Surface-enhanced Raman Scattering (surface-enhanced + raman_scattering)

Distribution by Scientific Domains


Selected Abstracts


Surface Nanometer-Scale Patterning in Realizing Large-Scale Ordered Arrays of Metallic Nanoshells with Well-Defined Structures and Controllable Properties

ADVANCED FUNCTIONAL MATERIALS, Issue 15 2010
Shikuan Yang
Abstract Surface patterns of nanoshell arrays play an important role in diverse applications including surface-enhanced Raman scattering (SERS) sensors, lithium-ion batteries, solar cells, and optical devices. This paper describes an innovative surface nanopatterning technique for realizing large-scale ordered arrays of metallic spherical nanoshells with well-defined structures. Ag nanoshell arrays are prepared using polystyrene sphere templates by an electrophoretic process in Ag colloidal solutions. The fabricated Ag nanoshell arrays have a high controllability of the structural parameters, including the diameter, the surface roughness, and the intershell spacing, giving rise to the tunable properties of nanoshell arrays. As an example, tunable SERS and localized surface plasmon resonance of the nanoshell arrays are demonstrated by controlling the structural parameters. The surface nanopatterning technique shown in this paper is a general fabrication process in achieving not only metallic nanoshell arrays, but also nanoshell arrays of semiconductors and metallic oxides. [source]


Fabrication of a Macroporous Microwell Array for Surface-Enhanced Raman Scattering

ADVANCED FUNCTIONAL MATERIALS, Issue 19 2009
Martina Zamuner
Abstract Here, a colloidal templating procedure for generating high-density arrays of gold macroporous microwells, which act as discrete sites for surface-enhanced Raman scattering (SERS), is reported. Development of such a novel array with discrete macroporous sites requires multiple fabrication steps. First, selective wet-chemical etching of the distal face of a coherent optical fiber bundle produces a microwell array. The microwells are then selectively filled with a macroporous structure by electroless template synthesis using self-assembled nanospheres. The fabricated arrays are structured at both the micrometer and nanometer scale on etched imaging bundles. Confocal Raman microscopy is used to detect a benzenethiol monolayer adsorbed on the macroporous gold and to map the spatial distribution of the SERS signal. The Raman enhancement factor of the modified wells is investigated and an average enhancement factor of 4,×,104 is measured. This demonstrates that such nanostructured wells can enhance the local electromagnetic field and lead to a platform of ordered SERS-active micrometer-sized spots defined by the initial shape of the etched optical fibers. Since the fabrication steps keep the initial architecture of the optical fiber bundle, such ordered SERS-active platforms fabricated onto an imaging waveguide open new applications in remote SERS imaging, plasmonic devices, and integrated electro-optical sensor arrays. [source]


Nanoporous Copper with Tunable Nanoporosity for SERS Applications

ADVANCED FUNCTIONAL MATERIALS, Issue 8 2009
Lu-Yang Chen
Abstract Nanostructured materials with designable microstructure and controllable physical and chemical properties are highly desired for practical applications in nanotechnology. In this article, it is reported that nanoporous copper with a tunable nanopore size can be fabricated by controlling the dealloying process. The influence of acid concentration and etching potential on the formation of nanoprosity is systematically investigated. With optimal etching conditions, the nanopore sizes can be tailored from ,15 to ,120,nm by controlling the dealloying time. It is found that the tunable nanoporosity leads to significant improvements in surface-enhanced Raman scattering (SERS) of nanoporous copper and peak values of SERS enhancements for both rhodamine 6G and crystal violet 10B molecules are observed at a pore size of ,30,50,nm. This study underscores the effect of complex three-dimensional nanostructures on physical and chemical properties and is helpful in developing inexpensive SERS substrates for sensitive instrumentations in molecular diagnostics. [source]


Influence of Side-Chain Structure and Irradiation Condition on Photoalignment of Ladder-Like Polysiloxane Films,

ADVANCED FUNCTIONAL MATERIALS, Issue 1 2005
H.-W. Gu
Abstract In this paper we consider the photo-induced aligning capability of various ladder-like polysiloxane-based photoalignment films,which could be used in liquid-crystal displays,bearing different photoreactive side chains, i.e., laterally grafted cinnamate/azobenzene-based dual photoreactive side chains with a short or longer spacer, and terminally fixed coumarin-containing side chains. Results from polarized optical microscopy (POM), Fourier-transform infrared (FTIR) spectroscopy, surface-enhanced Raman scattering (SERS), atomic force microscopy (AFM), etc., are integrated to elucidate the influence of side-chain structure and the irradiation conditions on the photoalignment of ladder-like polysiloxane films. It is demonstrated that the film containing the dual photoreactive group with a longer spacer exhibits better alignment properties. Reasonably, the concerted photoreactions of the dual photoreactive group and the longer spacer are beneficial to the cooperative motion of chromophores at the "domain level", resulting in improved alignment facility and stability. The complicated effects of irradiation conditions and moderate annealing are also discussed. High-quality alignment of the polysilsesquioxane (LPS)-based photoalignment film LPS-CA11 with a longer spacer between the LPS main chain and cinnamoyl/azobenzene side chains can be achieved only within an optimal range of exposure (5,8,J,cm,2), while the pretilt angles can be adjusted in the range 0.5°,7° by varying the incident light intensity. Additionally, moderate annealing before and after illumination can markedly improve the alignment uniformity by self-healing of defects. [source]


Photo-Induced Orientation of a Film of Ladderlike Polysiloxane Bearing Dual Photoreactive Side Groups,

ADVANCED MATERIALS, Issue 16 2003
H.W. Gu
A newly designed ladder-like polysiloxane (LPS) containing dual photoreactive side groups has been synthesized for the purpose of generating high-quality photo-alignment layers with controllable pretilt angle (,,1,7°, see Figure and cover). Integrated spectroscopic methods of UV dichroism, surface-enhanced Raman scattering (SERS), and FT-IR are used together for the first time to elucidate the photo-alignment mechanism and the real cause of the high pretilt angle. [source]


Adjustment and control of SERS activity of metal substrates by pressure

JOURNAL OF RAMAN SPECTROSCOPY, Issue 4 2010
Lixin Xia
Abstract Metal pellets of silver and copper for surface-enhanced Raman scattering (SERS) spectroscopy were prepared by compression with different pressures. It was found that the SERS activity of the pellet could be controlled by pressure. Enhanced Raman scattering properties of the metal pellets in the presence of adsorbed 4-mercaptobenzoic acid (4-MBA) with excitation at 632.8 or 514 nm could be obtained by choosing proper pressure of pellatization. The SERS peak intensity of the band at ,1584 cm,1 of 4-MBA adsorbed on the metal pellets varies as a function of applied pressure, and which is about 1.2,32 times greater than when it is adsorbed on silver and copper particles. The calculated results of three-dimensional finite-difference time-domain method (3D-FDTD) are in good agreement with the experimental data. Moreover, no spurious peaks appear in the SERS spectra of the samples because no other chemicals are involved in the simple preparation process of the metal pellets, which will facilitate its use as an SERS-active substrate for analytical purposes. In summary, SERS-active metal pellets can be produced simply and cost effectively by the method reported here, and this method is expected to be utilized in the development of SERS-based analytical devices. Copyright © 2009 John Wiley & Sons, Ltd. [source]


Optical probing and imaging of live cells using SERS labels

JOURNAL OF RAMAN SPECTROSCOPY, Issue 1 2009
Janina Kneipp
Abstract During surface-enhanced Raman scattering (SERS), molecules exhibit a significant increase in their Raman signals when attached, or in very close vicinity, to gold or silver nanostructures. This effect is exploited as the basis of a new class of optical labels. Here we demonstrate robust and sensitive SERS labels as probes for imaging live cells. These hybrid labels consist of gold nanoparticles with Rose Bengal or Crystal Violet attached as reporter molecules. These new labels are stable and nontoxic, do not suffer from photobleaching, and can be excited at any excitation wavelength, even in the near infrared. SERS labels can be detected and imaged through the specific Raman signatures of the reporters. In addition, surface-enhanced Raman spectroscopy in the local optical fields of the gold nanoparticles also provides sensitive information on the immediate molecular environment of the label in the cell and allows imaging of the native constituents of the cell. This is demonstrated by images based on a characteristic Raman line of the reporter as well as by displaying lipids based on the SERS signal of the CH deformation/bending modes at ,1470 cm,1. Copyright © 2008 John Wiley & Sons, Ltd. [source]


Surface-enhanced Raman scattering spectroscopy via gold nanostars

JOURNAL OF RAMAN SPECTROSCOPY, Issue 1 2009
E. Nalbant Esenturk
Abstract Anisotropic metallic nanoparticles (NPs) have unique optical properties, which lend them to applications such as surface-enhanced Raman scattering (SERS) spectroscopy. Star-shaped gold (Au) NPs were prepared in aqueous solutions by the seed-mediated growth method and tested for Raman enhancement using 2-mercaptopyridine (2-MPy) and crystal violet (CV) probing molecules. For both molecules, the SERS activity of the nanostars was notably stronger than that of the spherical Au NPs of similar size. The Raman enhancement factors (EFs) for 2-MPy on Au nanostars and nanorods are comparable and estimated as greater than 5 orders of magnitude. However, the enhancement for CV on nanostars was significantly higher than for nanorods, in particular at CV concentrations of 100 nM or lower. This article is a US Government work and is in the public domain in the USA. Published in 2008 by John Wiley & Sons, Ltd. [source]


In situ detection of flavonoids in weld-dyed wool and silk textiles by surface-enhanced Raman scattering

JOURNAL OF RAMAN SPECTROSCOPY, Issue 10 2008
Z. Jurasekova
Abstract Luteolin and apigenin flavonoid have been detected in silk and wool fibres dyed with weld (Reseda luteola L.) through surface-enhanced Raman scattering (SERS) measurements carried out ,on the fibre'. For such purpose, Ag nanoparticles were produced and immobilised in situ via the laser photoreduction of a silver nitrate water solution in contact with the fibre. Control SERS spectra of pure luteolin and apigenin, as well as of mixtures of them, on analogous Ag nanoparticles were also obtained. In this work flavonoids with a similar molecular structure were identified on dyed fibres for the first time without previously hydrolysing the mordant,dye complex. Copyright © 2008 John Wiley & Sons, Ltd. [source]


Nanostructures and nanostructured substrates for surface,enhanced Raman scattering (SERS)

JOURNAL OF RAMAN SPECTROSCOPY, Issue 10 2008
Richard J. C. Brown
Abstract We review the performance of various nanoscaled structures needed to support the propagation of the surface plasmons responsible for surface-enhanced Raman scattering (SERS), and assess the potential for the optimisation of the compromise between enhancement and reproducibility that they provide, and hence their utility for relevant applications. We divide these nanostructures into those comprising structured arrays of discrete nanoparticles in two or three dimensions, and those comprising structured or regularly patterned surfaces in two or three dimensions. The most promising in terms of this compromise are those that involve the tethering of functionalised metal nanoparticles to surfaces. They are not only reproducible, but the functionalisation provides a measure of selectivity to relevant target analytes that the majority of SERS applications require. Copyright © 2008 John Wiley & Sons, Ltd. [source]


Adsorption of 4,4,-thiobisbenzenethiol on silver surfaces: surface-enhanced Raman scattering study

JOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2008
Yuling Wang
Abstract Adsorption of 4,4,-thiobisbenzenethiol (4,4,-TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface-enhanced Raman scattering (SERS) for the first time, which indicates that 4,4,-TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H-atoms of the SH bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4,-TBBT in the two systems. It is inferred from the SERS signal that the two aromatic rings in 4,4,-TBBT molecule are parallel to the colloidal silver surface as seen from the disappearance of ,CH band (3054 cm,1), which is a vibrational mode to be used to determine the orientation of a molecule on metals according to the surface selection rule, while on the roughened silver electrode surface they are tilted to the surface as seen from the enhanced signal of ,CH. The orientation of the C-S bond is tilted with respect to the silver surface in both cases as inferred from the strong enhancement of the ,CS. SERS spectra of 4,4,-TBBT on the roughened silver electrode with different applied potentials reveal that the enhancement of 4,4,-TBBT on the roughened silver electrode surface may be related to the chemical mechanism (CM). More importantly, the adsorption of 4,4,-TBBT on the silver electrode is expected to be useful to covalently adsorb metal nanoparticles through the free SH bond to form two- or three- dimensional nanostructures. Copyright © 2007 John Wiley & Sons, Ltd. [source]


Nanostructured gold surfaces as reproducible substrates for surface-enhanced Raman spectroscopy

JOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2007
M. Sackmann
Abstract Raman spectroscopy is a common tool for the qualitative and quantitative chemical analysis of molecules. Although the unique identification of molecules is possible via their vibrational lines, high concentrations (mmol/l) are needed for their nonresonant excitation owing to their low scattering cross section. The intensity of the Raman spectra is amplified by the use of the surface-enhanced Raman scattering (SERS) technique. While the use of silver sols results only in a limited reproducibility of the Raman line intensities, lithographically designed, nanostructured gold surfaces used as SERS-active substrates should, in principle, combine the high sensitivity with better reproducibility. For this purpose, we have produced gratings of gold dots on Si(001) surfaces by means of electron beam lithography. Qualitative and quantitative investigations of crystal violet (CV) performed using nanostructured surfaces give high reproducibility and enhancement of the Raman lines. The substrates are reusable after cleaning; all results presented could be obtained from a single SERS substrate. For the experiments very low laser powers were used. Copyright © 2006 John Wiley & Sons, Ltd. [source]


Surface-enhanced Raman spectroscopy: advancements and applications

JOURNAL OF RAMAN SPECTROSCOPY, Issue 6-7 2005
Z. Q. Tian
Abstract Since the mid-1990s, surface-enhanced Raman scattering (SERS) has advanced greatly and gained wider application and a renewal of interest. There have been several new and creative developments, e.g. SERS of single molecules, nanostructures and transition metals, tip-enhanced Raman scattering (TERS), surface-enhanced hyper-Raman scattering (SEHRS), ultraviolet-excited SERS (UV-SERS) and surface-enhanced resonance Raman scattering (SERRS), and their wide applications in biology, medicine, materials science and electrochemistry. It is timely to publish a special issue reporting these initiatives and the progress made in the past 7 years. This issue consists of 30 invited articles that are roughly divided into three SERS research themes: theories, methods and applications. These up-to-date representatives of the research results clearly show that SERS is important not only for Raman spectroscopy and surface science but also for nanoscience. Copyright © 2005 John Wiley & Sons, Ltd. [source]


Improved surface-enhanced Raman scattering of polypyrrole electrodeposited on roughened substrates composed of Au,Ag bimetallic nanoparticles

JOURNAL OF RAMAN SPECTROSCOPY, Issue 6-7 2005
Thomas C. Chuang
Abstract We report here the first electrochemical method to prepare a roughened gold substrate with bimetallic silver and gold nanoparticles. First, a silver substrate was roughened by a triangular-wave oxidation,reduction cycle in 0.1 N HCl aqueous solutions. Silver-containing complexes were found in the solution after the ORC treatment. Then a gold substrate was subsequently roughened by a similar oxidation,reduction treatment in this solution. Scanning electron microscopy and atomic force microscopy reveal that the surface of the roughened gold was intrinsically modified with silver nanoparticles, which demonstrates two different kinds of deposition domains. Encouragingly, surface-enhanced Raman scattering of polypyrrole electrodeposited on the roughened gold substrate, modified with finer silver nanoparticles, exhibits an eightfold higher intensity. Copyright © 2005 John Wiley & Sons, Ltd. [source]


Monolayers of sulfur-containing molecules at metal surfaces as studied using SERS: 3, 3,-thiodipropionic acid and 3-mercaptopropionic acid adsorbed on silver and copper

JOURNAL OF RAMAN SPECTROSCOPY, Issue 6-7 2005
Andrzej Kudelski
Abstract The modification of metal surfaces with self-assembled thiol monolayers is the subject of intensive studies owing to both its fundamental interest in surface chemistry and its potential technological significance. In this work, the applicability of surface-enhanced Raman scattering (SERS) to determine the conformation and pKa values of ,-terminated thiol molecules was investigated. 3, 3,-Thiodipropionic acid (TDPA) and 3-mercaptopropionic acid (MPA) monolayers were spontaneously formed on silver and copper surfaces by adsorption from TDPA and MPA solutions, respectively. The structure of the monolayers formed was determined from SERS measurements. The SERS investigations showed that molecules forming TDPA monolayers prefer to adopt a gauche conformation of the,S,C,C chains, whereas in MPA monolayers formed from 1 mM MPA aqueous solution a significant part of the adsorbed molecules adopts a trans conformation. Formation on the metal surface of an MPA monolayer with high surface coverage of MPA makes dissociation of the carboxylic groups of MPA significantly more difficult. Analogous changes in the strength of similar adsorbed compounds have been reported by other groups. In contrast to those results, we found that the formation of monolayers from TDPA increases its acidic strength even at high surface coverage when monolayers are formed from relatively concentrated TDPA solutions. Probably the interaction of carboxylic groups with the metal surface is easier for TDPA than for MPA for geometric reasons. We consider that ionization of carboxylic groups increases the strength of this interaction. Copyright © 2005 John Wiley & Sons, Ltd. [source]


Structures of monolayers formed from different HS,(CH2)2,X thiols on gold, silver and copper: comparitive studies by surface-enhanced Raman scattering

JOURNAL OF RAMAN SPECTROSCOPY, Issue 11 2003
Andrzej Kudelski
Abstract Molecules of 2-aminoethanethiol (cysteamine, CYS), 2-mercaptoethanol (MET), 3-mercaptopropionic acid (MPA), sodium 2-mercaptoethanesulphonate (MES) and 1-propanethiol (PTH) were spontaneously chemisorbed on electrochemically activated silver, copper and gold surfaces. The structure of monolayers formed was studied with surface-enhanced Raman scattering (SERS). In CYS and MPA monolayers the relative surface concentration of gauche conformers was higher than in MET, PTH and MES monolayers. This is probably due to double bonding to the metal surface by a fraction of adsorbed MPA and CYS molecules (via the sulphur moiety and the terminal carboxylic or amino group). In CYS, MET, MPA and PTH monolayers the surface concentration of trans conformers is significantly higher on Ag than on Au or Cu. The structures of MES monolayers on Ag, Au and Cu are similar, with very high surface concentrations of trans conformers. Statistically, the wavenumbers of ,(C,S) bands of both gauche and trans conformers are the highest on Au, slightly lower on Ag and the lowest for Cu. However the positions of ,(C,S) bands are also sensitive to the other parameters (e.g. C,C,S,metal torsion angle, the overall ordering of the monolayer). Therefore, the wavenumbers of ,(C,S) bands are not good indicators of differences in the interaction between chemisorbed thiols and the metal substrates. Desorption measurements suggest that part of the adsorbed molecules is bonded significantly weaker than the rest. Thiolate monolayers on Cu decomposed relatively easily, forming a layer of copper sulphide. The strength of adsorbed MPA acid is similar on all substrates. Copyright © 2003 John Wiley & Sons, Ltd. [source]


Adsorption of 4,4,-biphenyl diisocyanide on gold nanoparticle surfaces investigated by surface-enhanced Raman scattering

JOURNAL OF RAMAN SPECTROSCOPY, Issue 4 2003
Sang-Woo Joo
Abstract We investigated the spectral features of the ,(NC) bands when 4,4,-biphenyl diisocyanide (BPDNC) is adsorbed on gold nanoparticle surfaces by surface-enhanced Raman scattering (SERS). The mode of adsorption of BPDNC on gold nanoparticles was found to change with the bulk concentration. At low concentrations of BPDNC, only the ,(NC)bound band was conspicuous at ,2185 cm,1 and the free NC stretching band was barely detected in the SERS spectra. When the bulk concentration was increased, the ,(NC)free band became prominent at ,2123 cm,1. BPDNC was assumed to bridge two different gold particles at low concentrations, but as the concentration was increased, the bridge appeared to be broken and bonded to the gold particle only via one of the two isocyanide groups. On the basis of the electromagnetic surface selection rule, we attempted to explain the orientation of the adsorbate on Au surfaces by determining the relative enhancement factor of each vibrational band. Copyright © 2003 John Wiley & Sons, Ltd. [source]


Investigations on 1,5-diaminoanthraquinone by laser excitation

JOURNAL OF RAMAN SPECTROSCOPY, Issue 1 2003
M. Umadevi
Abstract Optical absorption and fluorescence emission spectra of 1,5-diaminoanthraquinone (1,5-DAAQ) in different solvents and the surface-enhanced Raman scattering (SERS) spectrum of 1,5-DAAQ in silver sol were investigated. Optical absorption and fluorescence emission studies revealed that the internal and external hydrogen bonds and reorientation of the solvent molecule around the excited state fluorophore are responsible for the observed bathochromic shift and the non-radiative decay process in polar solvents. SERS studies showed that 1,5-DAAQ molecules are chemisorbed through carbonyl groups and the lone pair of electrons on the nitrogen. The orientation of the molecule on the silver surface is found to be stand-on. Copyright © 2002 John Wiley & Sons, Ltd. [source]


Surface-enhanced Raman scattering of 4,4,-dicyanobiphenyl on gold and silver nanoparticle surfaces

JOURNAL OF RAMAN SPECTROSCOPY, Issue 6 2002
Chung-ro Lee
The adsorption behavior of 4,4,-dicyanobiphenyl (DCBP) on Ag and Au nanoparticle surfaces was studied by surface-enhanced Raman scattering (SERS). The absence of the ring CH band denoted a flat orientation of the biphenyl ring on Ag and Au. The red shift of the ,8a band indicated a direct ring ,-orbital interaction with the surfaces. The two benzene rings of DCBP appeared to lie on the same plane with a ,-type interaction upon adsorption on the surfaces. The ,(CN) bands were blue shifted in the Ag and Au SERS spectra by 2 and 22 cm,1, respectively from the ordinary Raman spectrum. The orientation of DCBP on the Ag and Au surfaces was analyzed by the relative enhancement factors of the vibrational bands based on the electromagnetic SERS selection rule. Copyright © 2002 John Wiley & Sons, Ltd. [source]


Nociceptin and its natural and specifically-modified fragments: Structural studies

BIOPOLYMERS, Issue 12 2010
E. Podstawka-Proniewicz
Abstract The vibrational structures of Nociceptin (FQ), its short bioactive fragments, and specifically-modified [Tyr1]FQ (1-6), [His1]FQ (1-6), and [His1,4]FQ (1-6) fragments were characterized. We showed that in the solid state, all of the aforementioned peptides except FQ adopt mainly turn and disordered secondary structures with a small contribution from an antiparallel ,-sheet conformation. FQ (1-11), FQ (7-17) [His1]FQ (1-6), and [His1,4]FQ (1-6) have an ,-helical backbone arrangement that could also slightly influence their secondary structure. The adsorption behavior of these peptides on a colloidal silver surface in an aqueous solution (pH = ,8.3) was investigated by means of surface-enhanced Raman scattering (SERS). All of the peptides, excluding FQ (7-17), chemisorbed on the colloidal silver surfaces through a Phe4 residue, which for FQ, FQ (1-11), FQ (1-6), [Tyr1]FQ (1-6), and [His1]FQ (1-6) lies almost flat on this surface, while for FQ (1-13) and FQ (1-13)NH2 adopts a slightly tilted orientation with respect to the surface. The Tyr1 residue in [Tyr1]FQ (1-6) does not interact with the colloidal silver surface, suggesting that the Tyr1 and Phe4 side chains are located on the opposite sides of the peptide backbone, which can be also true for His1 and Phe4 in [His1]FQ (1-6). The lone pair of electrons on the oxygen atom of the ionized carbonyl group of FQ (1-13) and FQ (7-17) appears to be coordinated to the colloidal silver nanoparticles, whereas in the case of the remaining peptides, it only assists in the adsorption process, similar to the NH2 group. We also showed that upon adsorption, the secondary structure of these peptides is altered. © 2010 Wiley Periodicals, Inc. Biopolymers 93: 1039,1054, 2010. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source]


Surface-enhanced Raman difference between bombesin and its modified analogues on the colloidal and electrochemically roughen silver surfaces

BIOPOLYMERS, Issue 10 2008
Edyta Podstawka
Abstract In this article, surface-enhanced Raman scattering (SERS) spectra of bombesin (BN) and its six modified analogues ([D-Phe12]BN, [Tyr4]BN, [Tyr4,D-Phe12]BN, [D-Phe12,Leu14]BN, [Leu13 -®-Leu14]BN, and [Lys3]BN) on a colloidal silver surface are reported and compared with SERS spectra of these species immobilized onto an ellectrochemically roughen silver electrode. Changes in enhancement and wavenumber of proper bands upon adsorption on different silver surfaces are consistent with BN and its analogues adsorption primarily through Trp8. Slightly different adsorption states of these molecules are observed depending upon natural amino acids substitution. For example, the indole ring in all the peptides interacts with silver nanoparticles in a edge-on orientation. It is additionally coordinated to the silver through the N1H bond for all the peptides, except [Phe12]BN. This is in contrary to the results obtained for the silver roughen electrode that show direct but not strong N1H/Ag interaction for all peptides except [D-Phe12,Leu14]BN and [Leu13 -®-Leu14]BN. For BN only CO is not involved in the chemical coordination with the colloidal surface. [Lys3]BN and BN also adsorb with the CN bond of NH2 group normal and horizontal, respectively, to the colloidal surface, whereas CNH2 in other peptides is tilted to this surface. Also, the Trp8 CH2 moiety of only [Tyr4]BN, [Lys3]BN, and [Tyr4,D-Phe12]BN coordinates to Ag, whereas the Phe12 ring of [Phe12]BN, [Tyr4,D-Phe12]BN, and [D-Phe12,Leu14]BN assists in the peptides binding only on the colloidal silver. © 2008 Wiley Periodicals, Inc. Biopolymers 89: 807,819, 2008. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source]


Study of interaction between aspartic acid and silver by surface-enhanced Raman scattering on H2O and D2O sols

BIOPOLYMERS, Issue 5 2001
J. F. Arenas
Abstract Three different surface-enhanced Raman scattering (SERS) spectra are recorded for aspartic acid on H2O silver sols under different concentrations and pH values. The analysis of the results shows that it interacts with the metal surface in its dianionic form in two different ways, depending on the pH and concentration. Moreover, in some cases the fumarate anion is detected, which results from the chemical surface transformation of the aspartate. The N -deuterated aspartic acid adsorbed on the D2O silver sols gives rise to only one SERS spectrum as a consequence of the interaction of amino and carboxylate functional groups of the dianion with the metal, independent of the concentration and pD. © 2001 John Wiley & Sons, Inc. Biopolymers (Biospectroscopy) 62: 241,248, 2001 [source]


Adsorption of 1,3-Benzenedithiol and 1,3-Benzenedimethanethiol on Gold Surfaces,

CHEMPHYSCHEM, Issue 12 2008
Jong Kuk Lim Dr.
Abstract The adsorption characteristics of 1,3-benzenedithiol (1,3-BDT) and 1,3-benzenedimethanethiol (1,3-BDMT) on Au surfaces are investigated by means of surface-enhanced Raman scattering, UV/Vis absorption spectroscopy, and cyclic voltammetry (CV). 1,3-BDMT is found to adsorb via two S,Au linkages at concentrations below monolayer coverage, but to have an upright geometry as the concentration increases on Au nanoparticles. On the other hand, 1,3-BDT is found to adsorb by forming two S,Au linkages, regardless of concentration, based on the disappearance of the ,(SH)free stretching band. Because of the absence of the methylene unit, 1,3-BDT appeares not to self-assemble efficiently on Au surfaces. The UV/Vis absorption spectroscopy and CV techniques are also applied to check the formation of self-assembled monolayers of 1,3-BDT and 1,3-BDMT on Au. Density functional theory calculations based on a simple adsorption model using an Au8 cluster are performed to better understand the nature of the adsorption characteristics of 1,3-BDT and 1,3-BDMT on Au surfaces. [source]