Influence of Line Tension on Spherical Colloidal Particles at Liquid-Vapor Interfaces

Atomic force microscopy (AFM) imaging of isolated submicron dodecyltrichlorosilane coated silica spheres, immobilized at the liquid polystyrene- (PS-) air interface at the PS glass transition temperature, Tg , allows for determination of the contact angle θ versus particle radius R . At Tg , all θ versus R measurements are well described by the modified Young’s equation for a line tension τ=0.93  nN . The AFM measurements are also consistent with a minimum contact angle θmin and minimum radius Rmin , below which single isolated silica spheres cannot exist at the PS-air interface

Improved In Situ Spring Constant Calibration for Colloidal Probe Atomic Force Microscopy

In colloidal probe atomic force microscopy (AFM) surface forces cannot be measured without an accurate determination of the cantilever spring constant. The effective spring constant k depends upon the cantilever geometry and therefore should be measured in situ; additionally, k may be coupled to other measurement parameters. For example, colloidal probe AFM is frequently used to measure the slip length b at solid/liquid boundaries by comparing the measured hydrodynamic force with Vinogradova slip theory (V-theory). However, in this measurement k and b are coupled, hence, b cannot be accurately determined without knowing k to high precision. In this paper, a new in situ spring constant calibration method based upon the residuals, namely, the difference between experimental force-distance data and V-theory is presented and contrasted with two other popular spring constant determination methods. In this residuals calibration method, V-theory is fitted to the experimental force-distance data for a range of systematically varied spring constants where the only adjustable parameter in V-theory is the slip length b. The optimal spring constant k is that value where the residuals are symmetrically displaced about zero for all colloidal probe separations. This residual spring constant calibration method is demonstrated by studying three different liquids (n-decanol, n-hexadecane, and n-octane) and two different silane coated colloidal probe-silicon wafer systems (n-hexadecyltrichlorosilane and n-dodecyltrichlorosilane)

Viscosity Dependent Liquid Slip at Molecularly Smooth Hydrophobic Surfaces

Colloidal probe atomic force microscopy is used to study the slip behavior of 18 Newtonian liquids from two homologous series, the n-alkanes and n-alcohols, at molecularly smooth hydrophobic n-hexadecyltrichlorosilane coated surfaces. We find that the slip behavior is governed by the bulk viscosity η of the liquid, specifically, the slip length b∼ηx with x∼0.33. Additionally, the slip length was found to be shear rate independent, validating the use of Vinogradova slip theory in this work

Long reach cantilevers for sub-cellular force measurements

Maneuverable, high aspect ratio poly 3-4 ethylene dioxythiophene (PEDOT) fibers are fabricated for use as cellular force probes that can interface with individual pseudopod adhesive contact sites without forming unintentional secondary contacts to the cell. The straight fibers have lengths between 5 and 40 μm and spring constants in the 0.07-23.2 nN μm-1 range. The spring constants of these fibers were measured directly using an atomic force microscope (AFM). These AFM measurements corroborate determinations based on the transverse vibrational resonance frequencies of the fibers, which is a more convenient method. These fibers are employed to characterize the time dependent forces exerted at adhesive contacts between apical pseudopods of highly migratory D. discoideum cells and the PEDOT fibers, finding an average terminal force of 3.1 ± 2.7 nN and lifetime of 23.4 ± 18.5 s to be associated with these contacts

Hydrolysis of p-Nitrophenyl Esters Promoted by Semi-fluorinated Quaternary Ammonium Polymer Latexes and Films

Semifluorinated polymer latexes were prepared by emulsion polymerization of 2.5-25% of a fluoroalkyl methacrylate, 25% chloromethylstyrene, 1% styrylmethyl(trimethyl)ammonium chloride, and the remainder 2-ethylhexyl methacrylate under surfactant-free conditions. The chloromethylstyrene units were converted to quaternary ammonium ions with trimethylamine. In aqueous dispersions at particle concentrations of less than 1 mg mL-1 the quaternary ammonium ion latexes promoted hydrolyses of p-nitrophenyl hexanoate (PNPH) in pH 9.4 borate buffer and of diethyl p-nitrophenyl phosphate (Paraoxon) in 0.1 M NaOH at 30 oC with half-lives of less than 10 minutes. Thin 0.7-2 μm films of the latexes on glass promoted fast hydrolysis of Paraoxon but not of PNPH under the same conditions. Even after annealing the quaternary ammonium ion polymer films at temperatures well above their glass transition temperatures, AFM images of the film surfaces had textures of particles. Contact angle measurements of the annealed films against water and against hexadecane showed that the surfaces were not highly fluorinated

Functionalized Polycarbonate Commercial Filters for Water Purification

Can commerercially available filtration membranes be easily functionalized in such a way to enhence the removal the charged contaminants in the water treatment process? The literature demonstrates there have been two pioneering works that demonstrated that Ultrathin Self-Assembled Nanoparticle (USANP) membranes (composed of ~5 nm diameter metallic gold nanoparticles surrounded by organic ligands) when applied to commercial membranes displayed charge sensitive rejection to molecular dyes and also have the ability to charge modify the openings in commercial filters. The rejection mechanisms in these works are proposed to be either size dependent or charged based. Recent experimental results have demonstrated that the supporting filter for these USANP membranes can be functionalized solely with highly charged molecular dye Direct Red 80 using no USANP membranes. After functionalization with direct red 80 alone, average rejection for tested molecular dyes at a concentration of 145 µM increased from 31.8 % to 85.6 % even without the addition of a USANP layer. This indicates that dyes themselves are capable of functionalizing the commercial membranes providing an additional method to enhanced rejection of charged contaminants. This poster highlights the efforts made by a Preservice and Early Career Research for Teachers (PERT) team and an Undergraduate student who was awarded an Summer Undergraduate Research Experience Award to measure the rejection results of these two different functionalization methods. Knowledge gained from these experiments may allow for enhanced rejection of charged based contaminants in polluted waters

Azo-Dye-Functionalized Polycarbonate Membranes for Textile Dye and Nitrate Ion Removal

Challenges exist in the wastewater treatment of dyes produced by the world’s growing textiles industry. Common problems facing traditional wastewater treatments include low retention values and breaking the chemical bonds of some dye molecules, which in some cases can release byproducts that can be more harmful than the original dye. This research illustrates that track-etched polycarbonate filtration membranes with 100-nanometer diameter holes can be functionalized with azo dye direct red 80 at 1000 µM, creating a filter that can then be used to remove the entire negatively charged azo dye molecule for a 50 µM solution of the same dye, with a rejection value of 96.4 ± 1.4%, at a stable flow rate of 114 ± 5 µL/min post-functionalization. Post-functionalization, Na+ and NO3− ions had on average 17.9%, 26.0%, and 31.1% rejection for 750, 500, and 250 µM sodium nitrate solutions, respectively, at an average flow rate of 177 ± 5 µL/min. Post-functionalization, similar 50 µM azo dyes had increases in rejection from 26.3% to 53.2%. Rejection measurements were made using ultraviolet visible-light spectroscopy for dyes, and concentration meters using ion selective electrodes for Na+ and NO3− ions

Mechanical properties of self-assembled nanoparticle membranes: stretching and bending

Monolayers composed of colloidal nanoparticles, with thickness less than ten nanometers, have remarkable mechanical strength and can suspend over micron-sized holes to form free-standing membranes. We discuss experiments probing the tensile strength and bending stiffness of these self-assembled nanoparticle sheets. The fracture behavior of monolayers and multilayers is investigated by attaching them to elastomer substrates which are then stretched. For different applied strain the fracture patterns are imaged down to the scale of single particles. The resulting detailed information about the crack width distribution allows us to relate the measured overall tensile strength to the distribution of local bond strengths within a layer. We then introduce two methods by which freestanding nanoparticle monolayers can be rolled up into hollow, tubular “nano-scrolls”, either by electron beam irradiation during imaging with a scanning electron microscope or by spontaneous self-rolling. Indentation measurements on the nano-scrolls yield values for the bending stiffness that are significantly larger than expected from the response to stretching. The ability to stretch, bend, and roll up nanoparticle sheets offers new possibilities for a variety of applications, including sensors and mechanical transducers

Forces at Individual Pseudopod-Filament Adhesive Contacts

On-chip cellular force sensors are fabricated from cantilever poly(3,4-ethylene dioxythiophene) filaments that visibly deflect under forces exerted at individual pseudopod-filament adhesive contacts. The shape of the deflected filaments and their ∼3 nN/μm spring constants are predicted by cantilever rod theory. Pulling forces exerted by Dictyostelium discoideumcells at these contacts are observed to reach ∼20 nN without breaking the contact

Fracture and Failure of Nanoparticle Monolayers and Multilayers

We present an experimental investigation of fracture in self-assembled gold nanoparticle mono- and multilayers attached to elastomer substrates and subjected to tensile stress. Imaging the fracture patterns down to the scale of single particles provides detailed information about the crack width distribution and allows us to compare the scaling of the average crack spacing as a function of strain with predictions by shear-lag models. With increasing particle size, the fracture strength is found to increase while it decreases as the film thickness is built up layer by layer, indicating stress inhomogeneity in the thickness dimension