Synthesis and Characterization of Ag@TiO2 Core-shell Nanoparticles and TiO2 Nanobubbles

Ag@TiO₂ core-shell structured particles of nano-size dimensions have been successfully prepared via a one-step way, which has proved quite effective in procuring stable colloids. Transmission electron microscopy (TEM) was employed to characterize the core size and the shell thickness, which typically were 20~40 nm and ~2 nm, respectively. X-ray diffraction (XRD) indicated the existence of silver. Optical absorption dependence on core size and synthetic temperature has been explored by UV–Vis absorption spectroscopy. Finally, the interesting titanium dioxide nanobubbles with silver core leached out by a unique means, were studied, which consequently proved the core-shell structure of the prepared nanoparticles, confirming the TEM observation.     

Thiol‐immobilized silver nanoparticle aggregate films for surface enhanced Raman scattering

We report a novel method for the fabrication of films of silver nanoparticle aggregates that are strongly attached to Si substrates (Thiol‐immobilized silver nanoparticle aggregates or TISNA). The attachment is achieved by chemically modifying the surface of a Si(100) surface in order to provide SH groups covalently linked to the substrate and then aggregating silver nanoparticles on these thiol covered surfaces. The transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) characterization show a high coverage with single nanoparticles or small clusters and a partial coverage with fractal aggregates that provide potential hot spots for surface enhanced Raman scattering (SERS). We have confirmed the SERS activity of these films by adsorbing rhodamine 6G and recording the Raman spectra at several concentrations. By using the silver‐chloride stretching band as an internal standard, the adsorbate bands can be normalized in order to correct for the effects of focusing and aggregate size, which determine the number of SERS active sites in the focal area. This allows a quantitative use of SERS to be done. The adsorption–desorption of rhodamine 6G on TISNA films is reversible. These features make our TISNA films potential candidates for their use in chemical sensors based on the SERS effect. Copyright © 2008 John Wiley & Sons, Ltd.     

Selective reduction of nitroaromatic compounds on silver nanoparticles by visible light

For the first time, we report experimentally and theoretically that nitroaromatic compounds, 2,4‐dinitrobenzenethiol and 4‐chloro‐2‐nitrobenzenethiol, on silver sols can be selectively reduced to 2‐amino‐4‐nitrobenzenethiol and 2‐amino‐4‐chlorobenzenethiol simply by irradiating with a visible light in ambient conditions, and the selective photoreduction is a very facile process. The results of quantum chemical calculations are in good agreement with our experimental data. Copyright © 2012 John Wiley & Sons, Ltd.     

Gold and gold–silver core-shell nanoparticle constructs with defined size based on DNA hybridization

Nanoparticles represent versatile building blocks in material science and nanotechnology. Thereby, the defined assembly of nanostructures (13 and 56 nm in diameter, respectively) is of significant importance. Short DNA sequences can be bound to the nanoparticle surface thus enabling highly specific DNA hybridization-driven events that direct the formation of nanoparticle constructs. In this paper, examples for the defined formation of gold nanoparticle constructs are demonstrated. In addition, gold–silver core-shell nanoparticles are introduced as further building blocks for the hybridization-controlled formation of nanoparticle constructs.     

Raman spectra of benzoic acid enhanced by the silver nanoparticles of various sizes

Using sodium borohydride as the reducing agent and polyvinyl pyrrolidone (PVP, MW = 10 000) as the stabilizer, we obtained silver nanoparticles of various diameters (8–78 nm) from silver nitrate aqueous solutions in the concentration range from 0.001 to 0.1 M. The surface‐enhanced Raman scattering (SERS) from benzoic acid's ring‐breathing mode at 1003 cm⁻¹ was detected from its dilute solutions (∼10⁻² M) doped with these silver nanoparticles under 488‐nm laser excitation. The observed size dependences of SERS intensities fit quite well with those calculated by Schatz's theoretical model for spherical silver nanoparticles. The only exception occurred with the smallest particles (8 nm), possibly due to the failure of Maxwell's electromagnetic theory used in this model. Copyright © 2009 John Wiley & Sons, Ltd.     

聚集效应对银纳米粒子的二阶非线性光学特性的影响研究

运用超瑞利散射(HRS)技术,对由KNO3诱导聚集的银纳米粒子的二阶光学非线性特性进行了实验研究.通过粒子尺寸测量和透射电镜观察，表明银纳米粒子的聚集方式为链状聚集.当聚集体平均尺寸为120nm时，银纳米粒子聚集体的HRS信号强度比聚集前增大了约15倍.分析表明，聚集导致银纳米粒子表面电场极化强度的增强和极化分布的改变，并通过表面和体贡献机理对二阶非线性极化过程产生影响. 关键词： 银纳米粒子 超瑞利散射 二阶光学非线性 聚集     

Glassy effects in the swelling/collapse dynamics of homogeneous polymers

We investigate, using numerical simulations and analytical arguments, a simple one-dimensional model for the swelling or the collapse of a closed polymer chain of size N, representing the dynamical evolution of a polymer in a Θ-solvent that is rapidly changed into a good solvent (swelling) or a bad solvent (collapse). In the case of swelling, the density profile for intermediate times is parabolic and expands in space as t ^1/3, as predicted by a Flory-like continuum theory. The dynamics slows down after a time ∝N ² when the chain becomes stretched, and the polymer gets stuck in metastable “zig-zag” configurations, from which it escapes through thermal activation. The size of the polymer in the final stages is found to grow as . In the case of collapse, the chain very quickly (after a time of order unity) breaks up into clusters of monomers (“pearls”). The evolution of the chain then proceeds through a slow growth of the size of these metastable clusters, again evolving as the logarithm of time. We enumerate the total number of metastable states as a function of the extension of the chain, and deduce from this computation that the radius of the chain should decrease as 1/ln(ln t). We compute the total number of metastable states with a given value of the energy, and find that the complexity is non-zero for arbitrary low energies. We also obtain the distribution of cluster sizes, that we compare to simple “cut-in-two” coalescence models. Finally, we determine the aging properties of the dynamical structure. The subaging behaviour that we find is attributed to the tail of the distribution at small cluster sizes, corresponding to anomalously “fast” clusters (as compared to the average). We argue that this mechanism for subaging might hold in other slowly coarsening systems. Received 23 October 2000     

Stress state of silver nanoparticles embedded in a silicate glass matrix investigated by HREM and EXAFS spectroscopy

Ag particles of 3.9 and 5.1 nm mean size in silicate glasses were produced by ion exchange and subsequent annealing at 480 and 600 ^°C. These thermal treatments may induce stresses in matrix and particles in addition to the well known effect of surface atoms because of the thermal expansion mismatch of both materials. Structural characterisation of the particles by high-resolution electron microscopy revealed a size-dependent lattice dilatation quite opposite to the so far observed lattice contraction of similar metal/glass composites. This result, confirmed by X-ray absorption spectroscopy at the Ag K-edge, is discussed in terms of an Ag-Ag bond length increase near the particle surface. The temperature-dependent EXAFS spectra (10-300 K) indicate an increased thermal expansion coefficient of the particles with an increased mean particle size calculated on the basis of an anharmonic Einstein model. With that the bond length increase can be explained. The results can be interpreted by a combination of both the particle size effects and the influence of the surrounding matrix. Received 30 November 2000     

SERS activity of carbon nanotubes modified by silver nanoparticles with different particle sizes

A two-dimensional (2D) surface-enhanced Raman scattering (SERS) substrate is fabricated by decorating carbon nanotube (CNT) films with Ag nanoparticles (AgNPs) in different sizes, via simple and low-cost chemical reduction method and self-assembling method. The change of Raman and SERS activity of carbon nanotubes/Ag nanoparticles (CNTs/AgNPs) composites with varying size of AgNPs are investigated by using rhodamine 6G (R6G) as a probe molecule. Meanwhile, the scattering cross section of AgNPs and the distribution of electric field of CNTs/AgNPs composite are simulated through finite difference time domain (FDTD) method. Surface plasmon resonance (SPR) wavelength is redshifted as the size of AgNPs increases, and the intensity of SERS and electric field increase with AgNPs size increasing. The experiment and simulation results show a Raman scattering enhancement factor (EF) of 10⁸ for the hybrid substrate.     

Heterogeneous nucleation and growth of silver nanoparticles on unmodified polystyrene spheres by in situ reduction

The in situ reduction growth of Ag nanoparticles (NPs) on unmodified polystyrene (PS) spheres is investigated via controlling Ag nucleation and growth rates by continuous dripping addition of reductant solution in the absence of surfactants. The sub-micro PS spheres were coated by a uniform coverage of Ag NPs with several shapes like elongated islands, spherical particles, and particle aggregates. The reaction temperature and reductant concentration are demonstrated to influence the crystal structure, distribution, and stability of the Ag NPs on the PS substrates. The heterogeneous nucleation and growth of Ag NPs on PS spheres are found to depend on the inhibition of in-solution reduction and homogeneous nucleation.     

Electrochemical deposition of silver nanoparticles on TiO2/FTO thin films

Silver nanoparticles were deposited on titanium oxide^IV (TiO₂) thin films supported on FTO (fluorine-doped tin oxide^IV) glass using a double pulse electrochemical deposition method. A systematic study of particle nucleation and growth is presented as a function of applied potential and time. Samples were analyzed by grazing-angle X-ray diffraction (GIXRD) technique and morphology was observed using Scanning Electron Microscopy and Energy Dispersive Spectroscopy device (SEM-EDS). Our results confirm the possibility of controlled electrochemical homogeneous deposition of metallic silver particles over TiO₂ surface, which exhibit a potential application in catalytic processes.     

The effect of liquid environment on size and aggregation of gold nanoparticles prepared by pulsed laser ablation

The effects of liquid environment on nucleation, growth and aggregation of gold nanoparticles were studied. Gold nanoparticles were prepared by pulsed laser ablation in deionised water with various concentrations of ethanol and also in pure ethanol. UV/visible extinction and TEM observations were employed for characterization of optical properties and particle sizes respectively. Preparation in water results in smaller size, shorter wavelength of maximum extinction and stable solution with an average size of 6 nm. Nanoparticles in solution with low concentration ethanol up to 20 vol% are very similar to those prepared in water. In the mixture of deionised water and 40 up to 80 vol% ethanol, wavelength of maximum extinction shows a red shift and mean size of nanoparticles was increased to 8.2 nm. Meanwhile, in this case, nanoparticles cross-linked each other and formed string type structures. In ethanol, TEM experiments show a mean size of 18 nm and strong aggregation of nanoparticles. The data were discussed qualitatively by considering effects of polarity of surrounding molecules on growth mechanism and aggregation. This study provided a technique to control size, cross-linking and aggregation of gold nanoparticles via changing the nature of liquid carrier medium.     

Effect of silver addition on the formation and deposition of titania nanoparticles produced by liquid flame spray

In this study, liquid flame spray (LFS) was used to produce titania, silver and silver–titania deposits of nanoparticles. Titanium(IV)ethoxide (TEOT) and silver nitrate in ethanol solutions were used as precursors and sprayed into turbulent hydrogen–oxygen flame. Production rates of 1.5–40 mg/min of titania were used with silver additions of 1, 2, 4, and 8 wt% compared to titania. Nanoparticle deposits were collected by thermophoretic sampling at six different axial distances from the flame torch head: 3, 5, 10, 12, 15, and 20 cm, of which the all but the last one occurred inside the flame. The deposit samples were analysed by TEM and SAED analysis. The powder samples of the particles were also collected by electric precipitator to XPS and specific surface area analysis. Particle size and effective density after the flame in the aerosol were analysed with SMPS and ELPI. The results from the previous studies i.e. controlling the particle size by setting the production rates of the particles were seen to apply also for this binary system. Characterisation of the deposits showed that when the substrate is inserted into the flame, in the beginning of the flame the deposit is formed by gas phase deposition whereas further down the flame the particles are first formed in the gas phase and then deposited. The location of the transition from gas phase deposition to gas phase nucleation prior to deposition depends on chemical/physical properties (e.g. thermodynamics and gas phase interactions) of the precursor, precursor concentration in the flame and also flame temperature profile. Therefore, the deposit collection distance from the burner also affected the collected particle size and degree of agglomeration. The two component deposits were produced in two different ways: one-step method mixing both precursors in the same solute, and two-step method spraying each precursor separately. The particle morphology differs between these two cases. In one-step method the primary (d _TEM) and agglomerate particle size (d _SMPS) decreased with the amount of silver addition, verifying the fact that when present, the silver has a clear effect on the titania nanoparticle formation and growth.     

In situ gas-phase catalytic properties of TiC-supported size-selected gold nanoparticles synthesized by diblock copolymer encapsulation

TiC-supported size- and shape-selected Au nanoparticles with well defined interparticle distances were synthesized by diblock copolymer encapsulation. Atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) have been used to investigate the correlation between the nanocatalyst morphological/electronic structure and its chemical reactivity. Using the low-temperature oxidation of CO as a model reaction, our TPD results showed an enhancement of the catalytic activity with decreasing particle size. Two desorption features were observed and assigned to kinks/steps in the gold surface and the Au-TiC interface. The role of the interparticle distance on the activity is discussed. AFM measurements showed drastic morphological changes (Ostwald ripening) on the nanoparticles after CO oxidation when the initial interparticle distance was small (∼30 nm). However, no sintering was observed for Au nanoparticles more widely spaced (∼80 nm).     

Thermal undulations of quasi-spherical vesicles stabilized by gravity

The classical treatment of quasi-spherical vesicle undulations has, in the present work, been reviewed and extended to systems, which are affected by a gravitational field caused by a density difference across the membrane. The effects have been studied by the use of perturbation theory leading to corrections to the mean shape and the fluctuation correlation matrix. These corrections have been included in an analytical expression for the flicker spectrum to probe how the experimentally accessible spectrum changes with gravity. The results are represented in terms of the gravitational parameter, g ₀ = ΔρgR ⁴/κ. The contributions from gravity are in most experimental situations small and thus negligible, but for values of g₀ above a certain limit, the perturbational corrections must be included. Expressions for the relative error on the flicker spectrum have been worked out, so that it is possible to define the regime where gravity is negligible. An upper limit of g₀ has also been identified, where the error in all modes of the flicker spectrum is significant due to distortion of the mean shape. Received 9 July 2002 and Received in final form 15 November 2002 RID="a" ID="a"e-mail: jonas@kemi.dtu.dk RID="b" ID="b"e-mail: ipsen@memphys.sdu.dk     

Polarization dependence of the permanent deformation of silver nanoparticles in glass by ultrashort laser pulses

Glass containing spherical silver nanoparticles has been irradiated with single, intense, ultrashort laser pulses, with a wavelength corresponding to the surface plasmon resonance of the particles. After irradiation with linear polarization, dichroism is observed. Transmission electron microscopy studies reveal that these spectral changes are caused by deformation of the particles to anisotropic (in the TEM projection approximately ellipsoidal) shapes with an additional halo of small silver particles around the central one. The deformed particles are uniformly oriented with their longer axes perpendicular to the laser polarization. Using laser pulses with circular polarization, again a halo is formed around the particles, but the central particles remain spherical, and no dichroism was observed in the optical spectra. Received 30 November 2000     

The electrostatic persistence length of polymers beyond the OSF limit

We use large-scale Monte Carlo simulations to test scaling theories for the electrostatic persistence length l _e of isolated, uniformly charged polymers with Debye-Hückel intrachain interactions in the limit where the screening length κ^-1 exceeds the intrinsic persistence length of the chains. Our simulations cover a significantly larger part of the parameter space than previous studies. We observe no significant deviations from the prediction l _e∝κ^-2 by Khokhlov and Khachaturian which is based on applying the Odijk-Skolnick-Fixman theories of electrostatic bending rigidity and electrostatically excluded volume to the stretched de Gennes-Pincus-Velasco-Brochard polyelectrolyte blob chain. A linear or sublinear dependence of the persistence length on the screening length can be ruled out. We show that previous results pointing into this direction are due to a combination of excluded-volume and finite chain length effects. The paper emphasizes the role of scaling arguments in the development of useful representations for experimental and simulation data. Received 12 February 2002     

The investigation of oxidized silver nanoparticles prepared by thermal evaporation and radio-frequency sputtering of metallic silver under oxygen

The investigation of oxidized silver nanoparticles by the photoemission (XPS, UPS) and HRTEM methods was performed. The nanoparticles of oxidized silver were obtained in the vacuum chamber by two methods of synthesis: thermal evaporation of silver nanoparticles followed by transferring in convective gas flow and sputtering of oxidized clusters under the action of plasma. Both methods indicated that oxygen interaction with silver nanoparticles depends strongly on its size. It was shown that the chemical bonding of oxygen species stabilized on small particles differs from the oxygen species adsorbed on bulk silver surfaces (monocrystals, foils and large particles). The low charged oxygen with molecular type of bonding stabilizes on particles of size approximately 5 nm and smaller. Increasing particle size leads to the dissociation of molecular oxygen species and the formation of strongly charged oxygen composed of oxide nanoparticles like Ag₂O or AgO type. The presence of extended defects in the microdomain large nanoparticles facilitates the formation of Ag₂O or AgO layers covering metallic nanosilver.     

Raman scattering of L‐tryptophan enhanced by surface plasmon of silver nanoparticles: vibrational assignment and structural determination

Vibrational bands of L ‐tryptophan which was adsorbed on Ag nanoparticles (∼10 nm in diameter) have been investigated in the spectral range of 200–1700 cm⁻¹ using surface‐enhanced Raman scattering (SERS) spectroscopy. Compared with the normal Raman scattering (NRS) of L ‐tryptophan in either 0.5 M aqueous solution (NRS‐AS) or solid powder (NRS‐SP), the intensified signals by SERS have made the SERS investigation at a lower molecular concentration (5 × 10⁻⁴ M ) possible. Ab initio calculations at the B3LYP/6‐311G level have been carried out to predict the optimal structure and vibrational wavenumbers for the zwitterionic form of L ‐tryptophan. Facilitated with the theoretical prediction, the observed vibrational modes of L ‐tryptophan in the NRS‐AS, NRS‐SP, and SERS spectra have been analyzed. In the spectroscopic observations, there are no significant changes for the vibrational bands of the indole ring in either NRS‐AS, NRS‐SP, or SERS. In contrast, spectral intensities involving the vibrations of carboxylate and amino groups are weak in NRS‐AS and NRS‐SP, but strong in SERS. The intensity enhancement in the SERS spectrum can reach 10³–10⁴‐fold magnification. On the basis of spectroscopic analysis, the carboxylate and amino groups of L ‐tryptophan are determined to be the preferential terminal groups to attach onto the surfaces of Ag nanoparticles in the SERS measurement. Copyright © 2008 John Wiley & Sons, Ltd.     

Pattern formation by growing droplets: The touch-and-stop model of growth

We investigate a novel model of pattern formation phenomena. In this model spherical droplets are nucleated on a substrate and grow at constant velocity; when two droplets touch each other they stop their growth. We examine the heterogeneous process in which the droplet formation is initiated on randomly distributed centers of nucleation and the homogeneous process in which droplets are nucleated spontaneously at constant rate. For the former process, we find that in arbitrary dimensiond the system reaches a jamming state where further growth becomes impossible. For the latter process, we observe the appearance of fractal structures. We develop mean-field theories that predict that the fraction of uncovered material (t) approaches to the jamming limit as (t)–()exp(Ct ^d ) for the heterogeneous process and as a power law for the homogeneous process. Exact solutions in one dimension are obtained and numerical simulations ford=1–3 are performed and compared with mean-field predictions.