Towards a new class of stimuli-responsive polymer-based materials – Recent advances and challenges

The rapidly-growing field of polymer stimuli-responsive materials (smart materials) resulted in many advances in designing and developing multi-functional systems, novel architectures, and new synthetic routes for many different applications. The smart polymer materials with a wide range of stimuli, such as pH, light, temperature, enzyme, redox, and electric and magnetic fields play an important role in many applications in many disciplines, including nanotechnology, biochemistry, medicine, materials science, polymer science, engineering, etc. This review aims to provide an introduction to stimuli-responsive polymeric materials, their preparation methods, and to discuss the design of various stimulus-responsive materials that are able to provide smart self-healing surfaces, sensors, actuators, and drug delivery systems in response to particular stimuli

Design of Ultra-Thin PEO/PDMAEMA Polymer Coatings for Tunable Protein Adsorption

Protein adsorption on solid surfaces provides either beneficial or adverse outcomes, depending on the application. Therefore, the desire to predict, control, and regulate protein adsorption on different surfaces is a major concern in the field of biomaterials. The most widely used surface modification approach to prevent or limit protein adsorption is based on the use of poly (ethylene oxide) (PEO). On the other hand, the amount of protein adsorbed on poly(2-(dimethylamine)ethyl methacrylate) (PDMAEMA) coatings can be regulated by the pH and ionic strength of the medium. In this work, ultra-thin PEO/PDMAEMA coatings were designed from solutions with different ratios of PEO to PDMAEMA, and different molar masses of PEO, to reversibly adsorb and desorb human serum albumin (HSA), human fibrinogen (Fb), lysozyme (Lys), and avidine (Av), four very different proteins in terms of size, shape, and isoelectric points. X-ray photoelectron spectroscopy (XPS), quartz crystal microbalance (QCM), and atomic force microscopy (AFM) were used to characterize the mixed polymer coatings, revealing the presence of both polymers in the layers, in variable proportions according to the chosen parameters. Protein adsorption at pH 7.4 and salt concentrations of 10-3 M was monitored by QCM. Lys and Av did not adsorb on the homo-coatings and the mixed coatings. The amount of HSA and Fb adsorbed decreased with increasing the PEO ratio or its molar mass in a grafting solution. It was demonstrated that HSA and Fb, which were adsorbed at pH 7.4 and at an ionic strength of 10-3 M, can be fully desorbed by rinsing with a sodium chloride solution at pH 9.0 and ionic strength 0.15 M from the mixed PEO5/PDMAEMA coatings with PEO/PDMAEMA mass ratios of 70/30, and 50/50, respectively. The results demonstrate that mixed PEO/PDMAEMA coatings allow protein adsorption to be finely tuned on solid surfaces

Nanoparticle and Bioparticle Deposition Kinetics: Quartz Microbalance Measurements

Controlled deposition of nanoparticles and bioparticles is necessary for their separation and purification by chromatography, filtration, food emulsion and foam stabilization, etc. Compared to numerous experimental techniques used to quantify bioparticle deposition kinetics, the quartz crystal microbalance (QCM) method is advantageous because it enables real time measurements under different transport conditions with high precision. Because of its versatility and the deceptive simplicity of measurements, this technique is used in a plethora of investigations involving nanoparticles, macroions, proteins, viruses, bacteria and cells. However, in contrast to the robustness of the measurements, theoretical interpretations of QCM measurements for a particle-like load is complicated because the primary signals (the oscillation frequency and the band width shifts) depend on the force exerted on the sensor rather than on the particle mass. Therefore, it is postulated that a proper interpretation of the QCM data requires a reliable theoretical framework furnishing reference results for well-defined systems. Providing such results is a primary motivation of this work where the kinetics of particle deposition under diffusion and flow conditions is discussed. Expressions for calculating the deposition rates and the maximum coverage are presented. Theoretical results describing the QCM response to a heterogeneous load are discussed, which enables a quantitative interpretation of experimental data obtained for nanoparticles and bioparticles comprising viruses and protein molecules

Human fibrinogen adsorption on positively charged latex particles

Fibrinogen (Fb) adsorption on positively charged latex particles (average diameter of 800 nm) was studied using the microelectrophoretic and the concentration depletion methods based on AFM imaging. Monolayers on latex were adsorbed from diluted bulk solutions at pH 7.4 and an ionic strength in the range of 10^{−3} to 0.15 M where fibrinogen molecules exhibited an average negative charge. The electrophoretic mobility of the latex after controlled fibrinogen adsorption was systematically measured. A monotonic decrease in the electrophoretic mobility of fibrinogen-covered latex was observed for all ionic strengths. The results of these experiments were interpreted according to the three-dimensional electrokinetic model. It was also determined using the concentration depletion method that fibrinogen adsorption was irreversible and the maximum coverage was equal to 0.6 mg m^{−2} for ionic strength 10^{−3} M and 1.3 mg m^{−2} for ionic strength 0.15 M. The increase of the maximum coverage was confirmed by theoretical modeling based on the random sequential adsorption approach. Paradoxically, the maximum coverage of fibrinogen on positively charged latex particles was more than two times lower than the maximum coverage obtained for negative latex particles (3.2 mg m^{−2}) at pH 7.4 and ionic strength of 0.15 M. This was interpreted as a result of the side-on adsorption of fibrinogen molecules with their negatively charged core attached to the positively charged latex surface. The stability and acid base properties of fibrinogen monolayers on latex were also determined in pH cycling experiments where it was observed that there were no irreversible conformational changes in the fibrinogen monolayers. Additionally, the zeta potential of monolayers was more positive than the zeta potential of fibrinogen in the bulk, which proves a heterogeneous charge distribution. These experimental data reveal a new, side-on adsorption mechanism of fibrinogen on positively charged surfaces and confirmed the decisive role of electrostatic interactions in this process

Nanoparticle and Bioparticle Deposition Kinetics: Quartz Microbalance Measurements

Controlled deposition of nanoparticles and bioparticles is necessary for their separation and purification by chromatography, filtration, food emulsion and foam stabilization, etc. Compared to numerous experimental techniques used to quantify bioparticle deposition kinetics, the quartz crystal microbalance (QCM) method is advantageous because it enables real time measurements under different transport conditions with high precision. Because of its versatility and the deceptive simplicity of measurements, this technique is used in a plethora of investigations involving nanoparticles, macroions, proteins, viruses, bacteria and cells. However, in contrast to the robustness of the measurements, theoretical interpretations of QCM measurements for a particle-like load is complicated because the primary signals (the oscillation frequency and the band width shifts) depend on the force exerted on the sensor rather than on the particle mass. Therefore, it is postulated that a proper interpretation of the QCM data requires a reliable theoretical framework furnishing reference results for well-defined systems. Providing such results is a primary motivation of this work where the kinetics of particle deposition under diffusion and flow conditions is discussed. Expressions for calculating the deposition rates and the maximum coverage are presented. Theoretical results describing the QCM response to a heterogeneous load are discussed, which enables a quantitative interpretation of experimental data obtained for nanoparticles and bioparticles comprising viruses and protein molecules

Reversible Protein Adsorption on Mixed PEO/PAA Polymer Brushes: Role of Ionic Strength and PEO Content

Proteins at interfaces are a key for many applications in the biomedical field, in biotechnologies, in biocatalysis, in food industry, etc. The development of surface layers that allow to control and manipulate proteins is thus highly desired. In previous works, we have shown that mixed polymer brushes combining the protein-repellent properties of poly(ethylene oxide) (PEO) and the stimuli-responsive adsorption behavior of poly(acrylic acid) (PAA) could be synthesized and used to achieve switchable protein adsorption. With the present work, we bring more insight into the rational design of such smart thin films by unravelling the role of PEO on the adsorption/desorption of proteins. The PEO content of the mixed PEO/PAA brushes was regulated, on the one hand, by using PEO with different molar masses and, on the other hand, by varying the ratio of PEO and PAA in the solutions used to synthesize the brushes. The influence of ionic strength on the protein adsorption behavior was also further examined. The behavior of three proteins—human serum albumin, lysozyme, and human fibrinogen, which have very different size, shape, and isoelectric point—was investigated. X-ray photoelectron spectroscopy, quartz crystal microbalance, atomic force microscopy, and streaming potential measurements were used to characterize the mixed polymer brushes and, in particular, to estimate the fraction of each polymer within the brushes. Protein adsorption and desorption conditions were selected based on previous studies. While brushes with a lower PEO content allowed the higher protein adsorption to occur, fully reversible adsorption could only be achieved when the PEO surface density was at least 25 PEO units per nm2. Taken together, the results increase the ability to finely tune protein adsorption, especially with temporal control. This opens up possibilities of applications in biosensor design, separation technologies, nanotransport, etc

Reversible Protein Adsorption on Mixed PEO/PAA Polymer Brushes: Role of Ionic Strength and PEO Content

Proteins at interfaces are a key for many applications in the biomedical field, in biotechnologies, in biocatalysis, in food industry, etc. The development of surface layers that allow to control and manipulate proteins is thus highly desired. In previous works, we have shown that mixed polymer brushes combining the protein-repellent properties of poly­(ethylene oxide) (PEO) and the stimuli-responsive adsorption behavior of poly­(acrylic acid) (PAA) could be synthesized and used to achieve switchable protein adsorption. With the present work, we bring more insight into the rational design of such smart thin films by unravelling the role of PEO on the adsorption/desorption of proteins. The PEO content of the mixed PEO/PAA brushes was regulated, on the one hand, by using PEO with different molar masses and, on the other hand, by varying the ratio of PEO and PAA in the solutions used to synthesize the brushes. The influence of ionic strength on the protein adsorption behavior was also further examined. The behavior of three proteinshuman serum albumin, lysozyme, and human fibrinogen, which have very different size, shape, and isoelectric pointwas investigated. X-ray photoelectron spectroscopy, quartz crystal microbalance, atomic force microscopy, and streaming potential measurements were used to characterize the mixed polymer brushes and, in particular, to estimate the fraction of each polymer within the brushes. Protein adsorption and desorption conditions were selected based on previous studies. While brushes with a lower PEO content allowed the higher protein adsorption to occur, fully reversible adsorption could only be achieved when the PEO surface density was at least 25 PEO units per nm². Taken together, the results increase the ability to finely tune protein adsorption, especially with temporal control. This opens up possibilities of applications in biosensor design, separation technologies, nanotransport, etc

Integrating proteins in layer-by-layer assemblies independently of their electrical charge

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