood. We have attempted to identify the roles of STPKs in response to heat stress in the prokaryotic cyanobacterium Synechocystis sp. PCC 6803, which has 12 genes for STPKs. Each gene was individually inactivated to generate a gene-knockout library of STPKs. We applied in vitro Ser/Thr protein phosphorylation and phosphoproteomics and identified the methionyl-tRNA synthetase, large subunit of RuBisCO, 6-phosphogluconate dehydrogenase, translation elongation factor Tu, heat-shock protein GrpE, and small chaperonin GroES as the putative targets for Ser/Thr phosphorylation. The expressed and purified GroES was used as an external substrate to screen the protein extracts of the individual mutants for their Ser/Thr kinase activities. The mutants that lack one of the three protein kinases, SpkC, SpkF, and SpkK, were unable to phosphorylate GroES in vitro, suggesting possible interactions between them towards their substrate. Complementation of the mutated SpkC, SpkF, and SpkK leads to the restoration of the ability of cells to phosphorylate the GroES. This suggests that these three STPKs are organized in a sequential order or a cascade and they work one after another to finally phosphorylate the GroES. PMID:21551175

Colloidal lithography with electrochemical nickel deposition as a unique method for improved silver decorated nanocavities in SERS applications

NASA Astrophysics Data System (ADS)

Petruš, Ondrej; Oriňak, Andrej; Oriňaková, Renáta; Orságová Králová, Zuzana; Múdra, Erika; Kupková, Miriam; Kovaľ, Karol

2017-11-01

Two types of metallised nanocavities (single and hybrid) were fabricated by colloid lithography followed by electrochemical deposition of Ni and subsequently Ag layers. Introductory Ni deposition step iniciates more homogenous decoration of nanocavities with Ag nanoparticles. Silver nanocavity decoration has been so performed with lower nucleation rate and with Ag nanoparticles homogeinity increase. By this, two step Ni and Ag deposition trough polystyrene nanospheres (100, 300, 500, 700, 900 nm), the various Ag surfaces were obtained. Ni layer formation in the first step of deposition enabled more precise controlling of Ag film deposition and thus final Ag surface morphology. Prepared substrates were tested as active surfaces in SERS application. The best SERS signal enhancement was observed at 500 nm Ag nanocavities with normalised thickness Ni layer ∼0.5. Enhancement factor has been established at value 1.078 × 1010; time stability was determined within 13 weeks; charge distribution at nanocavity Ag surfaces as well as reflection spectra were calculated by FDTD method. Newly prepared nanocavity surface can be applied in SERS analysis, predominantly.

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

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.

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.

Exposure to rosiglitazone, a PPAR-γ agonist, in late gestation reduces the abundance of factors regulating cardiac metabolism and cardiomyocyte size in the sheep fetus

PubMed Central

Lie, Shervi; Hui, Melisa; McMillen, I. Caroline; Muhlhausler, Beverly S.; Posterino, Giuseppe S.; Dunn, Stacey L.; Wang, Kimberley C.; Botting, Kimberley J.

2014-01-01

It is unknown whether cardiomyocyte hypertrophy and the transition to fatty acid oxidation as the main source of energy after birth is dependent on the maturation of the cardiomyocytes' metabolic system, or on the limitation of substrate availability before birth. This study aimed to investigate whether intrafetal administration of a peroxisome proliferator-activated receptor-γ (PPAR-γ) agonist, rosiglitazone, during late gestation can stimulate the expression of factors regulating cardiac growth and metabolism in preparation for birth, and the consequences of cardiac contractility in the fetal sheep at ∼140 days gestation. The mRNA expression and protein abundance of key factors regulating growth and metabolism were quantified using quantitative RT-PCR and Western blot analysis, respectively. Cardiac contractility was determined by measuring the Ca2+ sensitivity and maximum Ca2+-activated force of skinned cardiomyocyte bundles. Rosiglitazone-treated fetuses had a lower cardiac abundance of insulin-signaling molecules, including insulin receptor-β, insulin receptor substrate-1 (IRS-1), phospho-IRS-1 (Tyr-895), phosphatidylinositol 3-kinase (PI3K) regulatory subunit p85, PI3K catalytic subunit p110α, phospho-3-phosphoinositide-dependent protein kinase 1 (Ser-241), protein kinase B (Akt-1), phospho-Akt (Ser-273), PKCζ, phospho-PKCζ(Thr-410), Akt substrate 160 kDa (AS160), phospho-AS160 (Thr-642), and glucose transporter type-4. Additionally, cardiac abundance of regulators of fatty acid β-oxidation, including adiponectin receptor 1, AMPKα, phospho-AMPKα (Thr-172), phospho-acetyl CoA carboxylase (Ser-79), carnitine palmitoyltransferase-1, and PGC-1α was lower in the rosiglitazone-treated group. Rosiglitazone administration also resulted in a decrease in cardiomyocyte size. Rosiglitazone administration in the late-gestation sheep fetus resulted in a decreased abundance of factors regulating cardiac glucose uptake, fatty acid β-oxidation, and cardiomyocyte size. These findings suggest that activation of PPAR-γ using rosiglitazone does not promote the maturation of cardiomyocytes; rather, it may decrease cardiac metabolism and compromise cardiac health later in life. PMID:24477540

Exposure to rosiglitazone, a PPAR-γ agonist, in late gestation reduces the abundance of factors regulating cardiac metabolism and cardiomyocyte size in the sheep fetus.

PubMed

Lie, Shervi; Hui, Melisa; McMillen, I Caroline; Muhlhausler, Beverly S; Posterino, Giuseppe S; Dunn, Stacey L; Wang, Kimberley C; Botting, Kimberley J; Morrison, Janna L

2014-03-15

It is unknown whether cardiomyocyte hypertrophy and the transition to fatty acid oxidation as the main source of energy after birth is dependent on the maturation of the cardiomyocytes' metabolic system, or on the limitation of substrate availability before birth. This study aimed to investigate whether intrafetal administration of a peroxisome proliferator-activated receptor-γ (PPAR-γ) agonist, rosiglitazone, during late gestation can stimulate the expression of factors regulating cardiac growth and metabolism in preparation for birth, and the consequences of cardiac contractility in the fetal sheep at ∼140 days gestation. The mRNA expression and protein abundance of key factors regulating growth and metabolism were quantified using quantitative RT-PCR and Western blot analysis, respectively. Cardiac contractility was determined by measuring the Ca(2+) sensitivity and maximum Ca(2+)-activated force of skinned cardiomyocyte bundles. Rosiglitazone-treated fetuses had a lower cardiac abundance of insulin-signaling molecules, including insulin receptor-β, insulin receptor substrate-1 (IRS-1), phospho-IRS-1 (Tyr-895), phosphatidylinositol 3-kinase (PI3K) regulatory subunit p85, PI3K catalytic subunit p110α, phospho-3-phosphoinositide-dependent protein kinase 1 (Ser-241), protein kinase B (Akt-1), phospho-Akt (Ser-273), PKCζ, phospho-PKCζ(Thr-410), Akt substrate 160 kDa (AS160), phospho-AS160 (Thr-642), and glucose transporter type-4. Additionally, cardiac abundance of regulators of fatty acid β-oxidation, including adiponectin receptor 1, AMPKα, phospho-AMPKα (Thr-172), phospho-acetyl CoA carboxylase (Ser-79), carnitine palmitoyltransferase-1, and PGC-1α was lower in the rosiglitazone-treated group. Rosiglitazone administration also resulted in a decrease in cardiomyocyte size. Rosiglitazone administration in the late-gestation sheep fetus resulted in a decreased abundance of factors regulating cardiac glucose uptake, fatty acid β-oxidation, and cardiomyocyte size. These findings suggest that activation of PPAR-γ using rosiglitazone does not promote the maturation of cardiomyocytes; rather, it may decrease cardiac metabolism and compromise cardiac health later in life.

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-nanoparticles-decorated NiO-nanoflakes grafted Ni-nanorod arrays stuck out of porous AAO as effective SERS substrates.

PubMed

Zhou, Qitao; Meng, Guowen; Huang, Qing; Zhu, Chuhong; Tang, Haibin; Qian, Yiwu; Chen, Bin; Chen, Bensong

2014-02-28

NiO-nanoflakes (NiO-NFs) grafted Ni-nanorod (Ni-NR) arrays stuck out of the porous anodic aluminum oxide (AAO) template are achieved by a combinatorial process of AAO-confined electrodeposition of Ni-NRs, selectively etching part of the AAO template to expose the Ni-NRs, wet-etching the exposed Ni-NRs in ammonia to obtain Ni(OH)2-NFs grafted onto the cone-shaped Ni-NRs, and annealing to transform Ni(OH)2-NFs in situ into NiO-NFs. By top-view sputtering, Ag-nanoparticles (Ag-NPs) are decorated on each NiO-NFs grafted Ni-NR (denoted as NiO-NFs@Ni-NR). The resultant Ag-NPs-decorated NiO-NFs@Ni-NR (denoted as Ag-NPs@NiO-NFs@Ni-NR) arrays exhibit not only strong surface-enhanced Raman scattering (SERS) activity but also reproducible SERS-signals over the whole array. It is demonstrated that the strong SERS-activity is mainly ascribed to the high density of sub-10 nm gaps (hot spots) between the neighboring Ag-NPs, the semiconducting NiO-NFs induced chemical enhancement effect, and the lightning rod effect of the cone-shaped Ni-NRs. The three-level hierarchical nanostructure arrays stuck out of the AAO template can be utilized to probe polychlorinated biphenyls (PCBs, a kind of global environmental hazard) with a concentration as low as 5 × 10(-6) M, showing promising potential in SERS-based rapid detection of organic environmental pollutants.

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.

Molecular Basis for the Catalytic Specificity of the CTX-M Extended-Spectrum β-Lactamases

DOE PAGES

Adamski, Carolyn J.; Cardenas, Ana Maria; Brown, Nicholas G.; ...

2014-12-09

We report that extended-spectrum β-lactamases (ESBLs) pose a threat to public health because of their ability to confer resistance to extended-spectrum cephalosporins such as cefotaxime. The CTX-M β-lactamases are the most widespread ESBL enzymes among antibiotic resistant bacteria. Many of the active site residues are conserved between the CTX-M family and non-ESBL β-lactamases such as TEM-1, but the residues Ser237 and Arg276 are specific to the CTX-M family, suggesting that they may help to define the increased specificity for cefotaxime hydrolysis. To test this hypothesis, site-directed mutagenesis of these positions was performed in the CTX-M-14 β-lactamase. Substitutions of Ser237 andmore » Arg276 with their TEM-1 counterparts, Ala237 and Asn276, had a modest effect on cefotaxime hydrolysis, as did removal of the Arg276 side chain in an R276A mutant. The S237A:R276N and S237A:R276A double mutants, however, exhibited 29- and 14-fold losses in catalytic efficiency for cefotaxime hydrolysis, respectively, while the catalytic efficiency for benzylpenicillin hydrolysis was unchanged. Therefore, together, the Ser237 and Arg276 residues are important contributors to the cefotaximase substrate profile of the enzyme. High-resolution crystal structures of the CTX-M-14 S70G, S70G:S237A, and S70G:S237A:R276A variants alone and in complex with cefotaxime show that residues Ser237 and Arg276 in the wild-type enzyme promote the expansion of the active site to accommodate cefotaxime and favor a conformation of cefotaxime that allows optimal contacts between the enzyme and substrate. In conclusion, the conservation of these residues, linked to their effects on structure and catalysis, imply that their coevolution is an important specificity determinant in the CTX-M family.« less

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.

Exploring substrate binding and discrimination in fructose1, 6-bisphosphate and tagatose 1,6-bisphosphate aldolases.

PubMed

Zgiby, S M; Thomson, G J; Qamar, S; Berry, A

2000-03-01

Fructose 1,6-bisphosphate aldolase catalyses the reversible condensation of glycerone-P and glyceraldehyde 3-phosphate into fructose 1,6-bisphosphate. A recent structure of the Escherichia coli Class II fructose 1,6-bisphosphate aldolase [Hall, D.R., Leonard, G.A., Reed, C.D., Watt, C.I., Berry, A. & Hunter, W.N. (1999) J. Mol. Biol. 287, 383-394] in the presence of the transition state analogue phosphoglycolohydroxamate delineated the roles of individual amino acids in binding glycerone-P and in the initial proton abstraction steps of the mechanism. The X-ray structure has now been used, together with sequence alignments, site-directed mutagenesis and steady-state enzyme kinetics to extend these studies to map important residues in the binding of glyceraldehyde 3-phosphate. From these studies three residues (Asn35, Ser61 and Lys325) have been identified as important in catalysis. We show that mutation of Ser61 to alanine increases the Km value for fructose 1, 6-bisphosphate 16-fold and product inhibition studies indicate that this effect is manifested most strongly in the glyceraldehyde 3-phosphate binding pocket of the active site, demonstrating that Ser61 is involved in binding glyceraldehyde 3-phosphate. In contrast a S61T mutant had no effect on catalysis emphasizing the importance of an hydroxyl group for this role. Mutation of Asn35 (N35A) resulted in an enzyme with only 1.5% of the activity of the wild-type enzyme and different partial reactions indicate that this residue effects the binding of both triose substrates. Finally, mutation of Lys325 has a greater effect on catalysis than on binding, however, given the magnitude of the effects it is likely that it plays an indirect role in maintaining other critical residues in a catalytically competent conformation. Interestingly, despite its proximity to the active site and high sequence conservation, replacement of a fourth residue, Gln59 (Q59A) had no significant effect on the function of the enzyme. In a separate study to characterize the molecular basis of aldolase specificity, the agaY-encoded tagatose 1,6-bisphosphate aldolase of E. coli was cloned, expressed and kinetically characterized. Our studies showed that the two aldolases are highly discriminating between the diastereoisomers fructose bisphosphate and tagatose bisphosphate, each enzyme preferring its cognate substrate by a factor of 300-1500-fold. This produces an overall discrimination factor of almost 5 x 105 between the two enzymes. Using the X-ray structure of the fructose 1,6-bisphosphate aldolase and multiple sequence alignments, several residues were identified, which are highly conserved and are in the vicinity of the active site. These residues might potentially be important in substrate recognition. As a consequence, nine mutations were made in attempts to switch the specificity of the fructose 1,6-bisphosphate aldolase to that of the tagatose 1,6-bisphosphate aldolase and the effect on substrate discrimination was evaluated. Surprisingly, despite making multiple changes in the active site, many of which abolished fructose 1, 6-bisphosphate aldolase activity, no switch in specificity was observed. This highlights the complexity of enzyme catalysis in this family of enzymes, and points to the need for further structural studies before we fully understand the subtleties of the shaping of the active site for complementarity to the cognate substrate.

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.

Serine/threonine protein kinase PrkA of the human pathogen Listeria monocytogenes: biochemical characterization and identification of interacting partners through proteomic approaches.

PubMed

Lima, Analía; Durán, Rosario; Schujman, Gustavo Enrique; Marchissio, María Julia; Portela, María Magdalena; Obal, Gonzalo; Pritsch, Otto; de Mendoza, Diego; Cerveñansky, Carlos

2011-08-24

Listeria monocytogenes is the causative agent of listeriosis, a very serious food-borne human disease. The analysis of the proteins coded by the L. monocytogenes genome reveals the presence of two eukaryotic-type Ser/Thr-kinases (lmo1820 and lmo0618) and a Ser/Thr-phosphatase (lmo1821). Protein phosphorylation regulates enzyme activities and protein interactions participating in physiological and pathophysiological processes in bacterial diseases. However in the case of L. monocytogenes there is scarce information about biochemical properties of these enzymes, as well as the physiological processes that they modulate. In the present work the catalytic domain of the protein coded by lmo1820 was produced as a functional His(6)-tagged Ser/Thr-kinase, and was denominated PrkA. PrkA was able to autophosphorylate specific Thr residues within its activation loop sequence. A similar autophosphorylation pattern was previously reported for Ser/Thr-kinases from related prokaryotes, whose role in kinase activity and substrate recruitment was demonstrated. We studied the kinase interactome using affinity chromatography and proteomic approaches. We identified 62 proteins that interact, either directly or indirectly, with the catalytic domain of PrkA, including proteins that participate in carbohydrates metabolism, cell wall metabolism and protein synthesis. Our results suggest that PrkA could be involved in the regulation of a variety of fundamental biological processes. Copyright © 2011 Elsevier B.V. All rights reserved.

Cell cycle-dependent regulation of Greatwall kinase by protein phosphatase 1 and regulatory subunit 3B.

PubMed

Ren, Dapeng; Fisher, Laura A; Zhao, Jing; Wang, Ling; Williams, Byron C; Goldberg, Michael L; Peng, Aimin

2017-06-16

Greatwall (Gwl) kinase plays an essential role in the regulation of mitotic entry and progression. Mitotic activation of Gwl requires both cyclin-dependent kinase 1 (CDK1)-dependent phosphorylation and its autophosphorylation at an evolutionarily conserved serine residue near the carboxyl terminus (Ser-883 in Xenopus ). In this study we show that Gwl associates with protein phosphatase 1 (PP1), particularly PP1γ, which mediates the dephosphorylation of Gwl Ser-883. Consistent with the mitotic activation of Gwl, its association with PP1 is disrupted in mitotic cells and egg extracts. During mitotic exit, PP1-dependent dephosphorylation of Gwl Ser-883 occurs prior to dephosphorylation of other mitotic substrates; replacing endogenous Gwl with a phosphomimetic S883E mutant blocks mitotic exit. Moreover, we identified PP1 regulatory subunit 3B (PPP1R3B) as a targeting subunit that can direct PP1 activity toward Gwl. PPP1R3B bridges PP1 and Gwl association and promotes Gwl Ser-883 dephosphorylation. Consistent with the cell cycle-dependent association of Gwl and PP1, Gwl and PPP1R3B dissociate in M phase. Interestingly, up-regulation of PPP1R3B facilitates mitotic exit and blocks mitotic entry. Thus, our study suggests PPP1R3B as a new cell cycle regulator that functions by governing Gwl dephosphorylation. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

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

Serine 302 Phosphorylation of Mouse Insulin Receptor Substrate 1 (IRS1) Is Dispensable for Normal Insulin Signaling and Feedback Regulation by Hepatic S6 Kinase*

PubMed Central

Copps, Kyle D.; Hançer, Nancy J.; Qiu, Wei; White, Morris F.

2016-01-01

Constitutive activation of the mammalian target of rapamycin complex 1 and S6 kinase (mTORC1→ S6K) attenuates insulin-stimulated Akt activity in certain tumors in part through “feedback” phosphorylation of the upstream insulin receptor substrate 1 (IRS1). However, the significance of this mechanism for regulating insulin sensitivity in normal tissue remains unclear. We investigated the function of Ser-302 in mouse IRS1, the major site of its phosphorylation by S6K in vitro, through genetic knock-in of a serine-to-alanine mutation (A302). Although insulin rapidly stimulated feedback phosphorylation of Ser-302 in mouse liver and muscle, homozygous A302 mice (A/A) and their knock-in controls (S/S) exhibited similar glucose homeostasis and muscle insulin signaling. Furthermore, both A302 and control primary hepatocytes from which Irs2 was deleted showed marked inhibition of insulin-stimulated IRS1 tyrosine phosphorylation and PI3K binding after emetine treatment to raise intracellular amino acids and activate mTORC1 → S6K signaling. To specifically activate mTORC1 in mouse tissue, we deleted hepatic Tsc1 using Cre adenovirus. Although it moderately decreased IRS1/PI3K association and Akt phosphorylation in liver, Tsc1 deletion failed to cause glucose intolerance or promote hyperinsulinemia in mixed background A/A or S/S mice. Moreover, Tsc1 deletion failed to stimulate phospho-Ser-302 or other putative S6K sites within IRS1, whereas ribosomal S6 protein was constitutively phosphorylated. Following acute Tsc1 deletion from hepatocytes, Akt phosphorylation, but not IRS1/PI3K association, was rapidly restored by treatment with the mTORC1 inhibitor rapamycin. Thus, within the hepatic compartment, mTORC1 → S6K signaling regulates Akt largely through IRS-independent means with little effect upon physiologic insulin sensitivity. PMID:26846849

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.

Influence of the metal ion on the enzyme activity and kinetics of PepA from Lactobacillus delbrueckii.

PubMed

Ewert, Jacob; Glück, Claudia; Strasdeit, Henry; Fischer, Lutz; Stressler, Timo

2018-03-01

The aminopeptidase A (PepA; EC 3.4.11.7) belongs to the group of metallopeptidases with two bound metal ions per subunit (M1M2(PepA)) and is specific for the cleavage of N-terminal glutamic (Glu) and aspartic acid (Asp) and, in low amounts, serine (Ser) residues. Our group recently characterized the first PepA from a Lactobacillus strain. However, the characterization was performed using synthetic para-nitroaniline substrates and not original peptide substrates, as was done in the current study. Prior to the characterization using original peptide substrates, the PepA purified was converted to its inactive apo-form and eight different metal ions were tested to restore its activity. It was found that five of the metal ions were able to reactivate apo-PepA: Co 2+ , Cu 2+ , Mn 2+ , Ni 2+ and Zn 2+ . Interestingly, depending on the metal ion used for reactivation, the activity and the pH and temperature profile differed. Exemplarily, MnMn(PepA), NiNi(PepA) and ZnZn(PepA) had an activity optimum using MES buffer (50mM, pH 6.0) and 60°C, whereas the activity optimum changed to Na/K-phosphate-buffer (50mM, pH 7.0) and 55°C for CuCu(PepA). However, more important than the changes in optimum pH and temperature, the kinetic properties of PepA were affected by the metal ion used. While all PepA variants could release N-terminal Glu or Asp, only CoCo(PepA), NiNi(PepA) and CuCu(PepA) could release Ser from the particular peptide substrate. In addition, it was found that the enzyme efficiency (V max /K M ) and catalytic mechanism (positive cooperative binding (Hill coefficent; n), substrate inhibition (K IS )) were influenced by the metal ion. Exemplarily, a high cooperativity (n>2),K IS value >20mM and preference for N-terminal Glu were detected for CuCu(PepA). In summary, the results suggested that an exchange of the metal ion can be used for tailoring the properties of PepA for specific hydrolysis requirements. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

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.

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

11β-Hydroxysteroid Dehydrogenase Type 1 Regulates Glucocorticoid-Induced Insulin Resistance in Skeletal Muscle

PubMed Central

Morgan, Stuart A.; Sherlock, Mark; Gathercole, Laura L.; Lavery, Gareth G.; Lenaghan, Carol; Bujalska, Iwona J.; Laber, David; Yu, Alice; Convey, Gemma; Mayers, Rachel; Hegyi, Krisztina; Sethi, Jaswinder K.; Stewart, Paul M.; Smith, David M.; Tomlinson, Jeremy W.

2009-01-01

OBJECTIVE Glucocorticoid excess is characterized by increased adiposity, skeletal myopathy, and insulin resistance, but the precise molecular mechanisms are unknown. Within skeletal muscle, 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) converts cortisone (11-dehydrocorticosterone in rodents) to active cortisol (corticosterone in rodents). We aimed to determine the mechanisms underpinning glucocorticoid-induced insulin resistance in skeletal muscle and indentify how 11β-HSD1 inhibitors improve insulin sensitivity. RESEARCH DESIGN AND METHODS Rodent and human cell cultures, whole-tissue explants, and animal models were used to determine the impact of glucocorticoids and selective 11β-HSD1 inhibition upon insulin signaling and action. RESULTS Dexamethasone decreased insulin-stimulated glucose uptake, decreased IRS1 mRNA and protein expression, and increased inactivating pSer307 insulin receptor substrate (IRS)-1. 11β-HSD1 activity and expression were observed in human and rodent myotubes and muscle explants. Activity was predominantly oxo-reductase, generating active glucocorticoid. A1 (selective 11β-HSD1 inhibitor) abolished enzyme activity and blocked the increase in pSer307 IRS1 and reduction in total IRS1 protein after treatment with 11DHC but not corticosterone. In C57Bl6/J mice, the selective 11β-HSD1 inhibitor, A2, decreased fasting blood glucose levels and improved insulin sensitivity. In KK mice treated with A2, skeletal muscle pSer307 IRS1 decreased and pThr308 Akt/PKB increased. In addition, A2 decreased both lipogenic and lipolytic gene expression. CONCLUSIONS Prereceptor facilitation of glucocorticoid action via 11β-HSD1 increases pSer307 IRS1 and may be crucial in mediating insulin resistance in skeletal muscle. Selective 11β-HSD1 inhibition decreases pSer307 IRS1, increases pThr308 Akt/PKB, and decreases lipogenic and lipolytic gene expression that may represent an important mechanism underpinning their insulin-sensitizing action. PMID:19675138

Identification of Major Enzymes Involved in the Synthesis of Diadenosine Tetraphosphate and/or Adenosine Tetraphosphate in Myxococcus xanthus.

PubMed

Kimura, Yoshio; Tanaka, Chihiro; Oka, Manami

2018-07-01

Myxococcus xanthus generates diadenosine tetraphosphates (Ap 4 A) and diadenosine pentaphosphates (Ap 5 A) under various stress conditions. M. xanthus lysyl-tRNA synthetase (LysS) efficiently synthesizes Ap 4 A from ATP, Ap 5 A from ATP and adenosine tetraphosphate (Ap 4 ), and Ap 4 from ATP and triphosphate. To identify other M. xanthus enzymes that can catalyze Ap 4 A and Ap 4 synthesis, 15 M. xanthus aminoacyl-tRNA synthetases (aaRSs), four acyl-CoA synthetases (Acys), three acetyl-CoA synthetases (Aces), phosphoglycerate kinase (Pgk), and adenylate kinase (Adk) were expressed in Escherichia coli and examined for Ap 4 A or Ap 4 synthetase activity using ATP or ATP and triphosphate as substrates. Among the tested enzymes, LysS had the highest Ap 4 A synthetase activity. AlaRS, SerRS, and LeuRS1 showed high ADP synthetase activity with ATP as a substrate in the presence of pyrophosphatase, and also demonstrated the ability to produce Ap 4 from ATP and triphosphate in the absence of pyrophosphatase. Ap 4 formation by AlaRS, SerRS, and LeuRS1 was approximately 4- to 13-fold higher compared with that of Ap 4 A, suggesting that these enzymes prefer triphosphate over ATP as a substrate in the second reaction. Some of the recombinant M. xanthus Acys and Aces also synthesized Ap 4 from ATP and triphosphate. However, Pgk was capable of catalyzing the production of Ap 4 from ATP and 3-phosphoglycerate in the presence of Mg 2+ and did not require triphosphate, suggesting that this enzyme is mainly responsible for Ap 4 synthesis in M. xanthus.

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

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.

Identification of amphiphysin 1 as an endogenous substrate for CDKL5, a protein kinase associated with X-linked neurodevelopmental disorder.

PubMed

Sekiguchi, Mari; Katayama, Syouichi; Hatano, Naoya; Shigeri, Yasushi; Sueyoshi, Noriyuki; Kameshita, Isamu

2013-07-15

Cyclin-dependent kinase-like 5 (CDKL5) is a Ser/Thr protein kinase predominantly expressed in brain and mutations of its gene are known to be associated with neurodevelopmental disorders such as X-linked West syndrome and Rett syndrome. However, the physiological substrates of CDKL5 that are directly linked to these neurodevelopmental disorders are currently unknown. In this study, we explored endogenous substrates for CDKL5 in mouse brain extracts fractionated by a liquid-phase isoelectric focusing. In conjunction with CDKL5 phosphorylation assay, this approach detected a protein band with an apparent molecular mass of 120kDa that is remarkably phosphorylated by CDKL5. This 120-kDa protein was identified as amphiphysin 1 (Amph1) by LC-MS/MS analysis, and the site of phosphorylation by CDKL5 was determined to be Ser-293. The phosphorylation mimic mutants, Amph1(S293E) and Amph1(S293D), showed significantly reduced affinity for endophilin, a protein involved in synaptic vesicle endocytosis. Introduction of point mutations in the catalytic domain of CDKL5, which are disease-causing missense mutations found in Rett patients, resulted in the impairment of kinase activity toward Amph1. These results suggest that Amph1 is the cytoplasmic substrate for CDKL5 and that its phosphorylation may play crucial roles in the neuronal development. Copyright © 2013 Elsevier Inc. All rights reserved.

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

PubMed

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

2016-06-23

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

Plasmonic nanohole array for enhancing the SERS signal of a single layer of graphene in water

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

Mahigir, Amirreza; Chang, Te-Wei; Behnam, Ashkan

In this study, we numerically design and experimentally test a SERS-active substrate for enhancing the SERS signal of a single layer of graphene (SLG) in water. The SLG is placed on top of an array of silver-covered nanoholes in a polymer and is covered with water. Here we report a large enhancement of up to 2×10 5 in the SERS signal of the SLG on the patterned plasmonic nanostructure for a 532nm excitation laser wavelength. We provide a detailed study of the light-graphene interactions by investigating the optical absorption in the SLG, the density of optical states at the locationmore » of the SLG, and the extraction efficiency of the SERS signal of the SLG. Our numerical calculations of both the excitation field and the emission rate enhancements support the experimental results. We find that the enhancement is due to the increase in the confinement of electromagnetic fields on the location of the SLG that results in enhanced light absorption in the graphene at the excitation wavelength. We also find that water droplets increase the density of optical radiative states at the location of the SLG, leading to enhanced spontaneous emission rate of graphene at its Raman emission wavelengths.« less

Plasmonic nanohole array for enhancing the SERS signal of a single layer of graphene in water

DOE PAGES

Mahigir, Amirreza; Chang, Te-Wei; Behnam, Ashkan; ...

2017-10-25

In this study, we numerically design and experimentally test a SERS-active substrate for enhancing the SERS signal of a single layer of graphene (SLG) in water. The SLG is placed on top of an array of silver-covered nanoholes in a polymer and is covered with water. Here we report a large enhancement of up to 2×10 5 in the SERS signal of the SLG on the patterned plasmonic nanostructure for a 532nm excitation laser wavelength. We provide a detailed study of the light-graphene interactions by investigating the optical absorption in the SLG, the density of optical states at the locationmore » of the SLG, and the extraction efficiency of the SERS signal of the SLG. Our numerical calculations of both the excitation field and the emission rate enhancements support the experimental results. We find that the enhancement is due to the increase in the confinement of electromagnetic fields on the location of the SLG that results in enhanced light absorption in the graphene at the excitation wavelength. We also find that water droplets increase the density of optical radiative states at the location of the SLG, leading to enhanced spontaneous emission rate of graphene at its Raman emission wavelengths.« less

Substrate binding ability of chemically inactivated pectinase for the substrate pectic acid.

PubMed

Chiba, Y; Kobayashi, M

1995-07-01

Pectinase (polygalacturonase) was purified from a commercial pectinase preparation from a mold. Substrate binding of pectinase was measured by centrifugal affinity chromatography using an immobilized substrate, pectic acid. Desorption of pectinase from the affinity matrix with the substrate pectin and pectic acid gave Kd values of 5.3 and 8.5 mg/ml, respectively. Chemical modification of pectinase by 1-ethyl-3-(3-dimethyl-aminopropyl)carbodiimide (EDC) and diethyl pyrocarbonate (DEP) caused a loss of most of the enzyme activity, but the substrate binding ability was not impaired. Thus, the pectinase preparation was digested with lysyl endopeptidase and the resulting peptides were treated with pectic acid-affinity gel. Three peptide fragments, which were recovered from the affinity column and sequenced, were identical to sequences in the second pectinase gene from Aspergillus niger. The first peptide contained 17 amino acids, Asp101-Ser117, and the second and third peptides corresponded to 18 amino acids of Asn152-Asp169. These results indicate that the inactivated pectinase retained substrate binding ability and would function as an acidic polysaccharide recognizing protein.

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

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

Ren, Jinqi; Cook, Aaron A.; Bergmeier, Wolfgang

The dynamic regulation of ERK1 and -2 (ERK1/2) is required for precise signal transduction controlling cell proliferation, differentiation, and survival. However, the underlying mechanisms regulating the activation of ERK1/2 are not completely understood. In this study, we show that phosphorylation of RasGRP2, a guanine nucleotide exchange factor (GEF), inhibits its ability to activate the small GTPase Rap1 that ultimately leads to decreased activation of ERK1/2 in cells. ERK2 phosphorylates RasGRP2 at Ser394 located in the linker region implicated in its autoinhibition. These studies identify RasGRP2 as a novel substrate of ERK1/2 and define a negative-feedback loop that regulates the BRaf–MEK–ERKmore » signaling cascade. This negative-feedback loop determines the amplitude and duration of active ERK1/2. -- Highlights: •ERK2 phosphorylates the guanine nucleotide exchange factor RasGRP2 at Ser394. •Phosphorylated RasGRP2 has decreased capacity to active Rap1b in vitro and in cells. •Phosphorylation of RasGRP2 by ERK1/2 introduces a negative-feedback loop into the BRaf-MEK-ERK pathway.« less

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.

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.

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.

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.

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.

Structure of PINK1 in complex with its substrate ubiquitin

PubMed Central

Schubert, Alexander F.; Gladkova, Christina; Pardon, Els; Wagstaff, Jane L.; Freund, Stefan M.V.; Steyaert, Jan; Maslen, Sarah L.; Komander, David

2018-01-01

Autosomal recessive juvenile Parkinsonism (AR-JP) is caused by mutations in a number of PARK genes, in particular in the E3 ubiquitin ligase Parkin (PARK2), and in its upstream protein kinase PINK1 (PARK6). PINK1 phosphorylates ubiquitin and the Parkin ubiquitin-like domain on structurally protected Ser65 to trigger mitophagy. We here report a crystal structure of a nanobody stabilised complex between Pediculus humanus corporis (Ph)PINK1 bound to ubiquitin in the ‘C-terminally retracted’ (Ub-CR) conformation. The structure reveals many peculiarities of PINK1, including the architecture of the C-terminal region, and reveals how the PINK1 N-lobe binds ubiquitin via a unique insertion. The flexible Ser65-loop in the Ub-CR conformation reaches the activation segment, facilitating placement of Ser65 in a phosphate accepting position. The structure also explains how autophosphorylation in the N-lobe stabilises structurally and functionally important insertions, and reveals the molecular basis for AR-JP causing mutations, some of which disrupt ubiquitin binding. PMID:29160309

Interfacial self-assembled functional nanoparticle array: a facile surface-enhanced Raman scattering sensor for specific detection of trace analytes.

PubMed

Zhang, Kun; Ji, Ji; Li, Yixin; Liu, Baohong

2014-07-01

Surface-enhanced Raman scattering (SERS) has proven to be promising for the detection of trace analytes; however, the precise nanofabrication of a specific and sensitive plasmonic SERS-active substrate is still a major challenge that limits the scope of its applications. In this work, gold nanoparticles are self-assembled into densely packed two-dimensional arrays at a liquid/liquid interface between dimethyl carbonate and water in the absence of template controller molecules. Both the simulation and experiment results show that the particles within these film-like arrays exhibit strong electromagnetic coupling and enable large amplification of Raman signals. In order to realize the level of sensing specificity, the surface chemistry of gold nanoparticles (Au NPs) is rationally tailored by incorporating an appropriate chemical moiety that specifically captures molecules of interest. The ease of fabrication and good uniformity make this platform ideal for in situ SERS sensing of trace targets in complex samples.

Self-assembled silver nanoparticle films at an air-liquid interface and their applications in SERS and electrochemistry

NASA Astrophysics Data System (ADS)

Wang, Li; Sun, Yujing; Che, Guangbo; Li, Zhuang

2011-06-01

In this paper, we present a novel technique to prepare silver nanoparticle films by controlling the self-assembly of nanoparticles at an air-liquid interface. In an ethanol-water phase, silver nanoparticles were prepared by reduction of AgNO 3 aqueous solution with NaBH 4 in the presence of cinnamic acid. It was found that the silver nanoparticles in this process could be trapped at the air-liquid interface to form 2-dimensional nanoparticle films. The morphology of nanoparticle films could be controlled by systematic variation of the experimental parameters. It is worth noting that the nanoparticle films could serve as the active substrates for surface-enhanced Raman scattering (SERS). 4-Aminothiophenol (4-ATP) molecule was used as a test probe to investigate the SERS sensitivity of different nanoparticle films. The results indicated that the nanoparticle films showed excellent Raman enhancement effect. Furthermore, the nanoparticle films prepared by our strategy were found to be efficient electrocatalysts for anodic oxidation of formaldehyde in alkaline medium.

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.

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 ...

Indium nanoparticles for ultraviolet surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Das, Rupali; Soni, R. K.

2018-05-01

Ultraviolet Surface-enhanced Raman spectroscopy (UVSERS) has emerged as an efficient molecular spectroscopy technique for ultra-sensitive and ultra-low detection of analyte concentration. The generic SERS substrates based on gold and silver nanostructures have been extensively explored for high local electric field enhancement only in visible-NIR region of the electromagnetic spectrum. The template synthesis of controlled nanoscale size metallic nanostructures supporting localized surface plasmon resonance (LSPR) in the UV region have been recently explored due to their ease of synthesis and potential applications in optoelectronic, catalysis and magnetism. Indium (In0) nanoparticles exhibit active surface plasmon resonance (SPR) in ultraviolet (UV) and deep-ultaviolet (DUV) region with optimal absorption losses. This extended accessibility makes indium a promising material for UV plasmonic, chemical sensing and more recently in UV-SERS. In this work, spherical indium nanoparticles (In NPs) were synthesized by modified polyol reduction method using NaBH4 having local surface plasmon resonance near 280 nm. The as-synthesized spherical In0 nanoparticles were then coated with thin silica shells of thickness ˜ 5nm by a modified Stober method protecting the nanoparticles from agglomeration, direct contact with the probed molecules as well as prevent oxidation of the nanoparticles. Morphological evolution of In0 nanoparticles and SiO2 coating were characterized by transmission electron microscope (TEM). An enhanced near resonant shell-isolated SERS activity from thin film of tryptophan (Tryp) molecules deposited on indium coated substrates under 325nm UV excitation was observed. Finite difference time domain (FDTD) method is employed to comprehend the experimental results and simulate the electric field contours which showed amplified electromagnetic field localized around the nanostructures. The comprehensive analysis indicates that indium is a promising alternate exogenous contrast agent for efficient Raman spectroscopy from molecules.

Sex differences in the metabolic dysfunction and insulin resistance of skeletal muscle glucose transport following high fructose ingestion.

PubMed

Rattanavichit, Yupaporn; Chukijrungroat, Natsasi; Saengsirisuwan, Vitoon

2016-12-01

The role of high fructose ingestion (HFI) in the development of conditions mimicking human metabolic syndrome has mostly been demonstrated in male animals; however, the extent of HFI-induced metabolic alterations in females remains unclear. The present study investigated whether HFI-induced metabolic perturbations differ between sexes and whether HFI aggravates the metabolic disturbances under ovarian hormone deprivation. Male, female, and ovariectomized (OVX) Sprague-Dawley rats were given either water or liquid fructose (10% wt/vol) for 6 wk. Blood pressure, glucose tolerance, insulin-stimulated glucose transport activity and signaling proteins, including insulin receptor (IR), insulin receptor substrate 1 (IRS-1), Akt, Akt substrate of 160 kDa (AS160), AMPKα, JNK, p38 MAPK, angiotensin-converting enzyme (ACE), ANG II type 1 receptor (AT 1 R), ACE2, and Mas receptor (MasR) in skeletal muscle, were evaluated. We found that HFI led to glucose intolerance and hypertension in male and OVX rats but not in female rats with intact ovaries. Moreover, HFI did not induce insulin resistance in the skeletal muscle of female and OVX rats but impaired the insulin-stimulated glucose transport activity in the skeletal muscle of male rats, which was accompanied by lower insulin-stimulated IRS-1 Tyr 989 (44%), Akt Ser 473 (30%), and AS160 Ser 588 (43%), and increases in insulin-stimulated IRS-1 Ser 307 (78%), JNK Thr 183 /Tyr 185 (69%), and p38 MAPK Thr 180 /Tyr 182 (81%). The results from the present study show sex differences in the development of metabolic syndrome-like conditions and indicate the protective role of female sex hormones against HFI-induced cardiometabolic abnormalities. Copyright © 2016 the American Physiological Society.

Importance of a serine proximal to the C(4a) and N(5) flavin atoms for hydride transfer in choline oxidase.

PubMed

Yuan, Hongling; Gadda, Giovanni

2011-02-08

Choline oxidase catalyzes the flavin-dependent, two-step oxidation of choline to glycine betaine with the formation of an aldehyde intermediate. In the first oxidation reaction, the alcohol substrate is initially activated to its alkoxide via proton abstraction. The substrate is oxidized via transfer of a hydride from the alkoxide α-carbon to the N(5) atom of the enzyme-bound flavin. In the wild-type enzyme, proton and hydride transfers are mechanistically and kinetically uncoupled. In this study, we have mutagenized an active site serine proximal to the C(4a) and N(5) atoms of the flavin and investigated the reactions of proton and hydride transfers by using substrate and solvent kinetic isotope effects. Replacement of Ser101 with threonine, alanine, cysteine, or valine resulted in biphasic traces in anaerobic reductions of the flavin with choline investigated in a stopped-flow spectrophotometer. Kinetic isotope effects established that the kinetic phases correspond to the proton and hydride transfer reactions catalyzed by the enzyme. Upon removal of Ser101, there is an at least 15-fold decrease in the rate constants for proton abstraction, irrespective of whether threonine, alanine, valine, or cysteine is present in the mutant enzyme. A logarithmic decrease spanning 4 orders of magnitude is seen in the rate constants for hydride transfer with increasing hydrophobicity of the side chain at position 101. This study shows that the hydrophilic character of a serine residue proximal to the C(4a) and N(5) flavin atoms is important for efficient hydride transfer.

Insights into the glycyl radical enzyme active site of benzylsuccinate synthase: a computational study.

PubMed

Bharadwaj, Vivek S; Dean, Anthony M; Maupin, C Mark

2013-08-21

The fumarate addition reaction, catalyzed by the enzyme benzylsuccinate synthase (BSS), is considered to be one of the most intriguing and energetically challenging reactions in biology. BSS belongs to the glycyl radical enzyme family and catalyzes the fumarate addition reaction, which enables microorganisms to utilize hydrocarbons as an energy source under anaerobic conditions. Unfortunately, the extreme sensitivity of the glycyl radical to oxygen has hampered the structural and kinetic characterization of BSS, thereby limiting our knowledge on this enzyme. To enhance our molecular-level understanding of BSS, a computational approach involving homology modeling, docking studies, and molecular dynamics (MD) simulations has been used to deduce the structure of BSS's catalytic subunit (BSSα) and illuminate the molecular basis for the fumarate addition reaction. We have identified two conserved and distinct binding pockets at the BSSα active site: a hydrophobic pocket for toluene binding and a polar pocket for fumaric acid binding. Subsequent dynamical and energetic evaluations have identified Glu509, Ser827, Leu390, and Phe384 as active site residues critical for substrate binding. The orientation of substrates at the active site observed in MD simulations is consistent with experimental observations of the syn addition of toluene to fumaric acid. It is also found that substrate binding tightens the active site and restricts the conformational flexibility of the thiyl radical, leading to hydrogen transfer distances conducive to the proposed reaction mechanism. The stability of substrates at the active site and the occurrence of feasible radical transfer distances between the thiyl radical, substrates, and the active site glycine indicate a substrate-assisted radical transfer pathway governing fumarate addition.

A Separate Pool of Cardiac Phospholemman That Does Not Regulate or Associate with the Sodium Pump

PubMed Central

Wypijewski, Krzysztof J.; Howie, Jacqueline; Reilly, Louise; Tulloch, Lindsay B.; Aughton, Karen L.; McLatchie, Linda M.; Shattock, Michael J.; Calaghan, Sarah C.; Fuller, William

2013-01-01

Phospholemman (PLM), the principal quantitative sarcolemmal substrate for protein kinases A and C in the heart, regulates the cardiac sodium pump. Much like phospholamban, which regulates the related ATPase SERCA, PLM is reported to oligomerize. We investigated subpopulations of PLM in adult rat ventricular myocytes based on phosphorylation status. Co-immunoprecipitation identified two pools of PLM: one not associated with the sodium pump phosphorylated at Ser63 and one associated with the pump, both phosphorylated at Ser68 and unphosphorylated. Phosphorylation of PLM at Ser63 following activation of PKC did not abrogate association of PLM with the pump, so its failure to associate with the pump was not due to phosphorylation at this site. All pools of PLM co-localized to cell surface caveolin-enriched microdomains with sodium pump α subunits, despite the lack of caveolin-binding motif in PLM. Mass spectrometry analysis of phosphospecific immunoprecipitation reactions revealed no unique protein interactions for Ser63-phosphorylated PLM, and cross-linking reagents also failed to identify any partner proteins for this pool. In lysates from hearts of heterozygous transgenic animals expressing wild type and unphosphorylatable PLM, Ser63-phosphorylated PLM co-immunoprecipitated unphosphorylatable PLM, confirming the existence of PLM multimers. Dephosphorylation of the PLM multimer does not change sodium pump activity. Hence like phospholamban, PLM exists as a pump-inhibiting monomer and an unassociated oligomer. The distribution of different PLM phosphorylation states to different pools may be explained by their differential proximity to protein phosphatases rather than a direct effect of phosphorylation on PLM association with the pump. PMID:23532852

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.

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 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

Role of Ser-257 in the sliding mechanism of NADP(H) in the reaction catalyzed by the Aspergillus fumigatus flavin-dependent ornithine N5-monooxygenase SidA.

PubMed

Shirey, Carolyn; Badieyan, Somayesadat; Sobrado, Pablo

2013-11-08

SidA (siderophore A) is a flavin-dependent N-hydroxylating monooxygenase that is essential for virulence in Aspergillus fumigatus. SidA catalyzes the NADPH- and oxygen-dependent formation of N(5)-hydroxyornithine. In this reaction, NADPH reduces the flavin, and the resulting NADP(+) is the last product to be released. The presence of NADP(+) is essential for activity, as it is required for stabilization of the C4a-hydroperoxyflavin, which is the hydroxylating species. As part of our efforts to determine the molecular details of the role of NADP(H) in catalysis, we targeted Ser-257 for site-directed mutagenesis and performed extensive characterization of the S257A enzyme. Using a combination of steady-state and stopped-flow kinetic experiments, substrate analogs, and primary kinetic isotope effects, we show that the interaction between Ser-257 and NADP(H) is essential for stabilization of the C4a-hydroperoxyflavin. Molecular dynamics simulation results suggest that Ser-257 functions as a pivot point, allowing the nicotinamide of NADP(+) to slide into position for stabilization of the C4a-hydroperoxyflavin.

Silver-gelatine bionanocomposites for qualitative detection of a pesticide by SERS.

PubMed

Fateixa, S; Soares, S F; Daniel-da-Silva, A L; Nogueira, H I S; Trindade, T

2015-03-07

The controlled release of pesticides using hydrogel vehicles is an important procedure to limit the amount of these compounds in the environment, providing an effective way for crop protection. A key-step in the formulation of new materials for these purposes encompasses the monitoring of available pesticides in the gel matrix under variable working conditions. In this work, we report a series of bionanocomposites made of Ag nanoparticles (NPs) and gelatine A for the surface enhanced Raman scattering (SERS) detection of sodium diethyldithiocarbamate (EtDTC) as a pesticide model. These studies demonstrate the effectiveness of these substrates for the detection of EtDTC in aqueous solutions in a concentration as low as 10(-5) M. We have monitored the Raman signal enhancement of this analyte in bionanocomposites having an increasing amount of gelatine due to their relevance in formulating hydrogels of variable gel strengths. Under these conditions, the bionanocomposites have shown an effective SERS activity using EtDTC, demonstrating their effectiveness in the qualitative detection of this analyte. Finally, experiments involving the release of EtDTC from Ag/gelatine samples have been monitored by SERS, which attest the potential of this spectroscopic method in the laboratorial monitoring of hydrogels for pesticide release.

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.

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.