Phase transitions in DNA-linked nanoparticle assemblies: a decorated-lattice model

We use decorated-lattice models to explore the phase behavior of two types of DNA-linked colloidal mixtures: systems with identical nanoparticles functionalized with two different DNA strands (mixture Aab) and mixtures involving two types of particles each one functionalized with a different DNA strand (mixture Aa-Ab). The model allows us to derive the properties of the mixtures from the well-known behavior of underlying spin-n Ising models with temperature and activity dependent effective interactions. The predicted evolution of the dissolution profiles for the colloidal assemblies as a function of temperature and number of single DNA strands on a nanoparticle M is in qualitative agreement with that observed in real systems. According to our model, the temperature at which the assemblies dissolve can be expected to increase with increasing M only for concentrations of colloids below a certain threshold. For more concentrated solutions, the dissolution temperature is a decreasing function of M. Linker-mediated interactions between Aa and Ab particles in the Aa-Ab mixture render the phase separation involving disordered aggregates metastable with respect to a phase transition between a solvent-rich and an ordered phase. The stability of the DNA-linked assembly is enhanced by the ordering of the colloidal network and the ordered aggregates dissolve at higher temperatures. Our results may explain the contrasting evolution of the dissolution temperatures with increasing probe size in Aab and Aa-Ab mixtures as observed experimentally.     

Surface and bulk dissolution properties, and selectivity of DNA-linked nanoparticle assemblies

Using a simple mean-field model, we analyze the surface and bulk dissolution properties of DNA-linked nanoparticle assemblies. We find that the dissolution temperature and the sharpness of the dissolution profiles increase with the grafting density of the single-stranded DNA "probes" on the surface of colloids. The surface grafting density is controlled by the linker occupation number, in analogy with quantum particles obeying fractional statistics. The dissolution temperature increases logarithmically with the salt concentration. This is in agreement with the experimental findings [R. Jin, G. Wu, Z. Li, C. A. Mirkin, and G. C. Schatz, J. Am. Chem. Soc. 125, 1643 (2003)]. By exploiting the unique phase behavior of DNA-coated colloids, it should be possible to detect multiple "targets" in a single experiment by essentially mapping the DNA base-pair sequence onto the phase behavior of DNA-linked nanoparticle solution.     

Exciton dynamics of GaSe nanoparticle aggregates

Time-resolved and static spectroscopic results on GaSe nanoparticle aggregates are presented to elucidate the exciton relaxation and diffusion dynamics. These results are obtained in room-temperature TOP/TOPO solutions at various concentrations. The aggregate absorption spectra are interpreted in terms of electrostatic coupling and covalent interactions between particles. The spectra at various concentrations may then be interpreted in terms of aggregate distributions calculated from a simple equilibrium model. These distributions are used to interpret concentration-dependent emission anisotropy kinetics and time-dependent emission spectral shifts. The emission spectra are reconstructed from the static emission spectra and decay kinetics obtained at a range of wavelengths. The results indicate that the aggregate z axis persistence length is about 9 particles. The results also show that the one-dimensional exciton diffusion coefficient is excitation wavelength dependent and has a value of about 2 x 10(-5) cm(2)/s following 406 nm excitation. Although exciton diffusion results in very little energy relaxation, subsequent hopping of trapped electron/hole pairs occurs by a Forster mechanism and strongly red shifts the emission spectrum.     

Simulation of ESR spectra of metal nanoparticle aggregates

Aggregates of polydisperse particles characterized by the preset values of the fractal dimensions and prefactor are built with the use of a special algorithm. ESR spectra of such aggregates are calculated in the self-consistent field approximation. It is shown that, even in sufficiently large aggregates with fractal structure, spectra greatly depend on the character of packing of large and small particles in the aggregate.     

Controlled interparticle spacing for surface-modified gold nanoparticle aggregates

Aggregation of gold nanoparticles of increasing size has been studied as a consequence of adsorption of 2-aminothiophenol (ATP) on gold nanoparticle surfaces. The capping property of ATP in the acidic pH range has been accounted from UV-vis absorption spectroscopy and surface-enhanced Raman scattering (SERS) studies. The effect of nanoparticle size (8-55 nm) on the nature of aggregation as well as the variation in the optical response due to variable degree of interparticle coupling effects among the gold particles have been critically examined. Various techniques such as transmission electron microscopy, X-ray diffraction, zeta-potential, and average particle size measurement were undertaken to characterize the nanoparticle aggregates. The aggregate size, interparticle distances, and absorption band wavelengths were found to be highly dependent on the pH of the medium and the concentration of the capping agent, ATP. The acquired SERS spectra of ATP relate the interparticle spacing. It has been observed that the SERS signal intensities are different for different sized gold nanoparticles.     

Optical limiting of gold nanoparticle aggregates induced by electrolytes

The electronic absorption spectra and optical-limiting (OL) properties of gold nanoparticle (AuNP) aggregates induced by KCl and NaCl have been investigated using 4.1-ns laser pulses at 532 nm. Although the individual AuNP colloid shows no optical-limiting effect, the AuNP aggregates exhibit significant optical-limiting characteristics. With an increased concentration of KCl and NaCl, the surface plasmon resonance (SPR) band shifts to a longer wavelength, and the optical-limiting performance is enhanced. Both the electronic absorption and optical limiting are influenced by the particle size. The larger the individual nanoparticle, the further red-shifted the SPR band and the stronger the optical limiting. Optical limiting of aggregates induced by KCl is stronger than that of aggregates induced by NaCl. Mechanistic studies reveal that free-carrier absorption is the dominant contributor to the optical limiting, with negligible contribution from nonlinear scattering.     

Stimuli-responsive disassembly of nanoparticle aggregates for light-up colorimetric sensing

Controlled assembly of nanomaterials has been the focus of much research. In contrast, controlled disassembly has not received much attention, even though both processes have been shown to be important in biology. By using a Pb2+-dependent RNA-cleaving DNAzyme, we demonstrate here control of the disassembly of gold nanoparticle aggregates in response to Pb2+. In the process, we show that nanoparticle alignment plays an important role in the disassembly process, with the tail-to-tail configuration being the most optimal, probably because of the large steric hindrance of other configurations. The rate of disassembly is significantly accelerated by using small pieces of DNA to invade the cleaved substrate of the DNAzyme. Investigation of such a controlled disassembly process allows the transformation of previously designed "light-down" colorimetric Pb2+ sensors into "light-up" sensors.     

Photoisomerization of azobenzene derivatives confined in gold nanoparticle aggregates

Photoisomerization is an important reaction that confers photoresponsive functionality on nanoparticles. Although photoisomerization of molecules forming self-assembled monolayers on two-dimensional surfaces or three-dimensional clusters has been studied, a detailed picture of interactions of molecules undergoing isomerization with nanoparticles is not available. In this paper, we report on the photoisomerization of azobenzene derivatives spatially confined in gold nanoparticle (AuNP) aggregates. AuNP aggregates allow us to simultaneously probe the structural changes of molecules via surface-enhanced Raman spectroscopy (SERS) and the accompanying changes in interparticle interactions via surface plasmon couplings. AuNP aggregates are formed by the adsorption of synthesized azobenzene-derivatized sulfides (Az) onto the surfaces of AuNPs. The photoisomerization of the adsorbed Az from trans to cis by excitation at 365 nm causes the AuNPs to move close to each other in the aggregates, leading to a redshift of the surface plasmon coupling band in the UV-vis spectra and a concomitant rise in SERS intensity. SERS spectra reveal that the vibrational modes containing the N=N stretching character redshift upon irradiation, suggesting that the N=N bond is significantly weakened when Az is in the cis form in the AuNP aggregates. The weakening of the N=N bond is attributed to the interaction of the N=N bond, which is more exposed to the outside in the cis conformation, with the nearby AuNPs that have come closer by the isomerization of adsorbed Az. We find that backisomerization from cis to trans occurs much faster in the AuNP aggregates (k = 1.9 × 10(-2) min(-1)) than in solution (k = 1.3 × 10(-3) min(-1)) because of the reduced N=N bond order of cis-Az in the aggregates.     

Sharp melting in DNA-linked nanostructure systems: thermodynamic models of DNA-linked polymers

Sharp melting that has been found for DNA-linked nanostructure systems such as DNA-linked gold nanoparticles enhances the resolution of DNA sequence detection enough to distinguish between a perfect match and single base pair mismatches. One intriguing explanation of the sharp melting involves the cooperative dehybridization of DNA strands between the nanostructures. However, in the DNA-linked gold nanoparticle system, strong optical absorption by the gold nanoparticles hinders the direct observation of cooperativity. Here, with a combination of theory and experiment, we investigate a DNA-linked polymer system in which we can show that the optical profile of the system at 260 nm is directly related to the individual DNA dehybridization profile, providing a clear distinction from other possible mechanisms. We find that cooperativity plays a crucial role in determining both the value of the melting temperature and the shape of the melting profile well away from the melting temperature. Our analysis suggests that the dehybridization properties of DNA strands in confined or dense structures differ from DNA in solution.     

Control of gold nanoparticle aggregates by manipulation of interparticle interaction

The size of gold nanoparticle aggregates was controlled by manipulating the interparticle interaction. To manipulate the interparticle interaction of gold nanoparticles prepared by citrate reduction, we applied the substitutive adsorption of benzyl mercaptan on the particle surface in the absence of the cross-linking effect. Various experimental techniques such as UV-vis absorption spectroscopy, surface-enhanced Raman scattering, quasi-elastic light scattering, and zeta-potential measurement were used to characterize the nanoparticle aggregates. Our results suggest that the replacement of the trivalent citrate ions adsorbed on the nanoparticle surface with monovalent benzyl mercaptan ions should destabilize the particles, causing aggregation and hence the increase in the size of nanoparticle aggregates. These experimental results were successfully rationalized by the classical DLVO (Derjaguin-Landau-Vervey-Overbeek) theory that describes the interparticle interaction and colloidal stability in solution. Our findings suggest that the control of surface potential is crucial in the design of stable gold nanoparticle aggregates.     

Preparation of controlled gold nanoparticle aggregates using a dendronization strategy

In this work, a dendronization strategy was used to control interparticle spacing and the optical properties of gold nanoparticle (NP) aggregates in aqueous media. To achieve this goal, two dendritic disulfides bearing different functionalities on their periphery were synthesized and used as ligands to dendronize gold NPs. The dendronized NPs then undergo aggregation; this process was followed by UV-vis spectroscopy, dynamic light scattering (DLS), and transmission electronic microscopy (TEM) measurements and correlated with Generalized Mie Theory electrodynamics calculations. For comparison, NP functionalization was also studied using a nondendritic ligand. It was found that the use of dendritic disulfides allows for the preparation of controlled NP aggregates. This study demonstrates how different dendronization parameters, such as disulfide concentration, temperature, time and nature of the ligand (dendritic vs nondendritic), determine the control exerted over the size and stability of the NP aggregates.     

Stability of DNA-linked nanoparticle crystals: effect of number of strands, core size, and rigidity of strand attachment

Three-dimensional ordered lattices of nanoparticles (NPs) linked by DNA have potential applications in novel devices and materials, but most experimental attempts to form crystals result in amorphous packing. Here we use a coarse-grained computational model to address three factors that impact the stability of bcc and fcc crystals formed by DNA-linked NPs : (i) the number of attached strands to the NP surface, (ii) the size of the NP core, and (iii) the rigidity of the strand attachment. We find that allowing mobility in the attachment of DNA strands to the core NP can very slightly increase or decrease melting temperature T(M). Larger changes to T(M) result from increasing the number of strands, which increases T(M), or by increasing the core NP diameter, which decreases T(M). Both results are consistent with experimental findings. Moreover, we show that the behavior of T(M) can be quantitatively described by the model introduced previously [F. Vargas Lara and F. W. Starr, Soft Matter, 7, 2085 (2011)].     

Fluorescence enhancement at hot-spots: the case of Ag nanoparticle aggregates

We report the enhancement of the fluorescence emitted from dye-labeled DNA upon co-aggregation with silver nanoparticles. The co-aggregation process is induced by the polycationic molecule spermine, which both neutralizes the charge of the DNA backbone and aggregates the nanoparticles. This simple method generates nanoparticle aggregates with very short (1-2 nm) inter-particle distance. Even though no spacer layer was used, large enhancements of the fluorescence, in the range of 15-740× (depending on the original quantum yield of the dye used), were observed. Theoretical modeling shows that this occurs as the local enhancement of the electromagnetic field near the hotspots is sufficiently large to overcome the quenching by the surface, even at short distances of 1 nm. The predicted trend of increased SEF enhancement with a decrease in initial quantum yield is observed. The average enhancements observed in this system are on-par with the best results obtained on nanostructured surfaces to date.     

SERS effect in CO physisorbed on homogeneous and core-shell nanoparticle aggregates

Surface Enhanced Raman Scattering (SERS) is studied for a simple molecule (CO) physisorbed on a nanoparticle belonging to a nanoparticle aggregate, with well defined composition and architecture, in order to assess the effect of metal nanostructure on the Raman enhancement. The approach involves explicit consideration of the molecule, with due allowance for the characteristics of its radiated field, which are believed to be particularly important elements in determining enhancement from complex-shape aggregates. The electrodynamic problem for a nonresonant polarizable point dipole in the presence of an aggregate of spherical scatterers has been resolved numerically, extending to a multi-particle system the treatment put forward by Kerker. Contribution to the Fernando Bernardi Memorial Issue.     

Spatially controlled SERS patterning using photoinduced disassembly of gelated gold nanoparticle aggregates

Controlling the assembly of the nanoparticles is important because the optical properties of noble metal nanoparticles, such as the surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS), are critically dependent on interparticle distances. Among many approaches available, light-induced disassembly is particularly attractive because it enables spatial modification of the optical properties of nanoparticle assemblies. In this study, we prepare gold nanoparticle (AuNP) aggregates in a gel matrix. Irradiation of the gelated AuNP aggregates at 532 nm leads to the disassembly of the aggregates, changing the color (SPR) from dark blue to red and extinguishing the SERS signal along the irradiated pattern, which opens the possibility of facile fabrication of spatially controlled SERS-generating microstructures. The photoinduced disassembly of the AuNP aggregates in solution is also investigated using UV-vis spectroscopy and transmission electron microscopy.     

Reversible generation of gold nanoparticle aggregates with changeable interparticle interactions by UV photoactivation

Evolution of exclusively spherical tiny gold nanoparticle aggregates is reported by UV photoactivation of aqueous HAuCl4 solution in cetyltrimethylammonium chloride micelles. In the photoactivation process, citrate is introduced for the first time to obtain aggregates of interacting particles with a tight size distribution. It is seen that the spectrum is substantially altered from the usual Au plasma resonance while the particles are present in the aggregate. Due to the interparticle interaction, the solution renders a blue color. Blue-pink color transformation of the gold sol has been observed in relation to the change in the interparticle distances without any change in the aspect ratio of the particles.     

Ultrafast electronic relaxation and coherent vibrational oscillation of strongly coupled gold nanoparticle aggregates

We report the first direct observation of the ultrafast electronic relaxation and coherent vibrational oscillation of strongly interacting gold nanoparticle aggregates measured by femtosecond laser spectroscopy. The electronic relaxation, reflected as a fast decay component with a time constant of 1.5-2.5 ps, becomes faster with decreasing pump power, similar to earlier observations of isolated gold nanoparticles. Surprisingly, periodic oscillations have been observed in the transient absorption/bleach signal and have been attributed to the coherent vibrational excitation of the gold nanoparticle aggregates. The oscillation period has been found to depend on the probe wavelength. As the probe wavelength is varied from 720 to 850 nm, the period changes from 37 to 55 ps. This suggests that the broad extended plasmon band (EPB) contains contributions from gold nanoparticle aggregates with different sizes and/or different fractal structures. Each of the different probe wavelengths therefore interrogates one subset of the aggregates with similar size or structure. Interestingly, the observed oscillation period for a given aggregate size determined by dynamic light scattering is longer than that predicted based on a elastic sphere model. One possible explanation is that the actual size of the aggregates is larger than what was observed from dynamic light scattering. An alternative, perhaps more likely, explanation is that the vibration of the aggregates is "softer" than that of hard spherical gold nanoparticles possibly because the longitudinal speed of sound is lower in the aggregates than in bulk gold. Persistent spectral hole burning was performed and yielded a hole in the nanoparticle aggregate's extended plasmon band, further supporting that the near-IR band is composed of absorption subbands from differently sized/structured aggregates.     

Construction of simple gold nanoparticle aggregates with controlled plasmon–plasmon interactions

We have developed a colloidal assembly for the study of plasmon–plasmon interactions between gold nanoparticles. Colloidal aggregates of controlled size and interparticle spacing were synthesized on silica nanoparticle substrates. Following the immobilization of isolated gold nanoparticles onto silica nanoparticles, the surfaces of the adsorbed gold nanoparticles were functionalized with 4-aminobenzenethiol. This molecular linker attached additional gold nanoparticles to the ‘parent' gold nanoparticle, forming small nanoparticle aggregates. The optical absorption spectrum of these clusters differed from that of gold colloid in a manner consistent with plasmon–plasmon interactions between the gold nanoparticles.