91 research outputs found
Absorption/Expulsion of Oligomers and Linear Macromolecules in a Polymer Brush
The absorption of free linear chains in a polymer brush was studied with
respect to chain size and compatibility with the brush by means of
Monte Carlo (MC) simulations and Density Functional Theory (DFT) /
Self-Consistent Field Theory (SCFT) at both moderate, , and
high, , grafting densities using a bead-spring model.
Different concentrations of the free chains are
examined. Contrary to the case of when all species are almost
completely ejected by the polymer brush irrespective of their length , for
we find that the degree of absorption (absorbed amount)
undergoes a sharp crossover from weak to strong () absorption,
discriminating between oligomers, , and longer chains. For a
moderately dense brush, , the longer species, ,
populate predominantly the deep inner part of the brush whereas in a dense
brush they penetrate into the "fluffy" tail of the dense
brush only. Gyration radius and end-to-end distance of absorbed
chains thereby scale with length as free polymers in the bulk. Using both
MC and DFT/SCFT methods for brushes of different chain length , we demonstrate the existence of unique {\em critical} value of
compatibility . For the energy of free
chains attains the {\em same} value, irrespective of length whereas the
entropy of free chain displays a pronounced minimum. At all density
profiles of absorbing chains with different intersect at the same distance
from the grafting plane. The penetration/expulsion kinetics of free chains into
the polymer brush after an instantaneous change in their compatibility
displays a rather rich behavior. We find three distinct regimes of penetration
kinetics of free chains regarding the length : I (), II (), and III (), in which the time of absorption grows with
at a different rate. During the initial stages of penetration into the
brush one observes a power-law increase of with power
whereby penetration of the free chains into the
brush gets {\em slower} as their concentration rises
Photocatalytic Nanolithography of Self-Assembled Monolayers and Proteins
Self-assembled monolayers of alkylthiolates on gold and alkylsilanes on silicon dioxide have been patterned photocatalytically on sub-100 nm length-scales using both apertured near-field and apertureless methods. Apertured lithography was carried out by means of an argon ion laser (364 nm) coupled to cantilever-type near-field probes with a thin film of titania deposited over the aperture. Apertureless lithography was carried out with a helium–cadmium laser (325 nm) to excite titanium-coated, contact-mode atomic force microscope (AFM) probes. This latter approach is readily implementable on any commercial AFM system. Photodegradation occurred in both cases through the localized photocatalytic degradation of the monolayer. For alkanethiols, degradation of one thiol exposed the bare substrate, enabling refunctionalization of the bare gold by a second, contrasting thiol. For alkylsilanes, degradation of the adsorbate molecule provided a facile means for protein patterning. Lines were written in a protein-resistant film formed by the adsorption of oligo(ethylene glycol)-functionalized trichlorosilanes on glass, leading to the formation of sub-100 nm adhesive, aldehyde-functionalized regions. These were derivatized with aminobutylnitrilotriacetic acid, and complexed with Ni2+, enabling the binding of histidine-labeled green fluorescent protein, which yielded bright fluorescence from 70-nm-wide lines that could be imaged clearly in a confocal microscope
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Effect of crosslinking on the microtribological behavior of model polymer brushes
Polymer brushes in good solvents are known to exhibit excellent tribological properties. We have modeled polymer brushes and their gels using a multibead-spring model and studied their tribological behavior via nonequilibrium molecular-dynamics (MD) simulations. Simulations of brush- against-wall systems were performed using an implicit solvent-based approach. Polymer chains were modeled as linear chains, randomly grafted on a planar surface. Quantities extracted from the simulations are the normal stress, shear stress and concentration profiles. We find that while an increase in the degree of crosslinking leads to an increase in the coefficient of friction, an increase of the length of crosslinker chains does the opposite. Effect of crosslinking can be understood in two ways: (i) there are fewer polymer chains in the outer layer as the degree of crosslinking increases to take part in brush-assisted lubrication, and (ii) crosslinked polymer chains are more resistant to shear than non-crosslinked ones
Surface-Initiated Polymer Brushes in the Biomedical Field: Applications in Membrane Science, Biosensing, Cell Culture, Regenerative Medicine and Antibacterial Coatings
The composition dependence of the electronic properties of CuHf and CuZr amorphous metals
Detailed studies of the density of states of amorphous NBSI obtained by synchrotron radiation photoemission
Partial densities of states in amorphous-Alloys from resonant photoemission and cooper minima
Partial densities of states in amorphous-Alloys from resonant photoemission - CUTI, CUZR, CUHF
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