Controlling drop size and polydispersity using chemically patterned surfaces

We explore numerically the feasibility of using chemical patterning to control the size and polydispersity of micrometer-scale drops. The simulations suggest that it is possible to sort drops by size or wetting properties by using an array of hydrophilic stripes of different widths. We also demonstrate that monodisperse drops can be generated by exploiting the pinning of a drop on a hydrophilic stripe. Our results follow from using a lattice Boltzmann algorithm to solve the hydrodynamic equations of motion of the drops and demonstrate the applicability of this approach as a design tool for micofluidic devices with chemically patterned surfaces.     

Nanoscale evaluation of lubricity on well-defined polymer brush surfaces using QCM-D and AFM

For preparing a “highly lubricated biointerface”, which has both excellent lubricity and biocompatibility, we investigated the factors responsible for resistance to friction during polymer grafting. We prepared poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(methyl methacrylate) (PMMA) brush layers with high graft density and well-controlled thickness using atom transfer radical polymerization (ATRP). We measured the water absorptivity in the polymer brush layers and the viscoelasticity of the polymer-hydrated layers using a quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The PMPC brush layer had the highest water absorptivity, while the PMPC-hydrated layer had the highest fluidity. The friction properties of the polymer brush layers were determined in air, water, and toluene by atomic force microscopy (AFM). The friction on each polymer brush decreased only when a good solvent was chosen for each polymer. In conclusion, the brush layer possessing high water absorptivity and fluidity in water contributes to reduce friction. PMPC grafting is an effective and promising method for obtaining highly lubricated biointerfaces.     

Polypyrrole-palladium nanocomposite coating of micrometer-sized polymer particles toward a recyclable catalyst

A range of near-monodisperse, multimicrometer-sized polymer particles has been coated with ultrathin overlayers of polypyrrole-palladium (PPy-Pd) nanocomposite by chemical oxidative polymerization of pyrrole using PdCl(2) as an oxidant in aqueous media. Good control over the targeted PPy-Pd nanocomposite loading is achieved for 5.2 μm diameter polystyrene (PS) particles, and PS particles of up to 84 μm diameter can also be efficiently coated with the PPy-Pd nanocomposite. The seed polymer particles and resulting composite particles were extensively characterized with respect to particle size and size distribution, morphology, surface/bulk chemical compositions, and conductivity. Laser diffraction studies of dilute aqueous suspensions indicate that the polymer particles disperse stably before and after nanocoating with the PPy-Pd nanocomposite. The Fourier transform infrared (FT-IR) spectrum of the PS particles coated with the PPy-Pd nanocomposite overlayer is dominated by the underlying particle, since this is the major component (>96% by mass). Thermogravimetric and elemental analysis indicated that PPy-Pd nanocomposite loadings were below 6 wt %. The conductivity of pressed pellets prepared with the nanocomposite-coated particles increased with a decrease of particle diameter because of higher PPy-Pd nanocomposite loading. "Flattened ball" morphologies were observed by scanning/transmission electron microscopy after extraction of the PS component from the composite particles, which confirmed a PS core and a PPy-Pd nanocomposite shell morphology. X-ray diffraction confirmed the production of elemental Pd and X-ray photoelectron spectroscopy studies indicated the existence of elemental Pd on the surface of the composite particles. Transmission electron microscopy confirmed that nanometer-sized Pd particles were distributed in the shell. Near-monodisperse poly(methyl methacrylate) particles with diameters ranging between 10 and 19 μm have been also successfully coated with PPy-Pd nanocomposite, and stable aqueous dispersions were obtained. The nanocomposite particles functioned as an efficient catalyst for the aerobic oxidative homocoupling reaction of 4-carboxyphenylboronic acid in aqueous media for the formation of carbon-carbon bonds. The composite particles sediment in a short time (相似文献   

Size-dependent self-organization of colloidal particles on chemically patterned surfaces

A study of the self-organization of colloidal particles during the evaporation of particle solutions on chemically patterned surfaces is presented. On a surface with hydrophilic and hydrophobic regions, colloidal particles form compact structures on the hydrophilic sites. When a colloidal solution containing a mixture of particles with a variation in size is used, the number density of each type of particle deposited on the hydrophilic islands after evaporation decreases with increasing particle size. This makes it possible to produce a concentration gradient of the particles on islands of different sizes. It is shown that this technique could allow for particle separation.     

Assembly of colloidal particles by evaporation on surfaces with patterned hydrophobicity

Drops containing suspended particles are placed on surfaces of patterned wettability created using soft lithography; the drop diameter is large compared to the dimensions of the patterns on the substrate. As the three-phase contact line of the drop recedes, spontaneous dewetting of the hydrophobic domains and flow into the hydrophilic domains create discrete fluid elements with peripheries that can mimic the underlying surface topography. Suspended particles are carried with the fluid into the wetted regions and deposit there as the discrete fluid domains evaporate. If particle volume fractions are sufficiently high, the entire wetted domain can be covered with colloidal crystals. At lower volume fractions, flow within the evaporating fluid element can direct the deposition of colloidal particles at the peripheries of the domains. High-resolution arrays of particles were obtained with a variety of features depending upon the relative size of the wetting regions to the particles. When the wetting region is larger than the particles, three-dimensional and two-dimensional arrays of ordered particles mimicking the shape of the wetting pattern form, depending on the particle volume fraction. For lower volume fractions, one-dimensional (1-D) arrays along the wet/non-wet boundaries form. When the particle size is similar to the height of fluid on the wetted domain, zero-dimensional distributions of single particles centered in the wet regions can form for wetted squares or 1-D distributions (stripes) form along the axis of striped domains. Finally, when the wetting region is smaller than the particle size, the particles do not deposit within the features but are drawn backward with the receding drop. These results indicate that evaporation on surfaces of patterned wetting provides a highly parallelizable means of tailoring the geometry of particle distributions to create patterned media.     

Graphoepitaxial deposition of cationic polymer micelles on patterned SiO2 surfaces

We have studied the deposition of polymer micelles formed from poly(styrene)-block-poly(2-vinylpyridine) (PS-PVPH+) from room-temperature aqueous solutions at pH 1 onto a hydrophilic Si/SiO2 surface with a relief pattern 100 nm deep with variable widths. It has been found that the micelle density is substantially higher and the ordering of the micelles is improved for micelles that adsorb in the 100 nm depressions in the width range of ca. 500-5000 nm. We ascribe these effects to capillary forces that pull the aqueous solution into the canyons where the micelles can be trapped. While the ordering of the micelles can be substantial, they do not form a perfect hexagonal crystal. If the surface is chemically modified by a Au coating, the micelle-surface interaction is strengthened and the degree of ordering is diminished. These results demonstrate that a combination of graphoepitaxy and processing conditions (speed of substrate withdrawal or evaporation of solvent) can be used to make fairly ordered polymer micelle arrays over a space of (at least) several millimeters.     

Preparation of micrometer-sized polymer particles with control of initiator dissociation during soap-free emulsion polymerization

A previously proposed method of soap-free emulsion polymerization employing an amphoteric initiator, 2,2'-azobis [N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (VA-057), was extended to synthesize micrometer-sized polystyrene particles with low polydispersity in an acidic region of pH from 3.3 to 4.6. A buffer system of CH3COOH/CH3COONa was used for the adjustment of pH, which was aimed at effective promotion of particle coagulation in early stage of the polymerization. In these experiments, CH3COOH concentration was varied from 20 to 360 mM at a CH3COONa concentration of 10 mM. Polymer particles with an average size of 1.8 microm and low polydispersity were obtained at the CH3COOH concentration of 40 mM for the concentrations of 1.1 M styrene monomer and 10 mM initiator. To more precisely control dispersion stability of particles, experiments in which pH was stepwisely changed during the polymerization were also carried out. This polymerization method could enhance the average size of particles to 2.2 microm while retaining the monodispersity of particles. Furthermore, combination of pH stepwise change and monomer addition during the polymerization could produce particles with an average size of 3.0 microm and low polydispersity.     

Size-selective deposition and sorting of lyophilic colloidal particles on surfaces of patterned wettability

A highly parallelizable means of positioning or sorting particles in a size-selective manner into arrays is demonstrated based on the placement of particle suspensions on surfaces of patterned wettability and the subsequent evaporation of the suspending solvent. The method relies on creating lyophilic features of dimensions similar to or greater than those of the particles to be arrayed and smaller than those of the particles to be excluded. As the contact line recedes, it fills lyophilic features, creating discrete fluid elements that mimic the underlying lyophilic pattern. The fluid elements have aspect ratios dictated by the contact angle. By adjusting the size of the lyophilic features, the heights of the fluid elements can be adjusted to sequester or exclude particles based on their diameter. The principal interest of this work is its broad applicability. No prior understanding of the particle properties is needed except for the size of the particle and its ability to be suspended in a solvent.     

Removal of nanoparticles from plain and patterned surfaces using nanobubbles

It is the aim of this paper to quantitatively characterize the capability of surface nanobubbles for surface cleaning, i.e., removal of nanodimensioned polystyrene particles from the surface. We adopt two types of substrates: plain and nanopatterned (trench/ridge) silicon wafer. The method used to generate nanobubbles on the surfaces is the so-called alcohol-water exchange process (use water to flush a surface that is already covered by alcohol). It is revealed that nanobubbles are generated on both surfaces, and have a remarkably high coverage on the nanopatterns. In particular, we show that nanoparticles are-in the event of nanobubble occurrence-removed efficiently from both surfaces. The result is compared with other bubble-free wet cleaning techniques, i.e., water rinsing, alcohol rinsing, and water-alcohol exchange process (use alcohol to flush a water-covered surface, generating no nanobubbles) which all cause no or very limited removal of nanoparticles. Scanning electron microscopy (SEM) and helium ion microscopy (HIM) are employed for surface inspection. Nanobubble formation and the following nanoparticle removal are monitored with atomic force microscopy (AFM) operated in liquid, allowing for visualization of the two events.     

Drying dissipative structures of spindle-shaped hematite particles coated with polymer brush

Macroscopic and microscopic drying patterns were observed on a cover glass, a watch glass, and a Petri glass dish during dryness of aqueous suspensions of spindle-shaped particles of hematite coated with polymer brush (SHB). Outer and inner broad rings formed and the spoke-lines appeared especially on a watch glass at the intermediate initial concentration of SHB. Cooperative drying processes of the convection, sedimentation, and solidification were supported also for the anisotropic particles. Most of the long axes of SHB particles distributed parallel to the substrate plane. There appeared the microscopic alignment of the several ten micrometers similar-sized aggregates composed of the SHB particles. The parallel and/or flower-like (or spoke-like) arrangements of SHB particles were observed in the scanning electron microscopy. Effective shape of SHB particles including the electrical double layers during the convection flow processes are deduced to be near spherical. However, the effective shape came to be spindle-like during the sedimentary and solidification processes by the thinning of the double layers. The distorted paralleled and/or flower-like alignments of SHB particles were observed in the dried film.     

Interactions between protein coated particles and polymer surfaces studied with the rotating particles probe

Nonspecific interactions between proteins and polymer surfaces have to be minimized in order to control the performance of biosensors based on immunoassays with particle labels. In this paper we investigate these nonspecific interactions by analyzing the response of protein coated magnetic particles to a rotating magnetic field while the particles are in nanometer vicinity to a polymer surface. We use the fraction of nonrotating (bound) particles as a probe for the interaction between the particles and the surface. As a model system, we study the interaction of myoglobin coated particles with oxidized polystyrene surfaces. We measure the interaction as a function of the ionic strength of the solution, varying the oxidation time of the polystyrene and the pH of the solution. To describe the data we propose a model in which particles bind to the polymer by crossing an energy barrier. The height of this barrier depends on the ionic strength of the solution and two interaction parameters. The fraction of nonrotating particles as a function of ionic strength shows a characteristic shape that can be explained with a normal distribution of energy barrier heights. This method to determine interaction parameters paves the way for further studies to quantify the roles of protein coated particles and polymers in their mutual nonspecific interactions in different matrixes.     

Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules

Dense poly(N-isopropylacrylamide) (PIPAAm) brushes were created on silica bead surfaces by surface-initiated atom transfer radical polymerization (ATRP). Interfacial properties of PIPAAm brushes were characterized by thermoresponisve interaction with biomolecules. The grafted amounts of PIPAAm on silica bead surfaces exceeded that from previously reported polymer-hydrogel-modified silica beads prepared by conventional radical polymerization by nearly 1 order of magnitude. Temperature-dependent chromatographic interactions with soluble analytes were modulated by changing the grafted PIPAAm chain lengths. Short PIPAAm-grafted silica beads produce insufficient dehydration and chain aggregation to separate steroids using weak hydrophobic interactions. In contrast, broad unresolved peaks were observed on silica beads column grafted with long PIPAAm chains due to steroid partitioning into thick, densely grafted PIPAAm brush layers. Thus, silica beads column grafted with PIPAAm chains of proper length can demonstrate baseline separation of steroids with relatively high resolution among the tested columns. Relatively longer retention times for steroid analytes were observed on all columns compared to those previously reported for other PIPAAm-grafted silica beads. This indicates that densely PIPAAm-grafted chains enable control of strong hydrophobic interactions with steroids by changing the column temperature. Densely grafted PIPAAm columns were also successful in separating two peptides into two peaks as the column temperature was increased to 40 degrees C. This provides an effective separation alternative for peptides using substantial hydrophobicity without modification of hydrophobic surfaces and/or low mobile phase pH. In conclusion, densely PIPAAm-grafted surfaces exhibit strong, reversible temperature-modulated hydrophobic interactions, facilitating baseline separations of steroids and peptides in aqueous milieu without changes in the mobile phase pH and high ionic strength.     

Polar anchoring strengths of nematic liquid crystal on high-density polymer brush surfaces

ABSTRACT

Herein, the polar anchoring energy coefficient (A_θ) of nematic liquid crystal (NLC) was examined for high-density polymer brushes via capacitance measurements. The A_θ is 10^?4 J m^?2 for the brushes of poly(methyl methacrylate), poly(ethyl methacrylate) and poly(styrene). The value decreases to 10^?5 J m^?2 for poly(n-butyl methacrylate) and poly(hexyl methacrylate) with lower glass transition temperatures. However, each polymer brush displays a constant A_θ value over a temperature range of ?15°C to 90°C, which is hardly affected by the graft density and brush thickness. At 25°C, A_θ is 10 times greater than the corresponding azimuthal anchoring energy coefficient (A_φ); therefore, NLCs on polymer brushes can be preferentially aligned along the in-plane component of the applied field.     

Probing cooperative interactions of tailor-made nucleation surfaces and macromolecules: a bioinspired route to hollow micrometer-sized calcium carbonate particles

It is well known that the formation of biominerals by living organisms is governed by the cooperation of soluble and insoluble macromolecules with peculiar interfacial properties. To date, most of the studies on mineralization processes involve model systems that account only for the existence of one organic matrix and thus disregard the interaction between the soluble and insoluble organic components that is crucial for a better understanding of the processes taking place at the inorganic-organic interface. We have set up a model system composed of a matrix surface, which is composed of a self-assembled monolayer (SAM) and a soluble component, poly(aspartic acid). It could be demonstrated that the phase selection of calcium carbonate and the morphology of the resulting particles are determined by the stabilization of amorphous precursor particles by the polymer and the interaction between polymer and SAM. The morphology of the hollow vaterite microspheres are reminiscent to a 3D analogue of the so-called "coffee-stain effect", where the transformation from a voluminous hydrated, amorphous material to a more dense crystalline material leads to the formation of hollow spheres from massive spherical microparticles.     

Recognition of sugars on surface-bound cap-shaped gold particles modified with a polymer brush

A dithiolated random copolymer with pendent phenylboronic acid residues (Cys-Poly(3-acrylamidophenylboronic acid-co-2-dimethylaminopropyl methacrylamide), Cys-Poly(APBA-co-DMAPMA)) obtained by photo-iniferter method was accumulated as a polymer brush on a cap-shaped gold particles deposited on a vacuum-evaporated gold film, and the usefulness of the polymer brush as a sensing element for glycoprotein, ovalbumin (OVA), was examined by using UV-vis spectroscopy with a help of surface plasmon resonance. A similar system was constructed with a dithiolated mannose-carrying polymer, dithiolated-poly(2-methacryloyloxyethyl-D-mannopyranoside) (DT-PMEMan), prepared by the atom transfer radical polymerization (ATRP). The brush composed of this polymer was examined as a sensing element for lectin, concanavalin A (Con A). The sensor cells modified with Cys-Poly(APBA-co-DMAPMA) and DT-PMEMan showed a concentration-dependent binding of OVA and Con A, respectively, with a comparable detection limit to those with a monolayer of polymer brush-coated gold particle deposited on a glass substrate. Using this system, it can be expected to open a new perspective to various functional polymer brushes fixed to the cap-shaped gold particle on a solid substrate.     

Novel fabrication of Janus particles from the surfaces of electrospun polymer fibers

A novel synthetic approach for the efficient fabrication of Janus silica particles was demonstrated by embedment of zero-dimensional colloids on one-dimensional polymer fiber surfaces, followed by the surface modification on the exposed silica hemispheres. Electrospinning of poly(methyl methacrylate) and poly(4-vinyl pyridine) blends produced polymer fibers with high specific surface area and desired surface hydrophilicities. Fiber compositions determined the colloid adsorption density and uniformity. The colloid embedding resulted from the polymer softening was manipulated by the isothermal heat treatment. Subsequent silianization completed the amino functionalities on hemispherical surfaces of embedded silica colloids. Janus particles with uniform asymmetric chemical features were further labeled with gold nanoparticles before their recovery from fiber substrates. Fabrication of Janus particles, including colloid adsorption, temperature-driven embedding, and hemispherical surface modification, were investigated and are discussed.     

Zerovalent metal polymer composites. III. Metallization of metal oxide surfaces with the aid of metallized functional polymer microdispersions

The adsorption of poly[N-(m- and p-vinylbenzyl)-N,N,N-trimethylammonium tetrachloropal-ladate] complex on inorganic oxide surfaces followed by reduction of the palladium salt to form a catalytically active zerovalent metal polymer composite dispersed on the oxide surface and further deposition of transition metals, e.g., nickel, cobalt, and copper, by “additive” or “subtractive” deposition from electroless plating solutions is described. γ-Ferric oxide was used as a template for such intermetallic replacement reactions, providing materials with controlled amounts of metal. Multimetallic catalysts based on aluminum oxide, zinc oxide, lanthanum oxide, magnesium oxide, and silica were prepared. Iron oxide modified by subtractive deposition of rhodium and iridium on nickel-clad iron oxide were evaluated in Fischer–Tropsch carbonylation reactions leading from synthesis gas to alkanols.     

Colloidal crystallization of spindle-shaped hematite particles coated with polymer brush in deionized aqueous suspension

Colloidal crystallization of highly monodisperse spindle-shaped hematite particles coated with poly(poly(ethylene oxide) methyl ether methacrylate) brush (SHB) was studied by reflection spectroscopy and optical microscopy. SHB suspensions were deionized exhaustively with the mixtures of cation- and anion-exchange resins more than 6 months. The liquid thin film along the vertical cell wall above the horizontal air–liquid interface showed the strong color bands. Furthermore, the reflection spectra composed of many sharp peaks shifted continuously toward shorter wavelengths with time. These observations support the presence of thin film of SHB suspension, where the width is thickened downward by the gravity and the layered liquid further flow downward with time. The rigidities of SHB crystals in the bulk phase estimated from the optical microscopy in the sedimentation equilibrium were 0.007 to 0.7 Pa as SHB concentration increased from 0.006 to 0.35 wt.%. The fluctuation parameter, b-factors of the anisotropic crystals, was from 0.025 to 0.035 and decreased slightly as particle concentration increased. Rigidities and the fluctuation parameters of SHB suspensions support that the elastic properties of the anisotropic-shaped colloidal crystals are close to those of typical crystals of colloidal spheres. Compression of the SHB crystals by the gravity is also suggested in the sedimentation equilibrium state.     

Preparation of micrometer-sized, monodisperse "janus" composite polymer particles having temperature-sensitive polymer brushes at half of the surface by seeded atom transfer radical polymerization

Micrometer-sized, monodisperse polystyrene (PS)/poly[methyl methacrylate-(chloromethyl)styrene] [P(MMA-CMS)] composite particles having hemispherical structure were prepared by solvent evaporation from toluene droplets containing dissolved PS and P(MMA-CMS) dispersed in aqueous solution, which had been prepared using the membrane method. The formation of hemispherical ("Janus") morphology by phase separation between the PS and the P(MMA-CMS) was confirmed by both optical and electron microscopy. Atom transfer radical polymerization (ATRP) of 2-(dimethylamino)ethyl methacrylate (DM) was subsequently carried out in the presence of hemispherical PS/P(MMA-CMS) composite particles in an aqueous dispersed system. After polymerization, the morphology of the particles changed from spherical to "mushroom" shape as observed by scanning electron microscopy, indicating that DM polymerized inside or on the surface of half [P(MMA-CMS) phase] of the particles. 1H NMR spectra were consistent with chloromethyl functional groups in P(MMA-CMS) operating as ATRP initiators in the DM polymerization.