Polyelectrolyte Capsules Modified with YF3 Nanoparticles: An AFM Study

Summary: We studied changes in the mechanical properties of polyelectrolyte‐multilayer capsules induced by YF₃‐nanoparticle formation inside the layers. Using direct‐deformation measurements by colloidal probe atomic force microscopy (AFM), we found that the nanoparticle formation increases the capsule stiffness by one order of magnitude. At the same time, we observed that buckling instabilities of the capsules are suppressed after the nanoparticle modification.

RICM picture of an initial PAH/PSS capsule under high deformation.     

Anodic Stripping Voltammetry: An AFM Study of Some Problems and Limitations

The use of anodic stripping voltammetry for quantitative analytical measurements using solid electrodes is addressed in the light of generic limitations arising from i) electrode heterogeneity, ii) electrode morphology, iii) inhibited electrodeposition, and iv) incomplete stripping of deposited metal in the anodic sweep. It is shown, using direct imaging of electrode surfaces via AFM and optical microscopy, that each of the preceding factors may produce significant deviations from ideal electrode behavior. The use of atomic force microscopy to fully characterize any developed ASV procedures is strongly recommended. To ensure reproducible and accurate stripping voltammetry, steps should be taken to minimize the effects discussed.     

Simulation of the Adhesion of Particles to Surfaces

The removal of micrometer and submicrometer particles from dielectric and metal films represents a challenge in postchemical mechanical polishing cleaning. Proper modeling of the adhesive force between contaminant particles and these films is needed to develop optimal solutions to postchemical mechanical polishing cleaning. We have previously developed and experimentally validated a model to describe the adhesion between spherical particles and thin films. This simulation expands previous models to characterize the adhesive interaction between asymmetrical particles, characteristic of a polishing slurry, and various films. Our simulation accounts for the contact area between particles and substrates, as well as the morphology of the surfaces. Previous models fail to accurately describe the contact of asymmetrical particles interacting with surfaces. By properly accounting for nonideal and geometry and morphology, the simulation predicts a more accurate adhesive force than predictions based upon an ideal van der Waals model. The simulation is compared to experimental data taken for both semi-ideal particle-substrate systems (polystyrene latex spheres in contact with silicon films) and asymmetrical systems (alumina particles in contact with various films). Copyright 2001 Academic Press.     

Adhesion of Colloidal ZnO Particles on ZnS-Type Phosphor Surfaces

Chemical and physical aspects of the adhesion of colloidal ZnO particles (d(50)=81 nm) on the surface of ZnS-type phosphors have been studied. Here, the green-emitting phosphor ZnS:Cu,Al,Cu (d(50)=5.0 μm) applied in TV screens was chosen as model compound. The ZnS material was pretreated in various ways (H(2)O, HCl, H(2)O(2)) and reacted thereafter with a suspension containing colloidal ZnO particles. Analytical investigations (SEM, ESCA) have shown that the adhesion of colloidal ZnO particles is strongly affected by the degree of hydrolysis of the ZnS surface. Electroacoustic investigations (ESA) prove that both types of surfaces, hydrolyzed ZnS as well as colloidal ZnO, are positively charged. Even so, adhesion of ZnO particles is encouraged very much under these conditions, indicating that secondary attractive forces (electrostatic interaction, chemical bonding) determine the amount of colloidal ZnO adhered on a ZnS-type phosphor. Copyright 2000 Academic Press.     

Adsorption and Bioactivity of Protein A on Silicon Surfaces Studied by AFM and XPS

The adsorption of protein A on silicon surfaces was studied by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy. The deposition was made statically from various concentrations of protein A in water solution. The biological activity was checked by the immobilization of rabbit immunoglobulin G. The protein adsorption occurs in least two different phases and leads to a multilayer film. The first monolayer of proteins is rapidly adsorbed on the surface. The adsorption of the second layer of proteins occurs much more slowly (a thousand times slower) and also involves the third monolayer. The protein A of the first monolayer is denaturated and biologically inactive. On the contrary, the proteins of the second monolayer keep their natural diameter and remain biologically active. AFM artifacts such as the convolution with small objects and the resulting estimation of the coverage ratio are discussed. Copyright 2001 Academic Press.     

Adhesion of Colloidal SiO(2) Particles on ZnS-Type Phosphor Surfaces

The interaction between colloidal SiO(2) particles and the surface of ZnS-type phosphors has been studied. The green emitting phosphor ZnS:Cu,Al,Au applied in color television tubes was chosen as a model compound. After the surface of the phosphor particles (d(50)=5.0 μm) was treated in different manners like washing with H(2)O, HCl, or H(2)O(2) as well as precoating with colloidal ZnO particles (d(50)=81 nm), colloidal SiO(2) particles (d(50)=207 nm) were added. Thereafter, the amount of adhered SiO(2) was investigated based on SEM and ESCA analysis. By ESA measurements the surface charge of the colloids and the differently treated ZnS materials was investigated. Based on the experimental results it can be concluded that colloidal SiO(2) particles adhere sufficiently only if ZnO is present on the ZnS surface. The SiO(2) particles are located on top of the ZnO. Finally, the attractive interactions in the system ZnS-ZnO-SiO(2) are discussed in more detail. Copyright 2000 Academic Press.     

An AFM Study of the Correlation of Lead Dioxide Electrocatalytic Activity with Observed Morphology

PbO2 is widely employed as an electrocatalyst for anodic oxidation processes including the generation of oxygen and the degradation of various organic species in aqueous solution. However, despite extensive investigation, the precise mechanism of action remains obscure. In this paper we establish a previously unrecognized strong correlation between the morphology of the PbO2 deposits and their electrocatalytic activity. Cyclic voltammetric results are described for the electrodeposition of PbO2 on boron-doped diamond (BDD) electrodes from 2.5 mM solutions of lead(II) nitrate in nitric acid at pH values between approximately 0 and 7. A likely change in mechanism is observed around pH 4, consistent with the Pourbaix diagram of lead. The morphology of the PbO2 films is observed as a function of time and potential, using in situ AFM in each of the lead solutions. Information on the growth rates of the films is extracted, and the limitations of using AFM in such an application are discussed. It is shown that the deposit morphology depends strongly on the specific conditions used. The oxidation of a 100 mM glucose solution on electrodes modified by PbO2 deposition at a range of potentials and pH values is used as an indicator of the catalytic activity of the corresponding films, leading to the observation of the correlation between deposit morphology and catalytic activity mentioned above.     

Film Formation from Nanosized Copolymeric Latex Particles: A Photon Transmission Study

The photon transmission technique was used to monitor the evolution of transparency during film formation from nanosized copolymeric latex particles. The latex films were prepared from poly(methyl methacrylate-co-butyl methacrylate) (P(MMA-co-BMA)) particles which were produced by microemulsion polymerization. These films were annealed at elevated temperatures in various time intervals above the glass transition temperature (T(g)) of P(MMA-co-BMA). It is observed that the transmitted photon intensity (I(tr)) from these films increased as the annealing temperature increased. There are three different film formation stages. These stages are explained by the void closure, healing, and interdiffusion processes, respectively. The activation energies for viscous flow (DeltaH approximately 16 kcal/mol), minor chains (DeltaE(H) approximately 27 kcal/mol), and backbone motion (Delta E(b) approximately 132 kcal/mol) were obtained using various models. Void closure (tau(v), T(v)) and healing points (tau(H), T(H)) were determined. Using the time-temperature pairs, void closure and healing activation energies were measured and found to be 21 and 30 kcal/mol, respectively. Copyright 2001 Academic Press.     

ChemInform Abstract: An ab initio Study of Potential Energy Surfaces for N8 Isomers.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Limitations of Affinity Chromatography: Solvolytic Detachment of Ligands from Polymeric Supports

Ligands of the R? NH₂ type which are covalently bound to agarose, cellulose, or cross-linked dextranes by the conventional cyanogen bromide method are slowly detached from their supports by solvolytic processes occurring above pH 5 in aqueous surroundings. At pH values between 5 and 10, the free ligands, R? NH₂, appear in solution. Above about pH 10, the carbamyl derivative of the ligand, RNHCONH₂, is the main product. Dilute ammonia releases iminocarbamyl derivatives, RNHC(?NH)NH₂. The latter type of compound has also been observed in tris(hydroxymethyl)-aminomethane buffers at pH 8 and 9. Possible reaction mechanisms have been formulated on the basis of the structures suggested by Axén & Ernback for activated and substituted polysaccharides. Ligands attached to polyacrylamide gels ( A ) through amide bonds to carboxyl groups of the carrier, RNH? CO·A, are released at slower rates and invariably as the free, unsubstituted ligand molecules. The release reaction appear to be general and independent of the particular ligand structure. We therefore advise caution with all experiments that can be adversely influenced by the presence of free ligands (e.g. localization of hormone receptors on the cell surface). At pH5, sepharose-bound 8-(?-aminocaproyl-β-aminoethylthio)-adenosine-3′, 5′-cyclo-monophosphate removes cyclic 3′, 5′-adenosine-monophosphate-binding proteins from their solutions, but the corresponding polyacrylamide derivative does not (pH 7).     

Molecular Weight Effect on Latex Film Formation from Polystyrene Particles: A Photon Transmission Study

The photon transmission method was used to probe the time evolution of film formation from latex particles. Two different latex films were prepared from high molecular weight (HM) and low molecular weight (LM) polystyrene particles at room temperature and were annealed at various temperatures in 2.5-min time intervals above the glass transition. The increase in the transmitted photon intensity (Itr) is attributed to the increase in "crossing density" at the junction surface. The Prager-Tirrell model was employed to interpret the increase in crossing density at the junction surface. The back and forth activation energies were measured for HM and LM films and found to be around 59 and 87 kcal/mol for a reptating polymer chain across the junction surface. Monte Carlo simulations were performed for photon transmission through a rectangular lattice. The number of transmitted photons (Ntr) was calculated as a function of the mean free path of photons. It was observed that Ntr, similar to Itr, increases as the square of the mean free path of photons is increased. Copyright 1999 Academic Press.     

An atomic force microscope (AFM) and tapping mode AFM study of the solvent-induced crystallization of polycarbonate thin films

Thin films of bisphenol-A polycarbonate (PC) were progressively crystallized in a controllable manner under the action of an appropriate plasticizing agent. No conducting layer was applied to the polymer surface, so that imaging with the atomic force microscope (AFM) left the sample exposed for additional plasticizer treatment. The PC sample was observed many times throughout the crystallization process using the AFM in both the contact and tapping modes. Data regarding the growth process for spherulites in addition to high-resolution morphology studies were achieved. © 1996 John Wiley & Sons, Inc.     

Electrochemically Modified Carbon and Chromium Surfaces for AFM Imaging of Double‐Strand DNA Interaction with Transposase Protein

Carbon and chromium surfaces were modified by electrochemical reduction of a diazonium salt formed in situ from the sulfanilic acid. The organic layer formed was activated by phosphorus pentachloride (PCl₅) to form a benzene sulfonil chloride (Ar? SO₂Cl). An electrochemical study of the blocking effect and the activity of this surface was carried out on a carbon electrode. The chromium surface study was completed by X‐ray photoelectron spectroscopy and atomic force microscopy to characterize the formation of a compact monolayer (0.8 nm height and roughness 0.2–0.3 nm). The compactness and the activity of this organic monolayer allowed us to affix a length dsDNA with the aim of analyzing the formation of a complex between dsDNA and a protein. The interaction of a transposase protein with its target dsDNA was investigated. The direct imaging of the nucleoproteic complex considered herein gives new insights in the comprehension of transposase–DNA interaction in agreement with biochemical data.     

Surface Initiated Polymerization from Nanoparticle Surfaces

Abstract

The synthesis, characterization, and development of new nanoparticle materials have both scientific and technological significance. Surface initiated polymerization (SIP) from nanoparticle surfaces involves the growth of end‐tethered polymer brushes where the length or thickness can be more than twice the radius of gyration (Rg) compared to a free polymer in solution. Different mechanisms are possible on a variety of initiators, reaction conditions, monomers, and nanoparticles. Important differences to solution and bulk polymerization can be observed where the nanoparticles with grafted initiators behave as macroinitiators. In turn, the development of these materials will allow the preparation of thermodynamically and kinetically stable nanocomposites and colloids. Through the careful use of surface sensitive spectroscopic and microscopic techniques, much has been gained from the direct and in‐situ analysis of grafted polymers on the nanoparticles with regards to the kinetics and mechanism of the polymerization process. Parallels can be drawn to SIP on flat surfaces where surface sensitive spectroscopic and microscopic measurements are complementary to analysis methods for colloidal particles. Thus, this review surveys the different polymerization mechanisms and procedures towards forming core‐shell types of hybrid inorganic–organic polymer nanoscale materials.     

ATRP grafting of styrene from benzyl chloride functionalized polysiloxanes: An AFM and TGA study of the Cu(0)/bpy catalyst

Various combinations of Cu(0), CuCl, 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) were used as catalysts for the grafting polymerizations of styrene from polysiloxane macroinitiators functionalized with benzyl chloride. While Cu(0)/bpy alone promotes the grafting, narrower polydispersities were obtained in the presence of CuCl. Analysis of the Cu(0) surface before and after polymerization by a combination of AFM, TGA and FTIR investigations reveals the formation of bpy or phen films on Cu(0). In the presence of CuCl, the ligand film appears decorated with CuCl particles which increase in size with increasing the CuCl concentration. The initial layer occurs most likely as a result of complexation between the ligands and the Cu(0) surface and acts as a support for the rest of the film. These observations are consistent with the film formation on Cu(0) from related nitrogen donors and indicate that the reactivity of the Cu surface may depend not only on its prior treatment but also on the deposition of ligands from the reaction mixture.     

Detachment force of particles from air-liquid interfaces of films and bubbles

The detachment force required to pull a microparticle from an air-liquid interface is measured using atomic force microscopy (AFM) and the colloidal probe technique. Water, solutions of sodium dodecyl sulfate (SDS), and silicone oils are tested in order to study the effects of surface tension and viscosity. Two different liquid geometries are considered: the air-liquid interface of a bubble and a liquid film on a solid substrate. It was shown that detaching particles from liquid films is fundamentally different than from bubbles or drops due to the restricted flow of the liquid phase. Additional force is required to detach a particle from a film, and the maximum force during detachment is not necessarily at the position where the particle breaks away from the interface (as seen in bubble or drop systems). This is due to the dynamics of meniscus formation and viscous effects, which must be considered if the liquid is constrained in a film. The magnitude of these effects is related to the liquid viscosity, film thickness, and detachment speed.     

Bubble colloidal AFM probes formed from ultrasonically generated bubbles

Here we introduce a simple and effective experimental approach to measuring the interaction forces between two small bubbles (approximately 80-140 microm) in aqueous solution during controlled collisions on the scale of micrometers to nanometers. The colloidal probe technique using atomic force microscopy (AFM) was extended to measure interaction forces between a cantilever-attached bubble and surface-attached bubbles of various sizes. By using an ultrasonic source, we generated numerous small bubbles on a mildly hydrophobic surface of a glass slide. A single bubble picked up with a strongly hydrophobized V-shaped cantilever was used as the colloidal probe. Sample force measurements were used to evaluate the pure water bubble cleanliness and the general consistency of the measurements.     

Microemulsion Polymerization: An Undergraduate Experiment in the Synthesis of Nanosized Polystyrene Particles

The synthesis of polystyrene nanoparticles through microemulsion polymerization is presented as an undergraduate advanced organic laboratory exercise. The resultant polymers molecular weight and particle size are studied as a function of monomer and initiator concentration. A comparison of cationic vs. anionic surfactants, and their effects on the polymer produced through microemulsion polymerization are also investigated. A direct relationship is observed between molecular weight and monomer concentration. A direct relationship is also found for the particle size of the latex produced. An inverse relationship is observed for molecular weight and particle size as the initiator concentration was raised. Comparison of molecular weight and latex size for cationic and anionic surfactants demonstrates that the anionic surfactant produces both a higher molecular weight and a larger latex size over the entire monomer and initiator concentration ranges.     

Metal Nanoparticles on Polymer Surfaces: 3. Adsorption Kinetics of Gold Hydrosol Particles on Polystyrene and Poly(2-vinylpyridine)

The adsorption of gold hydrosol nanoparticles on the surfaces of polystyrene and poly(2-vinylpyridine) was studied using two techniques, quartz crystal microgravimetry and atomic force microscopy. The resultant experimental data indicated that the kinetics of this process is controlled by the diffusion. The nanoparticle adsorption, up to rather high polymer surface coverages (35%), is irreversible.