Metal-enhanced fluorescence of dyes with quadrupole surface plasmon resonance of silver nanoparticles.

Silver colloidal films (SCFs) composed of homogeneous 60-220 nm silver nanoparticles were synthesized for optimal fluorescence enhancement of chromophores with the dipole and quadrupole surface plasmons. The fluorescence enhancements with the SCFs of three chromophores, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran, 4-dimethylamino-4'-nitrobiphenyl, and coumarin 343 whose emission spectra are centered distinctively in the 470-560 nm wavelength range were compared. Fluorescence enhancements and lifetime changes were investigated via time-resolved fluorescence spectroscopy. The spectral overlap between the chromophore's emission and the dipole or quadrupole surface plasmon resonance (SPR) bands determined the fluorescence enhancements with the SCFs. The dipole and quadrupole SPR bands both appeared to provide effective fluorescence enhancements of chromophores. This knowledge allows researchers to develop sensitive fluorescence sensors by combining nanoparticles with optimal dipole or quadrupole SPR bands in order to achieve fluorescence enhancement of a specific chromophore. The emission dynamics measurements with the SCFs were combined with the finite-difference time-domain simulation results for the local electric fields around the silver nanoparticles to enable discussion of metal-enhanced fluorescence mechanisms, including excitation and emission enhancements.

Intramolecular Charge Transfer of Curcumin and Solvation Dynamics of DMSO Probed by Time-Resolved Raman Spectroscopy.

Intramolecular charge transfer (ICT) of curcumin in dimethyl sulfoxide (DMSO) solution in the excited state was investigated by femtosecond electronic and vibrational spectroscopy. Excited-state Raman spectra of curcumin in the locally-excited and charge-transferred (CT) state of the S1 excited state were separated due to high temporal (<50 fs) and spectral (<10 cm-1) resolutions of femtosecond stimulated Raman spectroscopy. The ultrafast (0.6-0.8 ps) ICT and subsequent vibrational relaxation (6-9 ps) in the CT state were ubiquitously observed in the ground- and excited-state vibrational modes of the solute curcumin and the νCSC and νS=O modes of solvent DMSO. The ICT of curcumin in the excited state was preceded by the disruption of the solvation shells, including the breakage of hydrogen bonding between curcumin and DMSO molecules, which occurs at the ultrafast (20-50 fs) time scales.

Surface adsorption of hydroxyanthraquinones on CTAB-modified gold nanosurfaces.

Gold nanosurfaces are widely applied to the surface-enhanced Raman spectroscopy (SERS) detection of the biological systems. The surface modification of gold nanoparticles (AuNPs) is often required when the analytes do not efficiently adsorb on the surface. In this paper, an aggregation of AuNPs with cetyltrimethylammonium bromide (CTAB) was introduced for the efficient surface adsorption and strong SERS enhancement for a number of hydroxyanthraquinones (HAQs). The SERS of HAQs including 1,2-dihydroxyanthraquinone (alizarin) were strongly enhanced with CTAB-modified AuNPs and deprotonation of alizarin was clearly observed upon the pH change. The CTAB-modified AuNPs are regarded as efficient SERS substrates for many biological molecules with weak surface adsorption.

Adsorption of dipeptide L-alanyl-L-tryptophan on gold colloidal nanoparticles studied by surface-enhanced Raman spectroscopy.

Surface adsorption of a dipeptide L-alanyl-L-tryptophan (Ala-Trp) on gold nanoparticles reduced by citrate (CT) and borohydride (BH) ions was investigated by a surface-enhanced Raman scattering (SERS) technique. Two distinct SERS spectra of Ala-Trp depending on the types of gold nanoparticles were observed, and the vibrational assignments were based on the density functional theory simulations and the previous SERS results of Trp. Ala-Trp mainly adsorbs through the amine group on CT gold nanoparticles with a perpendicular orientation of the indole ring to the surface. In contrast, the adsorption occurs via the π electrons of the indole ring on the BH gold surfaces while maintaining a flat geometry of the indole ring to the surface. The amide I band of Ala-Trp was observed only with the CT gold colloids in acidic and neutral conditions where partial surface adsorption via the amide group is expected.

Metal-enhanced fluorescence and excited state dynamics of carotenoids in thin polymer films.

Metal-enhanced fluorescence of carotenoids, all-trans-ß-carotene and 8'-apo-ß-carotene-8'-al dispersed in thin layers of polystyrene and polyethylene glycol were investigated by time-resolved fluorescence spectroscopy. The weak emission signals of carotenoids in polymer films were increased by 4-40 times in the presence of a silver island film and the emission lifetimes of both carotenoids were measured as significantly shortened. The energy transfer from the intermediate states of carotenoids to the silver islands and the subsequent surface plasmon coupled emission were proposed for the mechanisms of metal-enhanced fluorescence. The fluorescence enhancements of carotenoids in the polymer films were also investigated statistically over a wide area of the silver island films.

Homogeneous silver colloidal substrates optimal for metal-enhanced fluorescence.

Homogeneous silver colloidal films (SCFs), composed of silver nanoparticles 67-193 nm in diameter, were synthesized by a seeded-growth method as the substrates for metal-enhanced fluorescence (MEF). The homogeneity and uniform particle distribution of the SCFs showed many advantages for the exploration of the MEF mechanism. The fluorescence enhancement of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) and rhodamine 700 (Rh700) dyes dispersed in a thin layer of polystyrene (PS) with the SCFs was observed by time-resolved fluorescence spectroscopy. The fluorescence enhancements of DCM and Rh700 become larger when the surface plasmon resonance bands of SCFs overlap the emission bands of dyes. The particle-size-dependent changes of the radiative and non-radiative rate constants of both dyes with the SCFs are estimated by an improved analysis combining the fluorescence intensity and lifetime measurements and the finite-difference time-domain method simulations.

Plasmon coupling between silver nanoparticles: Transition from the classical to the quantum regime.

We explore plasmon coupling between silver nanoparticles (AgNPs) as two AgNPs approach each other within a subnanometer distance. We prepare AgNP dimers with two 21-nm AgNPs separated by alkanedithiol linkers in high yield. Changing the length of the alkanedithiol linkers enables us to control the interparticle distance down to the subnanometer level on the molecular scale. We observe that the longitudinal plasmon coupling band, which is sensitive to the interaction between AgNPs, gradually redshifts as the interparticle distance decreases. This observation is fully consistent with the classical electromagnetic model. The redshift of the plasmon coupling, however, undergoes a drastic change when the interparticle distance reaches ∼1nm. The longitudinal plasmon coupling band vanishes and a new intense band appears at a shorter wavelength. This band redshifts as the nanogap further narrows, but crosses over to a blueshift at ∼0.7nm. A comparison of our observation with finite-difference time-domain simulations reveals that this band arises from quantum effects. Controlled assembly of AgNP dimers in combination with simulations allows us to observe the transition of the plasmon coupling from the classical to the quantum regime at the ensemble level.

Bridging the Nanogap with Light: Continuous Tuning of Plasmon Coupling between Gold Nanoparticles.

The control of nanogaps lies at the heart of plasmonics for nanoassemblies. The plasmon coupling sensitively depends on the size and the shape of the nanogaps between nanoparticles, permitting fine-tuning of the resonance wavelength and near-field enhancement at the gap. Previously reported methods of molecular or lithographic control of the gap distance are limited to producing discrete values and encounter difficulty in achieving subnanometer gap distances. For these reasons, the study of the plasmon coupling for varying degrees of interaction remains a challenge. Here, we report that by using light, the interparticle distance for gold nanoparticle (AuNP) dimers can be continuously tuned from a few nanometers to negative values (i.e., merged particles). Accordingly, the plasmon coupling between the AuNPs transitions from the classical electromagnetic regime to the contact regime via the nonlocal and quantum regimes in the subnanometer gap region. We find that photooxidative desorption of alkanedithiol linkers induced by UV irradiation causes the two AuNPs in a dimer to approach each other and eventually merge. Light-driven control of the interparticle distance offers a novel means of exploring the fundamental nature of plasmon coupling as well as the possibility of fabricating nanoassemblies with any desired gap distance in a spatially controlled manner.