Studies on solution and solution-cast film of polyaniline colloids prepared in the absence and presence of ultrasonic irradiation

Spectroscopic and voltammetric features for the solution and solution-cast film of polyaniline (PANI) colloids prepared in the absence and presence of ultrasonic irradiation were examined. Significant differences in the color and absorption spectra between the solution of colloids prepared in the absence and presence of irradiation were observed. Effects of ambient atmosphere on the solution of colloids were also studied. A gradual decay in the absorption at approximately 365 nm was occurred upon ageing the solution in air for the colloid prepared under ultrasonic irradiation. PANI film, cast from its colloidal solution, exhibited excellent electroactivity. The films thus cast were applied to electrode modification to control electrochemical reaction. Clear voltammetric response was observed on the electrode modified with the colloid prepared in the presence of ultrasonic irradiation.     

Depletion interactions between colloidal particles in polymer solutions: density functional approach

A density functional theory for colloid–polymer mixtures based on the weighted-density approximation has been developed to investigate the depletion effects acting between two colloids immersed in a bath of polymers and the depletion effects for a colloid near a planar hard wall. The theoretical results for the polymer-induced depletion interactions and the local polymer density distributions are in good agreement with the computer simulations. The calculation shows that the depletion interaction for a colloid near a planar hard wall is much stronger than that between two colloids in a polymer solution because of the strong confinement effect. The behaviour of the depletion interactions has been analysed as a function of the polymer density, the polymer chain length, and the colloid/polymer size ratio. Strong depletion effects appear in short-chain systems and with large colloid/polymer size ratios.     

Design rule for colloidal crystals of DNA-functionalized particles

We report a Monte Carlo simulation study of the phase behavior of colloids coated with long, flexible DNA chains. We find that an important change occurs in the phase diagram when the number of DNAs per colloid is decreased below a critical value. In this case, the triple point disappears and the condensed phase that coexists with the vapor is always liquid. Our simulations thus explain why, in the dilute solutions typically used in experiments, colloids coated with a small number of DNA strands cannot crystallize. We understand this behavior in terms of the discrete nature of DNA binding.     

Characterization of laser-ablated and chemically reduced silver colloids in aqueous solution by UV/VIS spectroscopy and STM/SEM microscopy

Silver colloids in aqueous solution were studied by different scanning microscopy techniques and UV/VIS spectroscopy. The silver colloids were produced either by chemical reduction or by nanosecond laser ablation from a solid silver foil in water. Variation of laser power and ablation time leads to solutions of metal clusters of different sizes in water. We characterized the electronic absorption of the clusters by UV/VIS spectroscopy. STM (scanning tunneling microscope) imaging of the metal colloids shows atomic resolution of rod- or tenon-like silver clusters up to 10-nm length formed by laser ablation. Our scanning electron microscope measurements, however, show that much larger silver colloids up to 5-μm length are also formed, which are not visible in the STM due to their roughness. We correlate them with the long-wavelength tail of the multimodal UV/VIS spectrum. The silver colloids obtained by chemical reduction are generally larger and their electronic spectra are red-shifted compared to the laser-ablated clusters. Irradiation of the colloid solution with nanosecond laser pulses of appropriate fluence at 532 nm and 355 nm initially reduced the colloid size. Longer irradiation at 355 nm, however, leads to the formation of larger colloids again. There seems to be a critical lower particle size, where silver clusters in aqueous solution become unstable and start to coagulate. Received: 24 June 2002 / Revised version: 25 July 2002 / Published online: 25 October 2002 RID="*" ID="*"This work is part of the thesis of H. M?ltgen RID="**" ID="**"Corresponding author. Fax: +49-211/811-5195, E-mail: kleinermanns@uni-duesseldorf.de     

应用银溶胶膜探测水中抗生素的表面增强拉曼光谱研究

以自组装法制备的银溶胶膜为表面增强拉曼散射活性基底实现了对水中抗生素的痕量检测。采用微波加热法制备银溶胶,自组装法制备银溶胶膜。通过改变银溶胶的pH值及镀膜的次数,研究其对抗生素增强效果的影响。实验发现,采用不同pH值的银溶胶镀膜所获得的银溶胶膜的增强效果有很大差异,当银溶胶pH=4,且镀膜次数为五次时,增强效果最佳。以此银溶胶膜为基底对三种抗生素(氯霉素、环丙沙星、恩诺沙星)进行了SERS检测,可以检测到的最低浓度分别为120,15,120 nmol·L-1。结果表明,利用改进方法制备的银溶胶膜,可以对水中抗生素进行痕量检测,为实现养殖水中残留抗生素的检测提供了方法。     

Photoconductivity of potassium colloids in KCl single crystals

Detailed photoconductivity spectra of potassium colloids in KCl single crystals are presented. A broad band peaked at ～2 eV, together with a small shoulder at ～1.3 eV are observed for crystals containing colloids with radii in the 20–500 Å range.The spectrum shape is essentially independent of temperature and colloid radius. On the other hand, the maximum photoconductivity yield depends on the colloid radius reaching a maximum value at about 60 Å.     

Soret motion of a charged spherical colloid

The thermophoretic motion of a charged spherical colloidal particle and its accompanying cloud of counterions and coions in a temperature gradient is studied theoretically. Using the Debye-Hückel approximation, the Soret drift velocity of a weakly charged colloid is calculated analytically. For highly charged colloids, the nonlinear system of electrokinetic equations is solved numerically, and the effects of high surface potential, dielectrophoresis, and convection are examined. Our results are in good agreement with some of the recent experiments on highly charged colloids without using adjustable parameters.     

Influence of surface affinity of planar walls on effective interaction between the wall and colloids

Using density functional theory, we investigate the effective interaction between a big colloid immersed in a sea of small colloids and a wall which has different affinity to the small colloids. Steele 10-4-3 potential is introduced to mimic both short-range repulsive and long-range attractive interactions between the wall and the small colloids. It is found that the surface affinity of the wall has a significant influence on the effective interaction. In the short-range repulsive case, the repulsion greatly enhances the big colloid-wall effective attraction, which sensitively depends on the concentration of small colloids, and is not sensitive to the repulsive strength. In the long-range attractive case, both the concentration of small colloids and the attractive strength have great effect on the effective interaction, and with an increase of the attractive strength, a strong repulsion may be induced when the big colloid is close to the wall. In low density limit of small colloids, the present results agree well with those of the Asakura and Oosawa(AO) approximation.     

Synthesis and investigation of stable copper nanoparticle colloids

The synthesis of stable nanoparticle colloids by laser ablation of the copper target in water and fragmentation of Cu + CuO nanopowder with pulsed fiber laser irradiation with a wavelength of 1064 nm and pulse duration of 100 ns has been investigated experimentally. The influence of the technological parameters on the nanoparticle size and stability of the colloid has been studied. It has been shown that the laser ablation creates the CuO spherical nanoparticles. Subsequent fragmentation makes it possible to reduce the nanoparticle size in a colloid and to produce a stable colloidal solution from an aqueous suspension of Cu + CuO nanopowder.     

Colloids on free-standing smectic films

We study the structure of a free-standing smectic-A film around a micron-size polystyrene colloid adsorbed onto the film. We find that a colloid or a cluster of colloids is surrounded by an optically distinct and radially decorated meniscus ending with a sharp edge. The observed strong and finite-range attraction between the adsorbed colloids is driven by the fusion of menisci. We interpret the structure of the smectic meniscus in terms of a model dominated by the surface free energy and we argue that the characteristic appearance of the meniscus is due to layer undulations.     

The influence of long range interparticle correlations on the magnetically induced optical anisotropy in magnetic colloids

In this paper we develop a theoretical model for the magnetically induced optical anisotropy in dense magnetic colloids made of spherical and un-aggregated magnetic monodomain nanoparticles. Both dipole-field and dipole-dipole magnetic and electric interactions between the magnetic monodomain particles are taken into account in the Hamiltonian of the system. Using the pair correlation function in a colloidal suspension of magnetic nanoparticles developed by Ivanov and Kuznetsova (2001) [11], the complex dielectric constant of a magnetic colloid is modeled as a function of the light polarization direction, the magnetic field intensity and magnetic particle concentration and diameter. The two main features of the model are that, on the one hand, it predicts the possibility of magnetically induced optical anisotropy in dense magnetic colloids made of spherical and un-aggregated monodomain nanoparticles, and on the other hand, unlike the existing models for diluted samples, it predicts a non-linear dependence of dichroism and birefringence on magnetic particle concentration.     

受驱无序胶体动力学

利用Langevin分子动力学，本数值研究点钉扎中心随机分布的二维胶体动力学．随着钉扎中心强度的提高，我们发现了从弹性脱钉到塑性脱钉的渡越，并伴随临界钉扎力在渡越区的明显提高，类似于超导体中的峰值效应．另外，我们首次发现：当塑性流动发生时，高速运动胶体粒子感受到的平均钉扎力在从玻璃态到液态的转变过程中会出现峰值效应，并伴随有速度-驱动力曲线的交叠．     

Metal-Enhanced Fluorescence from Gold Surfaces: Angular Dependent Emission

The first observation of Metal-Enhanced Fluorescence (MEF) from large gold colloids is presented. Gold colloids, 40 and 200 nm diameter, were deposited onto glass substrates in a homogeneous fashion. The angular-dependent fluorescence emission of FITC-HSA, adsorbed onto gold colloids, was measured on a rotating stage which was used to evaluate MEF at all spatial angles. The emission intensity of FITC-HSA was found to be up to 2.5-fold brighter than the emission on bare glass substrates at an angle of 270 degrees. This is explained by the Radiating Plasmon Model, whereby the combined system, composed of the fluorophore and the metal colloids, emits with the photophysical characteristics of the fluorophore, after the excitation and the partial radiationless energy transfer between the excited states of the fluorophore and the surface plasmons of the gold colloids. The fluorescence enhancement was found to be higher with 200 nm gold colloids as compared to 40 nm colloids due to the increased contribution of the scattering portion of the 200 nm gold colloid extinction spectrum. These observations suggest that gold colloids could be used in MEF applications, offering more stable surfaces than the commonly used silvered surfaces, for applications requiring longer term storage and use.     

Polyelectrolyte-compression forces between spherical DNA brushes

Optical tweezers are employed to measure the forces of interaction within a single pair of DNA-grafted colloids, dependent on the molecular weight of the DNA chains, and the concentration and valence of the surrounding ionic medium. The resulting forces are short range and set in as the surface-to-surface distance between the colloidal cores reaches the value of the brush height. The measured force-distance relation is analyzed by means of a theoretical treatment that quantitatively describes the effects of compression of the chains on the surface of the opposite-lying colloid. Quantitative agreement with the experiment is obtained for all parameter combinations.     

Nonequilibrium forces between dragged ultrasoft colloids

The dynamical deformation of ultrasoft colloids as well as their dynamic frictional forces are numerically investigated, when one colloid is dragged past another at constant velocity. Hydrodynamic interactions are captured by a particle-based mesoscopic simulation method. At vanishing relative velocity, the equilibrium repulsive force-distance curve is obtained. At large drag velocities, in contrast, we find an apparent attractive force for departing colloids along the dragging direction. The deformation, in the close encounter of colloids, and the energy dissipation are examined as a function of the drag velocity and their separation.     

Key role of receptor density in colloid/cell specific interaction: a quantitative biomimetic study on giant vesicles

This paper presents an experimental study of the adsorption of colloids on model membranes mediated by specific ligand-receptor interactions. The colloids consist of lipid multilamellar liposomes (spherulites) functionalized with the B-subunit of Shiga Toxin (STxB), while the membranes are lipid Giant Unilamellar Vesicles (GUV) containing STxB lipid receptor, Globotriaosylceramide (Gb3). Through confocal microscopy and flow cytometry, we show the specificity of the adsorption. Moreover, we show that flow cytometry can be used to efficiently quantify the kinetics of colloid adsorption on GUVs with very good statistics. By varying the bulk colloid concentration and receptor density in the membrane, we point out the existence of an optimum Gb3 density for adsorption. We propose that this optimum corresponds to a transition between reversible colloid adsorption at low Gb3 density and irreversible adsorption, and likely spherulite fusion, at high density. We compare our results both to STxB-colloids adhering on living cells and to free STxB proteins interacting with GUVs containing Gb3. This biomimetic system could be used for a quantitative evaluation of the early stage of virus infection or drug delivery.     

Solution Lithography for Colloidal Crystal Patterning: Revisiting Flory–Huggins Interaction Parameters and Co-Nonsolvent Systems

For fundamental studies and practical applications, colloidal crystal patterns on substrates are typically fabricated through etching and conventional lithography. However, a wet-chemical based method is necessary for simplifying the procedure, preserving the substrate structure, and reproducibly fabricating the colloidal crystal patterns. The present study demonstrates that colloidal crystal patterns can be conveniently generated using thermodynamic relationships between a polymer colloid and surrounding solvents. Close-packed colloidal monolayers in good solvents that cause colloidal swelling spontaneously transform into non–close-packed crystal patterns when non-solvents that cause their shrinkage replace the good solvents. The colloid diameter in the close-packed monolayer decreases significantly when the polymer in the colloid is passing thermodynamic theta conditions (when Flory–Huggins interaction parameters increase to higher than ≈0.5). The close-packed monolayers also transform into the patterns in co-nonsolvent conditions. The “solution lithography” might be particularly useful for patterning colloids on curved microstructures and plastic/flexible films. The colloidal shapes in the patterns vary with the solvent pairs and substrates. The method does not require special facilities to reproducibly fabricate the patterns. The study further suggests methods simultaneously fixing the patterns. The patterns exhibit anti-reflection properties. Therefore, the solution lithography is applicable to optics, electronics, analytical science, and energy systems.     

Electric-field-induced polarization of the layer of condensed ions on cylindrical colloids

In concentrated suspensions of charged colloids, interactions between colloids can be induced by an external electric field through the polarization of charge distributions (within the diffusive double layer and the layer of condensed ions) and/or electro-osmotic flow. In case of rod-like colloids, these field-induced inter-colloidal interactions have recently been shown to lead to anomalous orientation perpendicular to the external field, and to phase/state transitions and dynamical states, depending on the field amplitude and frequency of the external field. As a first step towards a (semi-) quantitative understanding of these phenomena, we present a linear-response analysis of the frequency-dependent polarization of the layer of condensed ions on a single, long and thin cylindrical colloid. The in-phase and out-phase response functions for the charge distribution and the electric potential are calculated for arbitrary orientation of the cylindrical colloid. The frequency-dependent degree of alignment, which is proportional to the electric-field-induced birefringence, is calculated as well, and compared to experiments on dilute fd virus suspensions.     

Morphological diversity of DNA-colloidal self-assembly

We study theoretically a binary system in which an attraction of unlike particles is combined with a type-independent soft-core repulsion. The possible experimental implementation of the system is a mixture of DNA-covered colloids, in which both the repulsion and the attraction may be induced by DNA solution. The system is shown to exhibit surprisingly diverse and unusual morphologies. Among them are the diamond lattice and the membrane phase with in-plane square order, a striking example of spontaneous compactification.