Evaluation of Adhesion Forces for the Manipulation of Micro-Objects in Submerged Environment through Deposition of pH Responsive Polyelectrolyte Layers.

Optimization of surface treatment for reversible adhesion of micro-objects in liquid environment for the need in microassembly processes is presented. A spherical borosilicate probe and planar oxidized silicon wafer substrates were modified by deposition of pH sensitive polyelectrolyte films through layer-by-layer technique. Branched polyethylenimine (b-PEI) and poly(sodium styrenesulfonate) (PSS) were deposited in alternating manner on surfaces, and the influence of polyelectrolyte concentration, pH of deposition, and number of layers on the adhesion were successively examined. The multilayer buildup was followed by optical reflectometry (OR) and dissipative quartz crystal microbalance (QCM-D). The adhesion forces were monitored in aqueous environment at variable pH values by colloidal probe AFM microscopy. The thermodynamic work of adhesion was derived from the pull-off forces by using the Johnson-Kendall-Roberts (JKR) model and compared to the work of adhesion determined from contact angle measurements. It was found out that they correlate well, however, the values accessed from JKR model were underestimated, which was attributed mainly to the effect of surface roughness. Obtained results have demonstrated that it is possible to achieve repeatable reversible adhesion with the change of pH of submerged environment by appropriately tailoring the surface properties and therefore the prevailing surface forces.

Preparation of polyelectrolyte-modified membranes for heavy metal ions removal.

Polyethersulfone membranes were modified by polyelectrolyte (PE) multilayers, made of poly(allylamine hydrochloride) with poly(styrene sulfonate), to remove Cu2+, Zn2+ and Ni2+ heavy metal cations from aqueous solutions in a wide range of metal concentration (50-1200 ppm). After characterization of the modified membranes, the efficiency of the process was estimated for single heavy metal ions solution leading to high rejection rates (>90% for 50 ppm) and good adsorption capacities (7.0-8.5 mg cm-2) whatever the metal ion tested. The stability in time of the modified membranes was proved by repeating successive filtrations with the same membrane. The filtration process was also used with mixed solutions composed of Cu2+, Zn2+ and Ni2+ ions. The rejection rates obtained for these ternary systems were very similar to the ones obtained for the single metal solutions, showing that the filtration process is still efficient for mixed solutions and can be applied for the decontamination of complex solutions. The long-term stability of the modified membranes was also demonstrated for mixed solutions. The high efficiency of the filtration process and the good adsorption capacities of the modified membranes are due to the ability of the PEs used to complex all the metallic dications tested in this study.

Functionalization of organic membranes by polyelectrolyte multilayer assemblies: application to the removal of copper ions from aqueous solutions.

The functionalization of an organic polyethersulfone membrane (PES) was performed by alternating deposition of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrene sulfonate) (PSS), leading to the formation of a polyelectrolyte multilayer film (PEM). The resulting assembly was characterized by tangential streaming potential measurements to determine the charge of the modified membranes as a function of the polyelectrolyte solution concentration and as a function of the immersion time of the membrane in the polyelectrolyte solutions. Then, the modified membranes were used to perform the ultrafiltration of aqueous solutions containing copper(II) ions. Different operating conditions were tested including: polyelectrolyte concentration, polyelectrolyte nature, thickness of the PEM film or pH of the Cu(2+) solutions. These filtration experiments demonstrated that it was possible to obtain a satisfactory retention of the copper ions (88%), thus proving that this type of assembly can be useful for the removal of copper ions from contaminated aqueous solutions.

Doping properties of PEDOT films electrosynthesized under high frequency ultrasound irradiation.

The present study presents the use of high frequency ultrasound (500 kHz, 25 W) for 3,4-ethylenedioxythiophene (EDOT) electropolymerization in aqueous medium in order to investigate its effects on conducting polymer properties. It was shown that mass transfer increases under ultrasound irradiation which improved electropolymerization and the comparison with experiments carried out at the same mass transfer level (4.6 × 10(-5) ms(-1)) puts in evidence that stirring effect is not the only phenomenon induced by ultrasound during electrodeposition. PEDOT films elaborated under ultrasonication present increased doping levels revealed by X-ray Photoelectron Spectroscopy (XPS) analysis, especially in the case of thick films (measured by mechanical probe), thanks to better incorporation of counter ions within polymer matrix as another consequence of mass transport improvement under ultrasound and probably film heating by wave absorption for the highest thicknesses. A dilation of the film under sonication leading to an increase in film thickness was also highlighted. Finally, a refining of the surface structure was also observed via SEM imaging.

Characterization of charge properties of an ultrafiltration membrane modified by surface grafting of poly(allylamine) hydrochloride.

A polyethersulfone ultrafiltration membrane was functionalized by a cationic polyelectrolyte, the poly(allylamine) hydrochloride (PAH). The influence of the time of adsorption of PAH on the membrane charge properties was studied. Several characterization techniques were used to investigate the membrane modification. Tangential and transmembrane streaming potential measurements were conducted to characterize the outer and inner surfaces of the membrane, respectively. Both techniques indicated that the surface modification of the membrane was efficient. The charge of the outer surface was reversed (from negative values for the unmodified membrane to positive values for the modified membrane) and the charge of the inner surface was neutralized after adsorption of the cationic polyelectrolyte onto the pore walls. The modification of both the outer surface of the membrane and the pore walls was also put in evidence with membrane potential measurements. It was found that the charge of the PAH-modified membrane is affected by the time of immersion in PAH solution. Experimental data seem to show a fast modification of the membrane for the first 15 min; nevertheless, the modification was more pronounced after 24 h of PAH adsorption. Diffusion experiments carried out with unmodified and modified membranes for four salts (KCl, NaCl, MgCl, and CaCl(2)) showed a decrease in the salt permeability after functionalization of the membrane. The permeability decrease was greater for 2:1 salts than for 1:1 salts. This decrease was explained by electrostatic interactions.

Effect of ultrasounds on the electrochemical synthesis of polypyrrole, application to the adhesion and growth of biological cells.

In this study, a new way to synthesize polypyrrole films is presented. This original way consists in the electropolymerization of polypyrrole under high frequency ultrasonic irradiation on conductive fluorine-doped tin oxide surfaces. The polypyrrole films obtained are then compared, in terms of chemical structure and morphology, to polypyrrole films synthesized by standard electrochemical methodology. Next, these polymer films are tested as an alternative to biomaterials that are commonly used as cell culture substrates. Thus, the adhesion and growth of osteoblastics cells and microbial cells on polymer-modified surfaces are investigated by using qualitative observation and quantitative tests. These studies proved the non-toxicity of the polymer films for osteoblastic and microbial cells but also a different behaviour of osteoblastic cells and microbial cells with polypyrrole films.