Spectroscopic and fluorescence properties of silver-dye composite nanoparticles

The aim of this work was to investigate the formation of J-aggregates of thiacyanine dye (TC, 5,5′-disulfopropyl-3,3′-dichlorothiacyanine sodium salt) in the presence of 6 nm spherical silver nanoparticles (Ag NPs) using spectrophotometric and fluorescence methods. The formation of J-aggregates was concentration dependent and characterized by the appearance of the new absorption band with the maximum at 481 nm. Spectrophotometric study of J-aggregate formation and time stability suggested that they were formed on the account of monomer form of TC. Moreover, the stability of J-aggregates increased with the lowering AgNPs concentration. The measurements of fluorescence of the NPs—dye assembly clearly indicated that the fluorescence of TC was quenched by Ag NPs on the concentration dependent manner. The spectrophotometric and fluorescence properties of NPs—dye assembly were found to be quantitatively related to the surface coverage of the dye on the Ag NPs.     

Exciton-coupled charge-transfer dynamics in a porphyrin J-aggregate/TiO(2) complex

Exciton-coupled charge-transfer (CT) dynamics in TiO(2) nanoparticles (NP) sensitized with porphyrin J-aggregates has been studied by femtosecond time-resolved transient absorption spectroscopy. J-aggregates of 5,10,15-triphenyl-20-(3,4-dihydroxyphenyl) porphyrin (TPPcat) form CT complexes on TiO(2) NP surfaces. Catechol-mediated strong CT coupling between J-aggregate and TiO(2) NP facilitates interfacial exciton dissociation for electron injection into the conduction band of the TiO(2) nanoparticle in pulse width limited time (<80 fs). Here, the electron-transfer (<80 fs) process dominates over the intrinsic exciton-relaxation process (J-aggregates: ca. 200 fs) on account of exciton-coupled CT interaction. The parent hole on J-aggregates is delocalized through J-aggregate excitonic coherence. As a result, holes immobilized on J-aggregates are spatially less accessible to electrons injected into TiO(2) , and thus the back electron transfer (BET) process is slower than that of the monomer/TiO(2) system. The J-aggregate/porphyrin system shows exciton spectral and temporal properties for better charge separation in strongly coupled composite systems.     

Preparation and optical properties of Eu(III) complexes J-aggregate formed on the surface of silver nanoparticles

Ag colloidal nanoparticles coated with Eu(TTA)₃ · 2H₂O complexes were prepared, and it was found that Eu(TTA)₃ · 2H₂O complexes J-aggregate was formed on the surface of Ag nanoparticles according to a red shift (18.2 nm) in UV–Vis spectra. However, there had similar excitation wavelength, which was attributed to existence of Ag nanoparticles. Highly luminescent properties of Ag colloidal nanoparticles were observed, and it was believed to result from low energy transfer between Eu(III) complexes and Ag and the large electromagnetic field arising from the excitation of surface plasmon polariton of Ag nanoparticles.     

Adsorption of cyanine dyes on gold nanoparticles and formation of J-aggregates in the nanoparticle assembly

This paper describes the results of an investigation of the interparticle interactions and reactivities in the assembly of gold nanoparticles mediated by cyanine dyes. The combination of the positively charged indolenine cyanine dyes and the negatively charged gold nanoparticles is shown to form a J-aggregate bridged assembly of nanoparticles, in addition to hydrophobic interparticle and electrostatic dye-particle interactions. Such interparticle interactions and reactivities are studied by probing the absorption of J-aggregates and fluorescence from the dyes and the surface plasmon resonance absorption from the nanoparticles. The J-aggregation of the dyes adsorbed on the nanoparticles is shown to play an important role in the assembly of nanoparticles. The spectral evolution of the J-band of the dyes and the surface plasmon resonance band of the nanoparticles was found to be sensitive to the nature of the charge and the structure of the dyes. The fluorescence quenching for the dyes was shown to be quantitatively related to the surface coverage of the dyes on the nanocrystal surfaces. These findings have provided important information for assessing a two-step process involving a rapid adsorption of the dyes on the nanoparticles and a subsequent assembly of the nanoparticles involving a combination of interparticle J-aggregation and hydrophobic interactions of the adsorbed dyes. The results are discussed in terms of the structural effects of the dyes, and the interparticle molecular interactions and reactivities, which provide important physical and chemical insights into the design of dye-nanoparticle structured functional nanomaterials.     

Porphyrin J-aggregates stabilized by ferric myoglobin in neutral aqueous solution

J-aggregates of a diacid form (H4TPPS2-) of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4-) were stabilized by binding with ferric myoglobin (metMb) in aqueous solution at neutral pH. The J-aggregates gradually dissociated to monomeric H2TPPS(4-). The average half-lifetime (t1/2) of the J-aggregates in the presence of sufficient amounts of metMb was ca. 3 h in phosphate buffer at pH 7.0 and 25 degrees C. The stabilization of the J-aggregate by metMb is ascribed to encapsulation and fixation of an edge-to-edge structure of the J-aggregate by the relatively rigid protein molecules. The secondary structure of metMb was altered in some extent in the presence of an excess amount of the J-aggregates while no effect on denaturation of metMb was observed with the H2TPPS(4-) monomer or polyacrylate. The hydrophobic nature of the J-aggregate seems to play an important role for denaturation of metMb. The ability of denatured metMb to bind the azide anion was higher than that of natural metMb. The denaturation of metMb by the J-aggregates seems to induce surfacing of hemin leading to an entropy gain in coordination of the N3(-) anion to the iron(III) center.     

J-aggregation and disaggregation of indocyanine green in water

J-aggregates of indocyanine green sodium iodide in water are formed by heat treatment. Starting from a dimeric solution the activation energy of molecule attachment (E_att ≈ 0.41 ev) to J-aggregates is determined by analysing the temperature dependence of the rate of J-aggregate absorption growth. The activation energy of molecule detachment (E_det ≈ 0.51 eV) from J-aggregates is deduced from the temperature dependent rate of J-aggregate absorption decrease after strong dilution.     

Preparation of J-aggregate liposome dispersions and their chromic transformation

We report the preparation of aqueous liposome dispersions of J-aggregates formed by the amphiphilic merocyanine dye (MD). A series of liposome-forming lipids were dispersed together with MD J-aggregates at different molar ratios of MD to lipid. The MD J-aggregate dispersions prepared with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) at the MD to DMPC ratio of 0.16 exhibit good dispersibility; that is, they can be readily redispersed without any flocculation even after their precipitation. By use of different counterions for the MD molecules, two types of J-aggregate dispersions, one that exhibits an absorption band (J-band) at 635 nm (type I) and the other at 600 nm (type II), were obtained. As an example of the use of MD J-aggregates liposome dispersions, the thermochromic transformation of MD J-aggregates was demonstrated. When the dispersions are heated, J-aggregates of type I transformed into type II at a certain temperature (T(disp)). The parameters that control the speed of the transformation and the value of T(disp) were determined.     

J-aggregation in alpha-sexithiophene submonolayer films on silicon dioxide

We report on the observation of J-aggregates in submonolayer films of alpha-sexithiophene grown on silicon dioxide. Photoluminescence spectroscopy reveals that submonolayers are formed by molecules lying flat on the substrate with a head to tail configuration. Excitation energy dependence of photoluminescence shows a red-shifted absorption with respect to isolated molecules and a negligible Stokes shift between absorption and emission. The pronounced structural order of J-aggregates is reflected in the fwhm of the emission bands. From time-resolved and low-temperature photoluminescence experiments, we infer a quantum yield of the J-aggregate between 0.6 and 1. The demonstration of spontaneous formation of J-aggregates of pi-conjugated systems on amorphous silicon-based substrates can be relevant for the development of organic-inorganic hybrid photonic devices.     

Interaction of cyanine dyes with nucleic acids. XVIII. Formation of the carbocyanine dye J-aggregates in nucleic acid grooves.

Spectral properties of carbocyanine dye 3-methyl-2-[3-methyl-2-(3-methyl-2,3-dihydro-1,3-benzothiazole-2-iliden)-1- butenyl]-1,3-benzothiazole-3-il iodide (Cyan betaiPr) in water solution, as well as in the presence of different types of double stranded DNA have been studied. While in water solution of 'free' dye Cyan betaiPr stays mainly in monomeric form, in the presence of DNA the dye molecules form J-aggregates. The molecular structure of these J-aggregates causes the Davydov splitting of their absorption band, corresponding to the first electronic transition. A study of site-specificity showed that in the presence of poly (dA/dT) the majority of Cyan betaiPr molecules form J-aggregates, while in the presence of poly (dGC/dGC) dye molecules stay mainly in monomeric form and in presence of chicken erythrocytes DNA both J-aggregate and monomeric forms of dye are present. We suppose that Cyan betaiPr molecules aggregate in DNA groove, which serves as a template for J-aggregate forming. An increase of ionic strength of solution leads to the release of dye molecules from DNA grooves and prevents J-aggregates formation.     

J-Aggregate-Based FRET Monitoring of Drug Release from Polymer Nanoparticles with High Drug Loading

Understanding drug-release kinetics is critical for the development of drug-loaded nanoparticles. We developed a J-aggregate-based Förster-resonance energy-transfer (FRET) method to investigate the release of novel high-drug-loading (50 wt %) nanoparticles in comparison with low-drug-loading (0.5 wt %) nanoparticles. Single-dye-loaded nanoparticles form J-aggregates because of the high dye-loading (50 wt %), resulting in a large red-shift (≈110 nm) in the fluorescence spectrum. Dual-dye-loaded nanoparticles with high dye-loading using FRET pairs exhibited not only FRET but also a J-aggregate red-shift (116 nm). Using this J-aggregate-based FRET method, dye-core–polymer-shell nanoparticles showed two release processes intracellularly: the dissolution of the dye aggregates into dye molecules and the release of the dye molecules from the polymer shell. Also, the high-dye-loading nanoparticles (50 wt %) exhibited a slow release kinetics in serum and relatively quick release in cells, demonstrating their great potential in drug delivery.     

Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.     

Plasmon-based free-radical photopolymerization: effect of diffusion on nanolithography processes

This Article interrogates the mechanisms responsible for nanoscale photopolymerization induced by confined and enhanced electromagnetic fields. Surface plasmon dipolar resonance of individual Ag nanoparticles was used as an optical near-field source to locally trigger the reaction of a photopolymerizable formulation. Laser excitation of the nanoparticles embedded in the formulation reproducibly generates polymer features with typical dimensions ranging from 2 nm to a few tens of nanometer. We have determined the physicochemical parameters and mechanisms controlling the spatial extent of the photopolymerization process. We found that the diffusion of the dye is the main process limiting the polymerization reaction, as opposed to what is observed at the microscale with an equivalent chemical system. This approach demonstrates that plasmon-based polymerization can achieve true nanometer scale resolution and also provides a unique opportunity to investigate photochemistry at this length scale.     

Chiral J-aggregates of atropo-enantiomeric perylene bisimides and their self-sorting behavior

Herein we report on structural, morphological, and optical properties of homochiral and heterochiral J-aggregates that were created by nucleation-elongation assembly of atropo-enantiomerically pure and racemic perylene bisimides (PBIs), respectively. Our detailed studies with conformationally stable biphenoxy-bridged chiral PBIs by UV/Vis absorption, circular dichroism (CD) spectroscopy, and atomic force microscopy (AFM) revealed structurally as well as spectroscopically quite different kinds of J-aggregates for enantiomerically pure and racemic PBIs. AFM investigations showed that enantiopure PBIs form helical nanowires of unique diameter and large length-to-width ratio by self-recognition, while racemic PBIs provide irregular-sized particles by self-discrimination of the enantiomers at the stage of nucleation. Steady-state fluorescence spectroscopy studies revealed that the photoluminescence efficiency of homochiral J-aggregated nanowires (47±3%) is significantly higher than that of heterochiral J-aggregated particle-like aggregates (12±3%), which is explained in terms of highly ordered molecular stacking in one-dimensional nanowires of homochiral J-aggregates. Our present results demonstrate the high impact of homochirality on the construction of well-defined nanostructures with unique optical properties.     

Photophysical property and photostability of J-aggregate thin films of thiacyanine dyes prepared by the spin-coating method

By use of electrostatic interactions of dye molecules and poly(diallyldimethylammonium chloride) (PDDA), the spin-coating technique has been successfully applied to the preparation of stable J-aggregate thin films of thiacarbocyanine dyes on a polycarbonate or quartz plate. The J-aggregate thin films were prepared by the spin-coating of PDDA aqueous solution on dye thin films prepared on a substrate by the spin-coating of 2,2,3,3-tetrafluoro-1-propanol solution of dyes. Photophysical properties of the dye thin films and J-aggregate thin films were studied by measuring the fluorescence spectra, quantum yields, and lifetimes. Coherent size of the J-aggregates was estimated to be 3-12 by means of the absorption bandwidth (full width at half maximum) or radiative lifetime. Photostability of the J-aggregate thin films was also studied in terms of photodegradation efficiency under argon and oxygen in comparison with the dye thin films, and J-aggregate thin films were found to be more stable than the corresponding dye thin films.     

J-Aggregates Formed by NaCl Treatment of Aza-Coating Heptamethine Cyanines and Their Application to Monitoring Salt Stress of Plants and Promoting Photothermal Therapy of Tumors

The cationic nature of heptamethine cyanines gives them the capacity to form aggregates with salts by electrostatic interactions. In this work, NaCl promoted J-aggregate formation of aza-coating heptamethine cyanines is explored. NaCl can induce the N-benzyloxycarbonyl Cy-CO₂Bz to assemble into a J-aggregate having an absorption at 890 nm. Its excellent fluorescence response to NaCl implies that it has great potential for use as a probe for tracing salt stress in plants. Moreover, NaCl also promotes formation of J-aggregates from the N-ethyloxycarbonyl Cy-CO₂Et . The aggregate shows an intense absorption at 910 nm compared to the monomer which absorbs at 766 nm. Its J-aggregated form can serve as a photothermal agent. And the photothermal conversion efficiency is increased from 29.37 % to 57.59 %. This effort leads to the development of two applications of new cyanine J-aggregates including one for tracing salt stress of plants and the other for promoting photothermal therapy of tumors.     

Raman scattering of 4-aminobenzenethiol sandwiched between Ag nanoparticle and macroscopically smooth Au substrate: effects of size of Ag nanoparticles and the excitation wavelength

A nanogap formed by a metal nanoparticle and a flat metal substrate is one kind of "hot site" for surface-enhanced Raman scattering (SERS). Accordingly, although no Raman signal is observable when 4-aminobenzenethiol (4-ABT), for instance, is self-assembled on a flat Au substrate, a distinct spectrum is obtained when Ag or Au nanoparticles are adsorbed on the pendent amine groups of 4-ABT. This is definitely due to the electromagnetic coupling between the localized surface plasmon of Ag or Au nanoparticle with the surface plasmon polariton of the planar Au substrate, allowing an intense electric field to be induced in the gap even by visible light. To appreciate the Raman scattering enhancement and also to seek the optimal condition for SERS at the nanogap, we have thoroughly examined the size effect of Ag nanoparticles, along with the excitation wavelength dependence, by assembling 4-ABT between planar Au and a variable-size Ag nanoparticle (from 20- to 80-nm in diameter). Regarding the size dependence, a higher Raman signal was observed when larger Ag nanoparticles were attached onto 4-ABT, irrespective of the excitation wavelength. Regarding the excitation wavelength, the highest Raman signal was measured at 568 nm excitation, slightly larger than that at 632.8 nm excitation. The Raman signal measured at 514.5 and 488 nm excitation was an order of magnitude weaker than that at 568 nm excitation, in agreement with the finite-difference time domain simulation. It is noteworthy that placing an Au nanoparticle on 4-ABT, instead of an Ag nanoparticle, the enhancement at the 568 nm excitation was several tens of times weaker than that at the 632.8 nm excitation, suggesting the importance of the localized surface plasmon resonance of the Ag nanoparticles for an effective coupling with the surface plasmon polariton of the planar Au substrate to induce a very intense electric field at the nanogap.     

The Chemical Potential of Plasmonic Excitations

By the photoexcitation of localized surface plasmon resonances of metal nanoparticles, one can generate reaction equivalents for driving redox reactions. We show that, in such cases, there is a chemical potential contributed by the plasmonic excitation. This chemical potential is a function of the concentration of light, as we determine from the light‐intensity‐dependent activity in the plasmon‐excitation‐driven reduction of CO₂ on Au nanoparticles. Our finding allows the treatment of plasmonic excitation as a reagent in chemical reactions; the chemical potential of this reagent is tunable by the light intensity.     

Two-photon absorption of a supramolecular pseudoisocyanine J-aggregate assembly

Linear spectral properties, including excitation anisotropy, of pseudoisocyanine or 1,1′-diethyl-2,2′-cyanine iodide (PIC) J-aggregates in aqueous solutions with J-band position at 573 nm were investigated. Two-photon absorption of PIC J-aggregates and monomer molecules was studied using an open aperture Z-scan technique. A strong enhancement of the two-photon absorption cross-section of PIC in the supramolecular J-aggregate assembly was observed in aqueous solution. This enhancement is attributed to a strong coupling of the molecular transition dipoles. No two-photon absorption at the peak of the J-band was detected.     

Photoinduced electron storage and surface plasmon modulation in Ag@TiO2 clusters

The reversible charging and discharging effects associated with photoexcitation of a TiO2 shell in a Ag@TiO2 composite are described. The photoinduced charge separation in the TiO2 shell is followed by electron injection into the silver core. Interestingly, the charging of the silver core is associated with the shift in the surface plasmon band from 460 to 430 nm. The stored electrons are discharged upon exposure of the charged Ag@/TiO2 composite to an electron acceptor. As the electrons from the silver core are discharged, the original surface plasmon absorption of the Ag core is restored.     

Kinetics and mechanism of the formation of Ag nanoparticles by electrochemical techniques: a plasmon and cluster time-resolved spectroscopic study

The formation of Ag nanoparticles by electrochemical techniques has been investigated through a time-resolved UV-vis spectroscopy study. The formation of Ag(4)(2+) clusters is suggested as the main precursors to the particle formation. The mechanism also considers the electrodeposition which occurs as a parallel process in the electrochemical particle formation. Experiments at different current densities show that the electrodeposition is more important at low current densities. From the fittings of the change of the plasmon (lambda approximately 430 nm) and the cluster (lambda = 250 nm) bands to the proposed mechanism, the kinetic constants of the formation and disappearance of the Ag(4)(2+) cluster are derived. The kinetic fittings also allowed an estimation of the Ag(4)(2+) cluster extinction coefficient (epsilon(250) = 1.0 x 10(4) M(-1) cm(-1)). It is observed that the plasmon bandwidth (fwhm) follows the theoretical predicted 1/R law only for particles with sizes d approximately >3 nm, but the law is broken for the smallest particles (d < 2.5 nm). The break is associated with the existence of single-electron (SE) transitions which are activated by the plasmon decay for the smallest nanoparticles. From the broken 1/R law, a limit relaxation time of about 4 fs is derived for the plasmon deactivation. Below this limit, the plasmon seems to decay mainly through a nonradiative channel with the formation of electron-hole (e-h) pairs. By comparison of the 1/R broken law with other literature results, it is concluded that large interactions of the Ag nanoparticles with the used capping molecule (tetrabutylammonium acetate) facilitate the e-h plasmon deactivation.