Compression of polymer brushes: quantitative comparison of self-consistent field theory with experiment

The self-consistent field theory (SCFT) prediction for the compression force between two semi-dilute polymer brushes is compared to the benchmark experiments of Taunton et al. [Nature, 1988, 332, 712]. The comparison is done with previously established parameters, and without any fitting parameters whatsoever. The SCFT provides a significant quantitative improvement over the classical strong-stretching theory (SST), yielding excellent quantitative agreement with the experiment. Contrary to earlier suggestions, chain fluctuations cannot be ignored for normal experimental conditions. Although the analytical expressions of SST provide invaluable aids to understanding the qualitative behavior of polymeric brushes, the numerical SCFT is necessary in order to provide quantitatively accurate predictions.

Unit-cell approximation for diblock−copolymer brushes grafted to spherical particles

This paper examines the equilibrium phase behavior of thin diblock-copolymer films tethered to a spherical core, using numerical self-consistent field theory (SCFT). The computational cost of the calculation is greatly reduced by implementing the unit-cell approximation (UCA) routinely used in the study of bulk systems. This provides a tremendous reduction in computational time, permitting us to map out the phase behavior more extensively and allowing us to consider far larger particles. The main consequence of the UCA is that it omits packing frustration, but evidently the effect is minor for large particles. On the other hand, when the particles are small, the UCA calculation can be readily followed up with the full SCFT, the comparison to which conveniently allows one to quantitatively assess the effect of packing frustration.

Compression of polyelectrolyte brushes in a salt-free theta solvent

This paper examines the normal force between two opposing polyelectrolyte brushes and the interpenetration of their chains that is responsible for sliding friction. It focuses on the special case of semi-dilute brushes in a salt-free theta solvent, for which Zhulina and Borisov [J. Chem. Phys., {\bf 107}, 5952, (1997)] have derived analytical predictions using the classical strong-stretching theory (SST) introduced by Semenov and developed by Milner, Witten and Cates. Interestingly, the SST predicts that the brushes contract maintaining a polymer-free gap as they are compressed together, which provides an explanation for the ultra-low frictional forces observed in experiment. We examine the degree to which the SST predictions are affected by chain fluctuations by employing self-consistent field theory (SCFT). While the normal force is relatively unaffected, fluctuations are found to have a strong impact on brush interpenetration. Even still, the contraction of the brushes does significantly prolong the onset of interpenetration, implying that a sizeable normal force can be achieved before the sliding friction becomes significant.

Effect of salt on the compression of polyelectrolyte brushes in a theta solvent

Classical strong-stretching theory (SST) predicts that, as opposing polyelectrolyte brushes are compressed together in a salt-free theta solvent, they contract so as to maintain a finite polymer-free gap, which offers a potential explanation for the ultra-low frictional forces observed in experiments even with the application of large normal forces. However, the SST ignores chain fluctuations, which would tend to close the gap resulting in physical contact and in turn significant friction. In a preceding study, we examined the effect of fluctuations using self-consistent field theory (SCFT) and illustrated that high normal forces can still be applied before the gap is destroyed. We now look at the effect of adding salt. It is found to reduce the long-range interaction between the brushes but has little effect on the short-range part, provided the concentration does not enter the salted-brush regime. Consequently, the maximum normal force between two planar brushes at the point of contact is remarkably unaffected by salt. For the crossed-cylinder geometry commonly used in experiments, however, there is a gradual reduction because in this case the long-range part of the interaction contributes to the maximum normal force.

Polymer brushes under shear: molecular dynamics simulations compared to experiments

Surfaces coated with polymer brushes in a good solvent are known to exhibit excellent tribological properties. We have performed coarse-grained equilibrium and nonequilibrium molecular dynamics (MD) simulations to investigate dextran polymer brushes in an aqueous environment in molecular detail. In a first step, we determined simulation parameters and units by matching experimental results for a single dextran chain. Analyzing this model when applied to a multichain system, density profiles of end-tethered polymer brushes obtained from equilibrium MD simulations compare very well with expectations based on self-consistent field theory. Simulation results were further validated against and correlated with available experimental results. The simulated compression curves (normal force as a function of surface separation) compare successfully with results obtained with a surface forces apparatus. Shear stress (friction) obtained via nonequilibrium MD is contrasted with nanoscale friction studies employing colloidal-probe lateral force microscopy. We find good agreement in the hydrodynamic regime and explain the observed leveling-off of the friction forces in the boundary regime by means of an effective polymer–wall attraction.

Effects of ultrasonic, electric, and manual toothbrushes on subgingival plaque composition in orthodontically banded molars

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Efficacy of ultrasonic, electric and manual toothbrushes in patients with fixed orthodontic appliances

Objective: This crossover study compared the efficacy of an ultrasonic toothbrush for the reduction of plaque, gingival inflammation, and levels of Streptococcus mutans, in relation to an electric and a manual toothbrush. Materials and Methods: Twenty-one patients with orthodontic appliances were divided into three groups. All patients were evaluated by a periodontist and samples of saliva were collected for quantification of S mutans. The patients received their first brushes with appropriate instructions. For each crossover leg, patients used each toothbrush for a period of 30 days. At the end of each washout period, participants received a periodontal evaluation and new samples of saliva were collected. After 15 days of using their own toothbrushes, patients received the next toothbrushes in the experimental sequence. Results: The ultrasonic brush group presented significant improvement in the reduction of visible plaque on the buccal surfaces (-6.36%, P = .007). The counts of S mutans decreased in the electric (2.04 × 105 to 1.36 × 105 colony-forming units [CFU]/mL) and ultrasonic (2.98 × 105 to 1.84 × 105 CFU/mL) groups. There were no statistical differences among the three brushes for the clinical and microbiological parameters evaluated. Conclusions: This study did not demonstrate that the ultrasonic toothbrush was better in reducing gingival inflammation in adolescent orthodontic patients, but plaque scores were lowered on buccal surfaces of teeth with orthodontic brackets. In addition, S mutans counts were markedly decreased in the electric and ultrasonic groups, which should be related to a reduced risk of oral disease. © 2006 by The EH Angle Education and Research Foundation, Inc.

Comparison of manual versus sonic and ultrasonic toothbrushes: a review.

PURPOSE: This review of the literature intends to evaluate the effect of brushes with high frequency motion when compared with manual toothbrushes regarding the indices of plaque and gingival bleeding. METHODS: Patients presenting gingivitis and/or chronic periodontitis were evaluated in addition to patients having osseointegrated implants and fixed orthodontic appliances. Pertinent literature was reviewed to select articles according to previously defined inclusion criteria. RESULTS: In the assessed studies results showed significant decreases in plaque and gingival indices by utilization of both types of brushes. However, in the selected studies where sonic brushes were tested in orthodontic and dental implant patients there was a more significant decrease in the indices. Furthermore, there was no indication of gingival recession attributed to product use. CONCLUSION: Future studies with a more homogeneous methodology and better experiment designs will be needed.

Edentulous patients' knowledge of dental hygiene and care of prostheses

Objective: The aim of this study was to analyse denture users' oral care habits with regard to the use of their prostheses. Background: Rehabilitative treatment is only successful when patients are motivated and aware of correct prosthesis use and hygiene. Materials and methods: Questionnaires were distributed to 150 complete denture users at the Federal University of Bahia School of Dentistry, the Esmeralda Natividade Health Center, the Bahian Science Development Foundation and a Salvador nursing home. The questionnaire included information on gender, age, length of prosthesis use, cleaning methods and materials, etc. The data were analysed using EpiInfo version 6 software. The chi-squared test was used for statistical analysis, with a significance level of 5%. Results: Questionnaire results showed that 78% of the subjects, with an average age of 67.3 years, had used the same complete denture for over 5 years. 64% slept with their prostheses and 44% removed them from the mouth only for cleaning. None of the patients interviewed knew anything about brushes designed specifically for complete dentures. 37.3% had a restricted diet and 44% believed that a complete denture would last for more than 10 years. Conclusion: Within the limitations of this study, it was concluded that the edentulous patients surveyed had limited awareness of prosthetic hygiene and long-term oral care despite extended periods of denture use. © 2008 The Authors.

Electrochemical studies based on local interfacial ph changes of gold nanoparticles immobilized on polystyrene brushes

The electrochemical behavior of polystyrene modified with gold nanoparticle (Au NPs) was investigated in terms of pH-responsive polymer brush. A pH-responsive of modified polymer brush from tethered polystyrene was prepared and used for selective gating transport of anions andcations across the thin-film. An ITO-coated glass electrode was used as substrate and applied to study the switchable permeability of the polymer brush triggered by changes in pH of the aqueous environment. The pH-sensitive behavior of the polymer brush interface has been demonstrated by means of cyclic voltammetry (CV) and Localized Surface Plasmon Resonance (LSPR). CV experiments showed at ph values of 4 and 8 induces swelling and shrinking of the grafted polymer brushes, respectively, and this behavior is fast and reversible. LSPR measurements showed a blue shift of 33 nm in the surface resonance band changes by local pH. The paper brings an easy methodology to fabrication a variety of nanosensors based on the polymer brushes-nanoparticle assemblies. © 2013 by ESG.

Toward pH-controllable bioelectrocatalysis for hydrogen peroxide based on polymer brushes

In the present work, a biosensor was built with smart material based on polymer brushes. The biosensor demonstrated a pH-sensitive on-off property, and it was further used to control or modulate the electrochemical responses of the biosensor. This property could be used to realize pH-controlled electrochemical reaction of hydrogen peroxide and HRP immobilized on polymer brushes. The composite film also showed excellent amperometric i-t response toward hydrogen peroxide in the concentration range of 0-13 μM. In future, this platform might be used for self-regulating targeted diagnostic, drug delivery and biofuel cell based on controllable bioelectrocatalysis. © 2013 Elsevier B.V.

Electrochemical studies based on local interfacial ph changes of gold nanoparticles immobilized on polystyrene brushes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Stimuli-Responsive Biointerface Based on Polymer Brushes for Glucose Detection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Role of Branching on the Structure of Polymer Brushes Formed from Comb Copolymers

The distinguishing feature of a polymer brush at equilibrium is the stretched configuration of the chains that results from tethering the polymer chains by one end at the solid-fluid interface. The stretched configuration of the chains and the crowded nature of the interfacial layer is the origin of many of the useful properties of polymer brushes: these layers resist compression and aggregation, effectively dissipate shear stresses, and respond reversibly to changes in their solution environment.

Impact of Solvent Quality on the Density Profiles of Looped Triblock Copolymer Brushes by Neutron Reflectivity Measurements

Preferential adsorption of poly(2-vinylpyridine)-deuterated polystyrene-poly(2-vinylpyridine) (PVP-dPS-PVP) triblock copolymers from toluene onto silicon leads to the formation of dPS loops tethered by the PVP end blocks. Using neutron reflectometry, we have determined the segment density profiles of these looped polymer brushes in toluene, a good solvent for the dPS block, and in cyclohexane at 20 °C (poor solvent), 32 °C, (near-Θ solvent), and 50 °C (marginal solvent). While the swelling behavior qualitatively agrees with that observed for singly grafted brushes, there are interesting differences in the local structural details: In a good solvent, the segment density profiles are composed of an inner parabolic region and a long, extended tail. In cyclohexane, the profiles are described by exponential decays. We ascribe these features to a novel polydispersity effect that arises due to tethering the PS loops by both ends. The results also show that the less dense layers undergo more significant changes in swollen height as solvent quality is changed and that the looped brushes of different molecular weight, asymmetry, and tethering density adhere to scaling relationships derived for lightly cross-linked polymer gels.