Size-dependent interaction of silica nanoparticles with different surfactants in aqueous solution

The size-dependent interaction of anionic silica nanoparticles with ionic (anionic and cationic) and nonionic surfactants has been studied using small-angle neutron scattering (SANS). The surfactants used are anionic sodium dodecyl sulfate (SDS), cationic dodecyltrimethyl ammonium bromide (DTAB), and nonionic decaoxyethylene n-dodecylether (C(12)E(10)). The measurements have been carried out for three different sizes of silica nanoparticles (8, 16, and 26 nm) at fixed concentrations (1 wt % each) of nanoparticles and surfactants. It is found that irrespective of the size of the nanoparticles there is no significant interaction evolved between like-charged nanoparticles and the SDS micelles leading to any structural changes. However, the strong attraction of oppositely charged DTAB micelles with silica nanoparticles results in the aggregation of nanoparticles. The number of micelles mediating the nanoparticle aggregation increases with the size of the nanoparticle. The aggregates are characterized by fractal structure where the fractal dimension is found to be constant (D ≈ 2.3) independent of the size of the nanoparticles and consistent with diffusion-limited-aggregation-type fractal morphology in these systems. In the case of nonionic surfactant C(12)E(10), micelles interact with the individual silica nanoparticles. The number of adsorbed micelles per nanoparticle increases drastically whereas the percentage of adsorbed micelles on nanoparticles decreases with the increase in the size of the nanoparticles.     

Polyacrylamide gel electrophoresis in vertical, inverse and double-crossing gradients of soluble polymers.

The presence of soluble dextrans, methylcellulose and polyethylene glycol polymers incorporated into vertical sodium dodecyl sulfate (SDS)-polyacrylamide slabs during electrophoresis can have a pronounced effect on protein separations. The effects of various standard and inverse gradients of polymers on the electrophoretic mobility of marker proteins in 10% T, 2.66% C Laemmli-style SDS gels, and the effects of simultaneous pore size and polymer gradients were investigated. These experiments demonstrate that the inclusion of polymers is a new, additional parameter that can be useful in resolving complex mixtures of proteins.     

Capillary electrophoretic protein separations in polyacrylamide-coated silica capillaries and buffers containing ionic surfactants

Capillary electrophoretic protein separations of high efficiency and resolution were obtained using polyacrylamide-coated silica capillaries and buffers containing ionic surfactants. The presence of micellar concentrations of sodium dodecyl sulfate or cetyltrimethyl- ammonium chloride minimized protein-capillary wall interactions, and facilitated concurrent separations of a mixture of both acidic and basic proteins, while the polyacrylamide coating provided increased resolution and migration time reproducibility via a reduction in electroosmotic flow. Attempts to obtain size-based protein separations via sieving through buffers containing the hydrophilic polymers methylcellulose and polyethylene glycol were unsuccessful.     

Absorption and emission spectra of fluorescent silica nanoparticles from TD-DFT/MM/PCM calculations

A multi-scale computational protocol, which combines Quantum Mechanics and Molecular Mechanics (QM/MM) calculations with the polarisable continuum model (PCM), has been used to study the tetramethylrhodamine isothiocyanate (TRITC) fluorophore, embedded in three different environments, namely in water, on an amorphous silica surface and covalently encapsulated in a silica nanoparticle (C dot). Absorption and emission spectra have been simulated by using TD-B3LYP/PCM calculations, performed on the TRITC ground and excited state geometries, optimized at the QM/MM level. The results are in good agreement with experimental data confirming the caging effect played by the silica shell on the mobility of the TRITC molecule when covalently encapsulated in silica nanoparticles. This could result in a decrease of the nonradiative decay rate and thus an increase of the quantum yield of the molecule.     

Structuring of macroions confined between like-charged surfaces

We investigate the structuring of charged spherical nanoparticles and micelles (i.e., "macroions") between two surfaces as a function of bulk macroion concentration. Structuring is deduced from measured force profiles between a silica particle and a silica plate in the presence of an aqueous macroion (Ludox silica nanoparticle or sodium dodecyl sulfate micelle) solution, obtained with an atomic force microscope. We observe oscillatory force profiles that decay with separation. We find that the wavelength of the force profiles scales with the bulk number density as rho(-)(1/3), rather than with the effective macroion size. Only at very high silica nanoparticle concentration (above 10 vol %) in a low ionic strength solution does the wavelength become smaller than that predicted by the simple rho(-)(1/3) scaling; however, the original scaling is recovered upon the addition of a small amount of electrolyte. A comparison between the measured wavelength and the predicted spacing between the macroions in the bulk shows that the two variables differ in both magnitude and bulk density scaling. This finding suggests that confined macroions are more ordered than those in the bulk and the nature of this ordering is maintained over a relatively wide range of bulk concentration.     

Factors controlling electroosmotic flow in open-tubular capillaries in electrokinetic chromatography

Effects of pH, concentration of sodium dodecyl sulfate (SDS), additives, and coatings of polymers on the inner wall of fused silica tubing on electrokinetic migration were investigated with SDS solutions. The increase in SDS concentrations caused a substantial increase of the electrophoretic velocity of the SDS micelle but little affected the electroosmotic velocity v_eo under a constant applied voltage. No significant change in v_eo was observed either when the pH of the solution was varied from 5.5 to 9 or when additives such as hydroxypropyl cellulose were employed. Compared with an uncoated tube, electroosmosis became stronger in a fused silica tube coated with methyl silicone but weaker in one coated with polyethylene glycol 20M.     

Integrities and Skin Permeation-Enhancing Characteristics of Behenic Acid Nanoparticles

Fatty acid nanoparticles containing hinokitiol (HKL) were prepared by a melt-emulsification method. Behenic acid (BA) was used as a lipid for the matrix material of the nanoparticle. The size distribution was quite mono-dispersive and the mean diameter was around 200 nm. On a differential scanning calorimeter, no endothermic peak of HKL was observed when it was encapsulated in the nanoparticles. This indicates that HKL in the lipid matrix of the nanoparticles is not in a crystalline state, but rather in a dissolved state. The nanoparticles were stable over the range of pH 2–10 in terms of size. The absolute values of the zeta potentials in the pH range were high enough to prevent a particle-to-particle aggregation. Compared with stearic acid (SA) nanoparticles, which were completely disintegrated in sodium lauryl sulfate (SLS) solution of 4%, the BA nanoparticles were robust and remained intact even in SLS solutions of 14%. Therefore, BA nanoparticles would be applicable to cleansing products containing detergents for personal care. When encapsulated either in SA nanoparticles or in BA nanoparticles, the in vitro flux of HKL through hairless mouse skin was 10–15 times higher than dissolved in propylene glycol. BA nanoparticles, however, enhanced the transdermal delivery of HKL less than SA nanoparticles did.     

Determination of molecular weight of silk fibroin by non-gel sieving capillary electrophoresis

A simple non-gel sieving capillary electrophoresis (NGSCE) method was established to determine the MW of silk fibroin using CE. The background electrolyte with a pH of 8.8 was based on three components: polyethylene glycol, tris(hydroxymethyl)aminomethane, and sodium dodecyl sulfate (SDS). NGSCE showed a good linear relationship with satisfactory reproducibility between the migration time and the MW of standard proteins. It was found that the regenerated silk fibroin had an MW around 83 kDa with a wide MW distribution (MWD). This absolute value is lower than the result obtained from SDS-polyacrylamide gel electrophoresis due to the different principles of the methods, but their similar MWD shapes indicated that NGSCE could be a feasible, highly sensitive, rapid method for determination of the MW of silk fibroin.     

Effect of anionic surfactants on synthesis and self-assembly of silica colloidal nanoparticles

Effects of the anionic surfactants, sodium dodecyl sulfate and sodium oleate, on the formation and properties of silica colloidal nanoparticles were investigated. At a concentration of approximately 1 x 10(-3) M, adsorption of anionic surfactants increased particle size, monodispersity, and negative surface charge density of synthesized silica particles. As uniformity of particle size and particle-particle interactions increase, colloidal photonic crystals readily self-assemble without extensive washing of the synthesized silica nanoparticles. The photonic crystals diffract light in the visible region according to Bragg's law. The assembled colloidal particle arrays exhibit a face-centered cubic structure in dried thin films. This study offers a new approach for producing ordered colloidal silica thin films.     

Basic Physicochemical Properties of Polyethylene Glycol Coated Gold Nanoparticles that Determine Their Interaction with Cells

A homologous nanoparticle library was synthesized in which gold nanoparticles were coated with polyethylene glycol, whereby the diameter of the gold cores, as well as the thickness of the shell of polyethylene glycol, was varied. Basic physicochemical parameters of this two‐dimensional nanoparticle library, such as size, ζ‐potential, hydrophilicity, elasticity, and catalytic activity ,were determined. Cell uptake of selected nanoparticles with equal size yet varying thickness of the polymer shell and their effect on basic structural and functional cell parameters was determined. Data indicates that thinner, more hydrophilic coatings, combined with the partial functionalization with quaternary ammonium cations, result in a more efficient uptake, which relates to significant effects on structural and functional cell parameters.     

二苯胺磺酸钠还原法制备粒径可控的金纳米粒子

采用二苯胺磺酸钠还原四氯合金酸的方法,在室温条件下,用SDS(十二烷基硫酸钠)、SDBS(十二烷基苯磺酸钠)作表面活性剂,成功地合成了金纳米粒子.分别讨论了还原剂二苯胺磺酸钠、表面活性剂(SDS、SDBS)及四氯台金酸的浓度等对金纳米粒子的粒径和形貌的影响.通过控制反应条件,可以合成出平均粒径大约为10、14、30、36nm的金纳米粒子.利用透射电镜(TEN)、紫外-可见(UV-Vis)吸收光谱对金纳米粒子进行了表征.研究结果表明不同的SDS或SDBS/HAuCl4的摩尔比,对金纳米粒子的尺寸大小有影响.     

Micellar phases based on sodium dodecyl sulfate for preconcentration

Features of phase formation from solutions of sodium dodecyl sulfate on cooling were examined. The effect of electrolyte and phenol additions on the parameters of phase formation and distribution of model substrates was examined. Conditions were found for albumin preconcentration with phases in the system sodium dodecyl sulfate-phenol-NaCl.     

Influences of surfactant and nanoparticle assembly on effective interfacial tensions

We have studied assembly at air-water and liquid-liquid interfaces with an emphasis on systems containing both surfactants and nanoparticles. Anionic surfactants, sodium dodecyl sulfate (SDS) and non-ionic surfactants, Triton X-100 and tetraethylene glycol alkyl ethers (C(8)E(4), C(12)E(4) and C(14)E(4)), effectively decrease the surface tension of air-water interfaces. The inclusion of negatively charged hydrophilic silica nanoparticles (diameters of approximately 13 nm) increases the efficiency of the SDS molecules but does not alter the performance of the non-ionic surfactants. The former is likely due to the repulsive Coulomb interactions between the SDS molecules and nanoparticles which promote the surfactant adsorption at air-water interfaces. For systems involving trichloroethylene (TCE)-water interfaces, the SDS and Triton X-100 surfactants effectively decrease the interfacial tensions and the nanoparticle effects are similar compared to those involving air-water interfaces. Interestingly, the C(12)E(4) and C(14)E(4) molecules, with or without the presence of nanoparticles, fail to decrease the TCE-water interfacial tensions. Our molecular dynamics simulations have suggested that the tetraethylene glycol alkyl ether molecules tend to disperse in the TCE phase rather than adsorb at the TCE-water interfaces.     

Polypyrrole-Coated and Polysulfate-Modified CE Capillaries

Fused-silica capillaries covalently coated with polypyrrole offer some interesting properties for capillary electrophoresis. The polymeric, surface-bonded coating is chemically stable and reduces the adsorptive properties of the silica surface. At the same time, the weak positive surface charges offer the possibility of creating a strongly anionic surface when poly-sulfates are used as counter-ions. This affords an electroosmotic flow which is largely independent of pH. With sodium dodecyl sulfate in the background electrolyte, this effect is further enhanced. The potential of the approach is demonstrated with the separation of herbicides by micellar electrokinetic chromatography. Repeatability of electroosmotic mobility of less than 1% RSD is achieved.     

New insoluble surfactant systems as aids in catalysis. A convenient method for nonbonded immobilization of catalytically active transition metal complexes

New insoluble surface-active substances are described here for the first time. They were synthesized by esterification of the surfactants sodium 11-hydroxy-undecane-1-sulfonate or dodeca-ethylene glycol monododecyl ether with an aliphatic amino acyl chloride, reaction of the amino group containing ester with the bifunctional reagent 3-(triethoxysilyl) propyl isocyanate, and anchoring the products obtained on silica 100 under mild conditions.The surfactants thus immobilized showed a micellar effect, as proved by their influence on reaction rate and selectivity in the enantioselective hydrogenation of methyl (Z)--acetamido-cinnamate to methylN-acetyl-phenylalaninate (R) by means of an optically active rhodium complex in water.The systems were compared with an inorganic ion exchanger with dodecyl sulfate counterions and with sodium dodecyl sulfate adsorbed to alumina. The influence of the immobilized surfactants on reaction rate and selectivity appeared to be dependent on the mobility of the hydrophobic chains.     

Salt Effects on the Aqueous Two-Phase System of Gemini(12-3-12, 2Br<Superscript>−</Superscript>)/SDS/PEG

The effect of added salts (NaCl, KCl and NaBr) on the aqueous two-phase system (ATPS) formed in mixtures of Gemini(12-3-12, 2Br⁻)/sodium dodecyl sulfate/polyethylene glycol has been investigated. Phase diagrams of the aqueous systems containing Gemini(12-3-12, 2Br⁻), sodium dodecyl sulfate (SDS), polyethylene glycol(PEG) and a salt have been determined experimentally at 313.15 K. The results indicate that the addition of salts not only induces the appearance of ATPS-A (in which anionic surfactant is in excess), shortens the phase separation time, enlarges the regions of ATPS-C (in which cationic surfactant is in excess), and decreases the minimum concentration required for forming an ATPS, but also alters the matching between anionic and cationic surfactants. Extractive experiments also showed that these salts notably enhance the extraction ability of ATPS; the Gemini-rich phase exhibits prominent cohesive action with xylenol orange, regardless of whether or not it is the upper phase or the lower phase.     

Separation of gold nanoparticles with a monolithic silica capillary column in liquid chromatography

A separation system for gold nanoparticles was developed using monolithic silica capillary columns with 50 μm i.d., which were prepared via in-situ sol-gel processes. Gold nanoparticles with five different average sizes were synthesized via reduction of tetrachloroauric acid (HAuCl(4)) under different synthesis conditions, and were evaluated by UV-visible spectrophotometry, dynamic light scattering as well as transmission electron microscopy before they were separated using the developed system. The results showed that all of the gold nanoparticles had a certain size distribution, and the mean sizes obtained were 13, 17, 33, 43 and 61 nm, with σ = 2.5, 2.7, 5.2, 5.1 and 5.6 nm, respectively. Transmission electron microscopy showed that the samples with mean sizes of 13 and 17 nm were almost spherical, while larger samples were slightly non-uniform. The agglomeration of gold nanoparticles as the sample could be prevented by using a sodium dodecyl sulfate aqueous solution as the mobile phase, and gold nanoparticles were retained by adsorption on the silica surface. Separation with 8 mM sodium dodecyl sulfate as the eluent and a 1000-mm column was successful, and the separation of gold nanoparticles with 61 and 17 nm or 61 and 13 nm was demonstrated. The separation results obtained using a nonporous silica packed column as well as monolithic silica columns with or without mesopore growth were compared. It was found that separation using the mesopore-less monolithic column achieved better resolution. Through the use of a 2000-mm separation column, the mixtures of 61, 43, 17 nm and 61, 33, 13 nm could be separated.     

Labeling of fibronectin by fluorescent and paramagnetic nanoprobes for exploring the extracellular matrix: bioconjugate synthesis optimization and biochemical characterization

In this study, fibronectin-nanoparticles bioconjugates are developed and characterized. Multilabeled nanoparticles are composed of a core of the rare-earth oxide Gd(2)O(3):Tb(3+), capped with a set of Rhodamine B isothiocyanate encapsulated in a silica matrix and functionalized by a carboxylated polyethylene glycol shell. These nanoparticles are stabilized in aqueous solution and are found to contain about 400 carboxyl groups on their surface. Nanoparticle bioconjugation with highly purified human plasma fibronectin (Fn) is mediated by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, resulting in an amide linkage between the carboxylic acid-terminated surface of the nanoparticle and the primary amine of Fn. The bioconjugation temperature and pH are optimized. The Local structure and global conformation of fibronectin-nanoparticle bioconjugates (FnNP*) are studied by fluorescence spectroscopy and enzymatic sites accessibility. Protein biochemical functionalities are globally conserved, and the protein is actually labeled. Elaboration of such complexes provides a promising bimodal contrasting agent for in vivo imaging.     

Cluster size analysis of two-dimensional order in colloidal gold nanoparticle arrays

A protocol for cluster size distribution analysis was developed in order to parametrize local two-dimensional (2D) order in a quantitative manner, using mean cluster sizes and fractional hcp cluster formation (fhcp). Cluster size analysis was performed on 2D arrays of Au nanoparticles encapsulated in resorcinarene tetrathiol, which were organized into close-packed films at aqueous interfaces. The degree of monolayer formation and 2D order within the self-assembled nanoparticle arrays was observed to be strongly dependent on the amount and type of electrolyte (chloride and/or citrate) adsorbed on the nanoparticle surface, prior to encapsulation and extraction to the solvent interface. Increasing the concentration of adsorbed electrolyte could promote monoparticulate film formation but had a variable effect on local 2D order.     

Multimodal electrophoresis of gold nanoparticles: A real time approach

A real time multimodal data acquisition imaging setup is developed for the electrophoretic movement of plasmonic nanoparticles. Movement of the nanoparticles is recorded by time-lapse digital imaging at 8-megapixel resolutions. The analysis of the moving nanoparticle band is performed using threshold image and color extraction at respective time frames. The migration dynamics is sensitive to size, nature and the extent of the surface conjugation to the nanoparticle. The dynamics of color intensity of the nanoparticles is shown to be dependent on the extent of stabilization of nanoparticle (by a given agent). The stability of nanoparticle is determined by stationary nature and also the relative proportions of pixel intensities in respective color planes (R, G and B). Detergents stabilize nanoparticles in a concentration dependent fashion. In case of neutral polymers the extent of stabilization depends on the relative proportion of the polymer and also on the nature of the same, e.g., PEG (polyethylene glycol) at low concentration imparts higher stability as compared to PVP (polyvinylpyrilidone). The ascending or declining temporal dynamics of color profiles observed in case of citrate stabilized or amino acid conjugated nanoparticles, represent enrichment of plasmonic particles, or their diffusion resulting from loss of charge during migration. The higher dimensional imaging technique thus can be exploited for discriminating the nanoparticles on the basis of their migration behavior and their stability as reflected from color dynamics. The technique is applicable to other nano-sized colored objects, e.g. proteins like hemoglobin where the protein color has important clinical value.