Rectangular Silver Nanorods: Controlled Preparation, Liquid-Liquid Interface Assembly, and Application in Surface-Enhanced Raman Scattering

In this paper, we for the first time report a polyol method for large-scale synthesis of rectangular silver nanorods in the presence of directing agent and seeds. This method has some clear advantages including simplicity, high quality, and ease of scaleup. Silver nanowires or silver nanorods with a submicrometer diameter could also be facilely prepared when the reaction parameters are slightly changed. Furthermore, a liquid-liquid assembly strategy has been employed to construct uniform rectangular silver nanorod arrays on a solid substrate which could be used as surface-enhanced Raman scattering (SERS) substrates with high SERS activity, stability, and reproducibility. It is found that the SERS spectra obtained from the probe molecules with the different concentrations show different SERS intensifies. As the concentration of 4-aminothiophenol (4-ATP) or rhodamine 6G (R6G) increases, the SERS intensities progressively increase. The enhancement factor for 4-ATP and R6G should be as large as 5.06 x 10(4) or much larger than the value of 5.06 x 10(8), respectively.

Silver nanoparticles coated with adenine: preparation, self-assembly and application in surface-enhanced Raman scattering

We describe herein the preparation of silver nanoparticles (AgNPs) using nucleobase adenine as protecting agent through the in situ chemical reduction of AgNO3 with NaBH4 in an aqueous medium at room temperature. As-prepared AgNPs were characterized by UV-visible spectra, transmission electron microscopy and x-ray photoelectron spectroscopy. All these data confirmed the formation of AgNPs. On the basis of electrostatic interactions between as-prepared AgNPs and anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS), we successfully fabricated (PSS/AgNP)n (n = 0-9) multilayers on a 3-mercaptopropyltrimethoxysilane/AgNP functionalized indium tin oxide (ITO) substrate via the layer-by-layer self-assembly technique and characterized as-formed multilayers with UV-visible spectra. Furthermore, these ITO substrates coated with multilayers of different thickness were investigated as surface-enhanced Raman scattering (SERS)-active substrates using p-aminothiophenol as a probe molecule, implying that these multilayers substrates may be promising for a new type of SERS-active substrate.

Surface-enhanced Raman scattering studies on aggregated silver nanoplates in aqueous solution

Four different sizes of citrate-protected silver nanoplates with the corresponding in-plane dipole resonance band at 530, 619, 778, and 858 nm, respectively, are synthesized for surface-enhanced Raman scattering (SERS) study. Their aggregation behaviors are monitored by use of UV-vis spectroscopy. During the aggregation process, a marked red shift of the in-plane dipole resonance of silver nanoplates is observed, whereas other resonance modes of them only have small alterations in the site or intensity. Aggregated silver nanoplates can serve as active SERS substrates with an enhancement factor of about 4.5 x 10(5) using 2-aminothiophenol as a probing molecule. The SERS performance of silver nanoplates is even superior to the commonly used Lee-Meisel silver colloid, making them very attractive for SERS applications.

Surface enhanced Raman scattering of p-aminothiophenol self-assembled monolayers in sandwich structure fabricated on glass

A sandwich structure consisting of Ag nanoparticles (NPs), p-aminothiophenol (p-ATP) self-assembled monolayers (SAMs), and Ag NPs was fabricated on glass and characterized by surface enhanced Raman scattering (SERS). The SERS spectrum of a p-ATP SAM in such sandwich structure shows that the electromagnetic enhancement is greater than that on Ag NPs assembled on glass. The obtained enhancement factors (EF) on solely one sandwich structure were as large as 6.0 +/- 0.62x10(4) and 1.2 +/- 0.62x10(7) for the 7a and 3b(b(2)) vibration modes, respectively. The large enhancement effect of p-ATP SAMs is likely a result of plasmon coupling between the two layers of Ag NP (localized surface plasmon) resonance, creating a large localized electromagnetic field at their interface, where p-ATP resides. Moreover, the fact that large EF values (similar to 1.9 +/- 0.7x10(4) and 9.4 +/- 0.7x10(6) for the 7a- and b(2)-type vibration modes, respectively) were also obtained on a single sandwich structure of Au NPs/p-ATP SAMs/Ag NPs in the visible demonstrates that the electromagnetic coupling does not exist only between Ag NPs but also between Au and Ag NPs.

Surface-enhanced Raman scattering of silver-gold bimetallic nanostructures with hollow interiors

Surface-enhanced Raman scattering (SERS) activity of silver-gold bimetallic nanostructures (a mean diameter of similar to 100 nm) with hollow interiors was checked using p-aminothiophenol (p-ATP) as a probe molecule at both visible light (514.5 nm) and near-infrared (1064 nm) excitation. Evident Raman peaks of p-ATP were clearly observed, indicating the enhancement Raman scattering activity of the hollow nanostructure to p-ATP. The enhancement factors (EF) at the hollow nanostructures were obtained to be as large as (0.8 +/- 0.3)x10(6) and (2.7 +/- 0.5)x10(8) for 7a and 19b (b(2)) vibration mode, respectively, which was 30-40 times larger than that at silver nanoparticles with solid interiors at 514.5 nm excitation. EF values were also obtained at 1064 nm excitation for 7a and b(2)-type vibration mode, which were estimated to be as large as (1.0 +/- 0.3)x10(6) and (0.9 +/- 0.2)x10(7), respectively. The additional EF values by a factor of similar to 10 for b(2)-type band were assumed to be due to the chemical effect. Large electromagnetic EF values were presumed to derive from a strong localized plasmas electromagnetic field existed at the hollow nanostructures.

Surface-enhanced Raman scattering of xanthopterin adsorbed on colloidal silver

Surface-enhanced Raman scattering (SERS) of xanthopterin adsorbed on colloidal silver was measured and the Raman spectrum calculated by the density functional theory method was also obtained. Xanthopterin can be detected down to 5 X 10(-9) m and the enhancement of the scattering intensity is at least 10(5)-fold. Xanthopterin molecules are adsorbed flatly on the surface of the Ag particles. This study shows that SERS could be another prospective method for the detection of pterines. Copyright (C) 2001 John Wiley Sons, Ltd.

Surface enhanced Raman evidence for Ag+ complexes of adenine, deoxyadenosine and 5'-dAMP formed in silver colloids

We report the formation of highly scattering silver complexes of adenine, deoxyadenosine and 5'-dAMP under alkaline pH conditions in the colloidal silver solutions which are used for surface-enhanced Raman spectroscopy. These complexes, and other pH-dependent phenomena, help to explain the diversity of previously reported adenine SERS spectra. Using conditions which promote complex formation allows nucleotides to be detected at <1 ppm, even in solutions with high salt concentrations.

Characterization of novel Ag on TiO2 films for surface-enhanced Raman scattering

Novel Ag on TiO₂ films are generated by semiconductor photocatalysis and characterized by ultraviolet-visible (UV/Vis) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM), as well as assessed for surface-enhanced Raman scattering (SERS) activity. The nature and thickness of the photodeposited Ag, and thus the degree of SERS activity, is controlled by the time of exposure of the TiO₂ film to UV light. All such films exhibit the optical characteristics (λ_max ≅ 390 nm) of small (<20 nm) Ag particles, although this feature becomes less prominent as the film becomes thicker. The films comprise quite large (>40 nm) Ag islands that grow and merge with increasing levels of Ag photodeposition. Tested with a benzotriazole dye probe, the films are SERS active, exhibiting activity similar to that of 6-nm-thick vapordeposited films. The Ag/TiO₂ films exhibit a lower residual standard deviation (∼25%) compared with Ag vapor-deposited films (∼45%), which is, however, still unacceptable for quantitative work. The sample-to-sample variance could be reduced significantly (<7%) by spinning the film during the SERS measurement. The Ag/TiO₂ films are mechanically robust and resistant to removal and damage by scratching, unlike the Ag vapor-deposited films. The Ag/TiO₂ films also exhibit no obvious loss of SERS activity when stored in the dark under otherwise ambient conditions. The possible extension of this simple, effective method of producing Ag films for SERS, to metals other than Ag and to semiconductors other than TiO₂, is briefly discussed. 

New insights on surface-enhanced Raman scattering based on controlled aggregation and spectroscopic studies, DFT calculations and symmetry analysis for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine adsorbed onto citrate-stabilized gold nanoparticles

Asystematic study on the surface-enhanced Raman scattering (SERS) for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine (bptz) adsorbed onto citrate-modified gold nanoparticles (cit-AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit-AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge-transfer (CT) effects. The most strongly enhanced vibrations belong to a(1) and b(2) representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system. Copyright (C) 2010 John Wiley & Sons, Ltd.

Sensing of 2,4-dichlorophenoxyacetic acid by surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) spectra of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was obtained by employing a bi-layer gold substrate, assembled by the reduction of Au(III) over gold-seeded nanoparticles immobilized on functionalized glass substrates. The SERS signal was linear with the logarithm of the solution concentrations between 1.0 x 10(-7) mol L(-1) and 1.0 x 10(-3) mol L(-1), indicating that the bi-layer gold substrate affords a significant dynamic range for SERS, providing an excellent analytical response within this concentration range, and revealing the high sensitivity of the gold surface towards such analyte. In addition, using the same gold substrate, a similar calibration curve was obtained for crystal-violet (CV), and it was possible to identify the concentration limit corresponding to the transition from the average SERS to the nonlinear SERS response. (C) 2010 Elsevier B.V. All rights reserved.

Using Polycarbonate Membranes as Templates for the Preparation of Au Nanostructures for Surface-Enhanced Raman Scattering

Polycarbonate membranes (PCM) of various pores sizes (400, 200, 100 and 50 nm) were used as templates for gold deposition. The electrodeposition from gold ions resulted in the formation of gold nanotubes when large pores size PCMs (400 and 200 nm) were used. On the other hand, gold nanowires were predominant for the PCMs with smaller pores size (100 and 50 nm). Surface-enhanced Raman scattering (SERS) from the probe molecule 4-mercaptopyridine (4-MPy) was obtained from all these nanostructures. The SERS efficiency of the substrates produced using the PC M templates were compared to two commonly used SERS platforms: a roughened gold electrode and gold nanostructures electrodeposited through organized polystyrene spheres (PSS). The SERS signal of the probe molecule increased as the pore diameter of the PCM template decreased. Moreover, the SERS efficiency from the nanostructures produced using 50 nm PCM templates was four and two times better than the signal from the roughened gold electrode and the PSS template, respectively. The SERS substrates prepared using PCM templates were more homogenous over a larger area (ca. 1 cm(2)), presented better spatial and sample to sample reproducibility than the other substrates. These results show that SERS substrates prepared using PCM templates are promising for the fabrication of planar SERS platforms for analytical/bioanalytical applications.

Surface-enhanced Raman scattering and micro-Raman imaging of Langmuir-Blodgett films of rhodium phthalocyanine

Rhodium phthalocyanine (RhPc) was synthesized and ultra thin Langmuir-Blodgett (LB) films of RhPc were successfully fabricated. The LB film characterization was carried out using both UV-vis absorption spectra and Raman scattering. The Raman spectroscopy was carried out using 633 and 780 nm laser lines. LB films were deposited onto Ag nanoparticles to achieve the surface-enhanced pre-resonance Raman scattering (pre-SERRS) and surface-enhanced Raman scattering (SERS) for both laser lines, respectively, which allowed the characterization of the RhPc ultra thin films. The morphology of the LB RhPc neat film is extracted from micro-Raman imaging. (C) 2003 Elsevier B.V. All rights reserved.

Metal-Organic Semiconductor Nanostructures for Surface-Enhanced Raman Scattering

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Detection of trace levels of atrazine using surface-enhanced Raman scattering and information visualization

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.