Femtosecond response of J aggregates adsorbed onto silver colloid surfaces

Ultrafast intraband Auger process in self-doped colloidal quantum dots

The SERS spectra of acrylamide and polyacrylamide adsorbed on the surface of silver colloid particles are reported. The SERS spectrum of acrylamide is interpreted as indicating that polymerization takes place on silver colloid surfaces. Evidence supporting this conclusion includes the fact that the CH2 stretching vibrations of acrylamide adsorbed on the silver colloid surfaces are at 2926 and 2972 cm−1, which correspond exactly to those of polyacrylamide, and are greatly different from those at 3050 and 3115 cm−1 observed for acrylamide in aqueous solution. Another possible indication of polymerization is the band at 1164 cm−1, which can be assigned to a polymer skeletal vibration.Although acrylamide is polymerized on the silver colloid surfaces, the SERS spectra of polyacrylamide polymerized before adsorption and acrylamide polymerized on the colloid surface are very different from each other. This observation is attributed to the different surface geometry of these two polymers, and the possible contibution of non‐polymerized species in the SERS spectrum of acrylamide.

Influence of aliphatic spacer group on adsorption mechanisms of phosphonate derivatives of l-phenylalanine: Surface-enhanced Raman, Raman, and infrared studies

Surface enhanced Raman scattering (SERS) is potentially tool in the characterization of biomolecules such as amino acids, complicated peptides and proteins, and even tissues or living cells. Amino acids and short peptides contain different functional groups. Therefore, they are suitable for the investigations of the competitive-interactions of these functional groups with colloidal silver surfaces. In this paper, Normal Raman and SERS of amino acids Leucine and Isoleucine and short peptide Leu-Leu were measured on the silver colloidal substrate. Raman shifts that stem from different vibrational mode in the molecular inner structure, and the variations of SERS of the samples were analyzed in this study. The results show that different connection of one methyl to the main chains of the isomer amino acids resulted in different vibration modes in the Normal Raman spectra of Leucine and Isoleucine. In the SERS spectra of the isomer amino acids, all frequency shifts are expressed more differently than those in Normal Raman spectra of solid state. Orientation of this isomer amino acids, as well as specific-competitive interactions of their functional groups with the colloidal silver surface, were speculated by detailed spectral analysis of the obtained SERS spectra. In addition, the dipeptide Leu-Leu, as the corresponding homodipeptide of Leucine, was also measured adsorbed on the colloidal silver surface. The SERS spectrum of Leu-Leu is different from its corresponding amino acid Leucine but both of them are adsorbed on the silver surface through the carboxylate moiety.

We investigated the Surface-enhanced Raman Spectroscopy (SERS) spectrum of ethephone (2-chloroethylphosphonic acid). We observed significant signals in the ordinary Raman spectrum for solid-state ethephone as well as when it was adsorbed on a colloidal silver surface, strong vibrational signals were obtained at a very low concentration. The SERS spectra were obtained by silver colloids that were prepared by the <TEX>$\gamma$</TEX>-irradiation method. The influence of pH and the influence of anion <TEX>$(Cl^-,\;Br^-,\;I^-)$</TEX> on the adsorption orientation were investigated. Two different adsorption mechanisms were deduced, depending on the experimental conditions. The chlorine atom or the chlorine and two oxygen atoms were adsorbed on the colloidal silver surface. Among halide ions, <TEX>$Br^-$</TEX> and <TEX>$I^-$</TEX> were more strongly adsorbed on the colloidal silver surfaces. As a result, the adsorption of ethephone was less effective due to their steric hinderance.

The vibrational structures of Nociceptin (FQ), its short bioactive fragments, and specifically-modified [Tyr¹]FQ (1-6), [His¹]FQ (1-6), and [His(1,4)]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 β-sheet conformation. FQ (1-11), FQ (7-17) [His¹]FQ (1-6), and [His(1,4)]FQ (1-6) have an α-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 --NH⁴ group. We also showed that upon adsorption, the secondary structure of these peptides is altered.

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 SH 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 νCH 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 νCH. 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 νCS. 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 SH bond to form two‐ or three‐ dimensional nanostructures. Copyright © 2007 John Wiley &amp; Sons, Ltd.

Here, we report a systematic surface-enhanced Raman spectroscopy (SERS) study of the structures of phosphonate derivatives of the N-heterocyclic aromatic compounds imidazole (ImMeP ([hydroxy(1H-imidazol-5-yl)methyl]phosphonic acid) and (ImMe)(2)P (bis[hydroxy-(1H-imidazol-4-yl)-methyl]phosphinic acid)), thiazole (BAThMeP (butylaminothiazol-2-yl-methyl)phosphonic acid) and BzAThMeP (benzylaminothiazol-2-yl-methyl)phosphonic acid)), and pyridine ((PyMe)(2)P (bis[(hydroxypyridin-3-yl-methyl)]phosphinic acid)) adsorbed on nanometer-sized colloidal particles. We compared these structures to those on a roughened silver electrode surface to determine the relationship between the adsorption strength and the geometry. For example, we showed that all of these biomolecules interact with the colloidal surface through aromatic rings. However, for BzAThMeP, a preferential interaction between the benzene ring and the colloidal silver surface is observed more so than that between the thiazole ring and this substrate. The PC(OH)C fragment does not take part in the adsorption process, and the phosphonate moiety of ImMeP and (ImMe)(2)P, being removed from the surface, only assists in this process.

Surface-enhanced Raman scattering (SERS) spectroscopy has been applied to investigate the interaction with a silver colloidal surface of following seven 6-14 fragments of bombesin (BN) C-terminus: cyclo[D-Phe(6),His(7),Leu(14)]BN(6-14), [D-Phe(6),Leu-NHEt(13),des-Met(14)]BN(6-14), [D-Phe(6),Leu(13)-(R)-p-chloro-Phe(14)]BN(6-14), [D-Phe(6),beta-Ala(11),Phe(13),Nle(14)]BN(6-14), [D-Tyr(6),beta-Ala(11),Phe(13),Nle(14)]BN(6-14), [D-Tyr(6),beta-Phe(11),Phe(13),Nle(14)OH]BN(6-14), and [D-Cys(6),Asn(7),D-Ala(11),Cys(14)]BN(6-14), potent r-GRP-R receptor antagonists used in chemotherapy and potential effective drugs in cancer treatment. The adsorption active sites and molecular orientations on the colloidal silver surface have been determined on the basis of SERS "surface selection rules" subsequent to a detailed SERS analysis. In addition, the similarities and differences of these spectra with the SERS spectra of the peptides immobilized on a roughened silver electrode surface have been examined. From the data, suggestion has been made about structural properties of these peptides on the colloidal surface.

Investigation of adsorption mode of a novel group of N-benzylamino(boronphenyl)methylphosphonic acids using SERS

SERS study of different configurations of pharmaceutical and natural product molecules ginsenoside Rg3 under the interaction with human serum albumin on simple self-assembled substrate

Phthalazine adsorbed on colloidal silver surfaces is found to convert photochemically to a product in which the NN bond of the molecule likely breaks to form an adsorbed species resembling an ortho-substituted benzene. The photochemical kinetics was studied using a simple flow cell. The photochemical rate constant was found to be large in the visible region of the spectrum, increasing toward the blue. We show, incidentally, that SERS spectra of phthalazine reported previously by us and by others were heavily contaminated by the spectral features of the photoproduct. Hence previous explanations of the unusual excitation wavelength and coverage dependence are incorrect. The photochemical reaction is found to be a one-photon process; hence, the large absorption cross section in the visible is likely due to a metal to molecule charge transfer transition. (Solution-phase phthalazine is transparent in the visible.) It is likely that a significant number of published SERS spectra of other molecules contain spectral features due to photoproducts. By using dynamic methods such as that described, one can avoid these complications.

SERS spectroscopy of kaempferol and galangin under the interaction of human serum albumin with adsorbed silver nanoparticles

In this article, surface-enhanced Raman scattering (SERS) spectra of bombesin (BN) and its six modified analogues ([D-Phe(12)]BN, [Tyr(4)]BN, [Tyr(4),D-Phe(12)]BN, [D-Phe(12),Leu(14)]BN, [Leu(13)-(R)-Leu(14)]BN, and [Lys(3)]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 Trp(8). 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 N(1)--H bond for all the peptides, except [Phe(12)]BN. This is in contrary to the results obtained for the silver roughen electrode that show direct but not strong N(1)--H/Ag interaction for all peptides except [D-Phe(12),Leu(14)]BN and [Leu(13)-(R)-Leu(14)]BN. For BN only C==O is not involved in the chemical coordination with the colloidal surface. [Lys(3)]BN and BN also adsorb with the C--N bond of NH(2) group normal and horizontal, respectively, to the colloidal surface, whereas C--NH(2) in other peptides is tilted to this surface. Also, the Trp(8) --CH(2)-- moiety of only [Tyr(4)]BN, [Lys(3)]BN, and [Tyr(4),D-Phe(12)]BN coordinates to Ag, whereas the Phe(12) ring of [Phe(12)]BN, [Tyr(4),D-Phe(12)]BN, and [D-Phe(12),Leu(14)]BN assists in the peptides binding only on the colloidal silver.

This study presents the complete solid‐state vibrational assignments for a series of five zwitterionic phosphonodipeptides containing an N‐terminal glycine: L‐Gly‐L‐CH(Me)‐PO3H2 (G1), L‐Gly‐C(Me,Me)‐PO3H2 (G2), L‐Gly‐L‐CH(Et)‐PO3H2 (G3), L‐Gly‐C(Me,Et)‐PO3H2 (G4), and L‐Gly‐L‐CH(iBu)‐PO3H2 (G5). The assignments are based primarily on Fourier‐transform Raman spectra (FT‐RS) and Fourier‐transform infrared spectra (FT‐IR) spectra, as well as density functional theory (DFT) calculations at the B3LYP; 6‐31 + + G** level of theory. Existing literature data are also taken into consideration. The surface geometry of these molecules on a colloidal silver surface was also determined by observing the wavenumber, width, and relative intensity changes of enhanced bands in their surface‐enhanced Raman scattering spectra. It is proposed that G1 mainly adsorbs onto the colloidal silver particles through the phosphonate terminus, whereas the PO bond in G3 and G5 assists in the interaction of these molecules with the silver surface. G3 interacts with Ag mainly via α‐methlyalanine and the amide bond. It is also shown that the amide bond and glycine backbone are involved in the adsorption of G3 on the silver nanoparticles. In addition, the differences recorded for G4 and G5 SERS spectra are mainly due to interactions between the silver surface and the amine group and N‐ and P‐terminus, respectively, and are manifestations of the characteristic vibrations of these groups. Copyright © 2008 John Wiley &amp; Sons, Ltd.