Rapid Desorption of Polyelectrolytes from Solid Surfaces Induced by Changes of Aqueous Chemistry

The short-term desorption induced by changes of aqueous chemistry of predeposited polyelectrolyte layers on solid surfaces was studied with reflectometry. The behavior of a strong polycation, polydiallydimethylammonium chloride (PDADMAC), interacting with flat silica was investigated in detail. Results showed that partial desorption of preadsorbed polymer chains can be quickly triggered by changes in ionic strength and pH. When lowering these parameters in the PDADMAC–silica system, the increased lateral repulsive potential of neighboring chains drove the desorption of some of the polymer. Furthermore, layer desorption was favored when electrostatic interactions between a polyelectrolyte and the underlying surface became less attractive or switched to being repulsive. At the investigated timescales (<1 h), adlayer desorption was always partial and often incomplete. When initiating desorption from a condition of large adsorbed mass, desorption effects did not result in the plateau mass obtained by adsorption on a clean surface: an excess mass remained deposited. The results thus suggest that a relatively large energy barrier needs to be overcome to induce redissolution of predeposited chains and that this barrier may be a function of the number of polymer–surface interactions, which are in turn correlated with polymer molecular mass. These mechanisms have important implications for environmental processes and colloidal systems because they imply that, once adsorbed, polymeric chains may be redissolved but only to a limited degree at typical engineering timescales

Bond- and mode-specific reactivity of methane on Ni(100)

In this work, the state-resolved reactivity of methane excited to different C-H stretch vibrations have been measured on a Ni(100) surface. Two kinds of experiments have been performed. In the first series of experiments, we have measured the reactivity of dideutero methane (CD2H2) excited in two different C-H stretch vibrational states which are nearly iso-energetic, but have different vibrational amplitudes. We observed that CD2H2 excited with two quanta of vibrational energy in one C-H bond were more reactive (by as much as a factor 5) than molecules excited with one quantum in each of two C-H bonds. This was the first time that state specificity has been observed in a gas-surface reaction. Our results clearly exclude the possibility of statistical models correctly describing the mechanisms of the methane chemisorption and highlight the importance of the dynamical calculations. We rationalize our results in terms of a spectator model and bond-specific reactivity, where the laser excited bond is broken in the reaction with the surface and the difference in reactivity of the two vibrational states is explained in terms of vibrational energy localized in a single C-H bond. Additionally, we have measured the state-resolved reactivity of CH4 in its totally symmetric C-H stretch vibration (ν1) on Ni(100). The methane molecules were excited to ν1 by stimulated Raman pumping prior the collision with the surface. We observed that the reactivity of the ν1 excited CH4 is about an order of magnitude higher than that of methane excited to the isoenergetic antisymmetric stretch (ν3) reported by Juurlink et al. [Phys. Rev. Lett. 83, 868 (1999)] and is similar to that we have previously observed for the excitation of the first overtone (2ν3). Since all four bonds initially carry vibrational amplitude for both ν1 and ν3, the difference in reactivity between the symmetric and antisymmetric vibrations cannot simply be explained in terms of bond-specific laser excitation. We refer to this reactivity difference as mode-specific. In this case, the relative reactivity between two different vibrational states does not only depend on the quantity of vibrational energy contained in each bond, but it is also influenced by the symmetry of the vibrational state excited. Our results are consistent with predictions of a vibrationally adiabatic model of the methane reaction dynamics [Halonen et al., J. Chem. Phys. 115, 5611 (2001)]

Size-dependent aggregation of graphene oxide

Graphene oxides (GO) of highly polydisperse size distribution were prepared by the Brodie method and their dispersion stability was characterized. Exfoliation and fractionation led to well-defined particle populations in the Nano, classical Colloidal (submicron) and Micrometer size ranges, as revealed by atomic force microscopy and light scattering measurements. Time-resolved dynamic light scattering experiments revealed that aggregation processes are fully impeded in the intermediate pH regime of 3–13 in the absence of electrolytes. While the resistance against salt-induced aggregation increases with the pH due to the progressive ionization of the surface functional groups of GO sheets, their dispersions are inherently unstable at supramillimolar concentrations of strong acids and submolar concentrations of bases, in line with the DLVO theory. However, the aggregation behavior quantified by the critical coagulation concentrations (CCCs) shows surprisingly substantial platelet size dependence. The CCC of Nano Brodie-GO reaches 360 mm at pH = 12, which is one of the highest values ever reported for GO aqueous dispersions. These results provide useful quantitative information to design processable GO dispersions of pH- and size-tunable stability for future applications

Formation of poly-L-lysine monolayers on silica : modeling and experimental studies

Modification of solid substrates by poly-l-lysine (PLL) layers has been widely employed in order to improve their biocompatibility, for promoting protein and cell immobilization for fabrication of biosensor arrays and antibacterial coatings. However, despite many studies conducted in the literature, there is a deficiency in a quantitative description of PLL adsorption processes. It is postulated that this becomes feasible by applying direct experimental techniques combined with thorough theoretical modeling. In this work, the kinetics of PLL adsorption on silica for various ionic strengths was determined in situ under controlled flow conditions using the optical reflectometry and the streaming potential methods. Both the initial adsorption rates and longer time kinetic runs were acquired and quantitatively interpreted in terms of the convective diffusion and the random sequential adsorption theoretical modeling based on the coarse-grained Monte Carlo approach. This unique combination of experimental and theoretical approaches enabled us to gain new insight into the mechanism of macroion adsorption controlled by the electrostatic interactions, which affect both the molecule conformations and the blocking effects. Besides significance for basic science, the results obtained in this work can be exploited for developing reliable procedures for preparing stable PLL monolayers of well-controlled coverage and electrokinetic properties

Mechanically induced cis-to-trans isomerization of carbon–carbon double bonds using atomic force microscopy

Cis-to-trans isomerization of carbon–carbon double bonds can be induced by the application of mechanical force. Using single molecule force spectroscopy by means of atomic force microscopy (AFM) we pulled polymer molecules which contained cis double bonds in the backbone. In the force versus extension profiles of these polymers, a sudden extension increase is observed which is due to the conversion of shorter cis isomers into longer trans isomers. The added length to the polymer results in relaxation in probed force. We find that the isomerization occurs at forces of 800 ± 60 pN, independent of AFM tip and solid substrate chemistries. Investigation of similar polymers which exclusively contained single bonds in the backbone showed no evidence of a similar transition

Exploring Forces between Individual Colloidal Particles with the Atomic Force Microscope

Forces between individual colloidal particles can be measured with the atomic force microscope (AFM), and this technique permits the study of interactions between surfaces across aqueous solutions in great detail. The most relevant forces are described by the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, and they include electrostatic double-layer and van der Waals forces. In symmetric systems, the electrostatic forces are repulsive and depend strongly on the type and concentration of the salts present, while van der Waals forces are always attractive. In asymmetric systems, the electrostatic force can become attractive as well, even when involving neutral surfaces, while in rare situations van der Waals forces can become repulsive too. The enormous sensitivity of the double layer forces on additives present is illustrated with oppositely charged polyelectrolytes, which may induce attractions or repulsions depending on their concentrations

Quantitative Nano-characterization of Polymers Using Atomic Force Microscopy

The present article offers an overview on the use of atomic force microscopy (AFM) to characterize the nanomechanical properties of polymers. AFM imaging reveals the conformations of polymer molecules at solid– liquid interfaces. In particular, for polyelectrolytes, the effect of ionic strength on the conformations of molecules can be studied. Examination of force versus extension profiles obtained using AFM-based single molecule force spectroscopy gives information on the entropic and enthalpic elasticities in pN to nN force range. In addition, single molecule force spectroscopy can be used to trigger chemical reactions and transitions at the molecular level when force-sensitive chemical units are embedded in a polymer backbone

Ordered and Oriented Supramolecular n/p-Heterojunction Surface Architectures: Completion of the Primary Color Collection

In this study, we describe synthesis, characterization, and zipper assembly of yellow p-oligophenyl naphthalenediimide (POP-NDI) donor−acceptor hybrids. Moreover, we disclose, for the first time, results from the functional comparison of zipper and layer-by-layer (LBL) assembly as well as quartz crystal microbalance (QCM), atomic force microscopy (AFM), and molecular modeling data on zipper assembly. Compared to the previously reported blue and red NDIs, yellow NDIs are more π-acidic, easier to reduce, and harder to oxidize. The optoelectronic matching achieved in yellow POP-NDIs is reflected in quantitative and long-lived photoinduced charge separation, comparable to their red and much better than their blue counterparts. The direct comparison of zipper and LBL assemblies reveals that yellow zippers generate more photocurrent than blue zippers as well as LBL photosystems. Continuing linear growth found in QCM measurements demonstrates that photocurrent saturation at the critical assembly thickness occurs because more charges start to recombine before reaching the electrodes and not because of discontinued assembly. The found characteristics, such as significant critical thickness, strong photocurrents, large fill factors, and, according to AFM images, smooth surfaces, are important for optoelectronic performance and support the existence of highly ordered architectures