Cationic Polymer Brushes Research Articles

Phytic Acid-Promoted Deposition of Gold Nanoparticles with Grafted Cationic Polymer Brushes for the Construction of Synergistic Contact-Killing and Photothermal Bactericidal Coatings.

Medical implants are constantly facing the risk of bacterial infections, especially infections caused by multidrug resistant bacteria. To mitigate this problem, gold nanoparticles with alkyl bromide moieties (Au NPs-Br) on the surfaces were prepared. Xenon light irradiation triggered the plasmon effect of Au NPs-Br to induce free radical graft polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA), leading to the formation of poly(DMAEMA) brush-grafted Au NPs (Au NPs-g-PDM). The Au NPs-g-PDM nanocomposites were conjugated with phytic acid (PA) via electrostatic interaction and van der Waals interaction. The as-formed aggregates were deposited on the titanium (Ti) substrates to form the PA/Au NPs-g-PDM (PAP) hybrid coatings through surface adherence of PA and the gravitational effect. Synergistic bactericidal effects of contact-killing caused by the cationic PDM brushes, and local heating generated by the Au NPs under near-infrared irradiation, conferred strong antibacterial effects on the PAP-deposited Ti (Ti-PAP) substrates. The synergistic bactericidal effects reduced the threshold temperature required for the photothermal sterilization, which in turn minimized the secondary damage to the implant site. The Ti-PAP substrates exhibited 97.34% and 99.97% antibacterial and antiadhesive efficacy, respectively, against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), compared to the control under in vitro antimicrobial assays. Furthermore, the as-constructed Ti-PAP surface exhibited a 99.42% reduction in the inoculated S. aureus under in vivo assays. In addition, the PAP coatings exhibited good biocompatibility in the hemolysis and cytotoxicity assays as well as in the subcutaneous implantation of rats.

Bactericidal Ability of Well-Controlled Cationic Polymer Brush Surfaces and the Interaction Analysis by Quartz Crystal Microbalance with Dissipation.

In this study, cationic poly(2-(methacryloyloxy)ethyl) trimethylammonium chloride) (PMTAC) brush surfaces were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP), and their properties were systematically investigated to discuss the factors affecting their bactericidal properties and interactions with proteins. Model equations for the analysis of electrophoretic behaviors were considered for accurate parameter estimation to indicate the charge density at the interface. The zeta potential dependency of the PMTAC brushes was successfully analyzed using Smolchowski's equation and the Gouy-Chapman model, which describes the diffusive electric double layer. The analysis of the quartz crystal microbalance with dissipation (QCM-D) indicated that the electrostatic interaction promoted protein adsorption, with a large quantity of a negatively charged protein, bovine serum albumin (BSA), being adsorbed. The bactericidal efficiency of the high-graft-density polymer brush (0.45 chains nm-2) was higher than that of the low-graft-density polymer brush (0.06 chains nm-2). To investigate the mechanism of this phenomenon, we applied the dissipation change (ΔD) of QCM-D analysis. The BSA was likewise adsorbed when the brush structure was changed; however, the negative ΔD indicated that the BSA-adsorbed, high-graft-density PMTAC brush became a rigid state. In the bacteria culture media, the behaviors were the same as BSA adsorption, and the high-graft-density polymer brush was also estimated to be more rigid than the low-graft-density polymer brush. Moreover, for S. aureus adhesion after incubating in TSB, a small slope of ΔD/ΔF plots considered initial adsorption of bacteria on the high-graft-density polymer brush strongly interacted compared to that of the low-graft-density polymer brush. The scattered value of the slope of ΔD/ΔF on the high-graft-density polymer brush was considered to be due to the dead bacteria between the bacteria and the polymer brush interface. These investigations for a well-defined cationic polymer brush will contribute to the design of antibacterial surfaces.

High-Efficient Anionic Dyes Removal from Water by Cationic Polymer Brush Functionalized Magnetic Mesoporous Silica Nanoparticles

High efficiency removal of methyl orange (MO) and bromothymol blue (BT) dyes from contaminated water has been reported using magnetic mesoporous nanoparticles modified with cationic polymer brush (poly(2-methacryloyloxy)ethyl] trimethylammonium chloride solution) (Fe3O4-MSNs-PMETAC). Atom transfer radical polymerization (ATRP) was utilized to grow the polymer chains on the magnetic mesoporous silica nanoparticles. The chemical surface modifications were confirmed using IR, TGA, SEM and TEM. The results show that the obtained Fe3O4-MSNs-PMETAC materials were nearly spherical in shape with approximately 30 nm magnetic core, and silica shell thicknesses ranged from 135 to 250 nm. The adsorption performance of the material was found to be unaffected by the pH (3-9) of the media, with a removal efficiency of 100% for both dyes. The adsorption of BT and MO on the surface of Fe3O4-MSNs-PMETAC was found to follow Freundlich and Langmuir models, respectively. Since the synthesized nanocomposite materials exhibit an enhanced properties such as large maximum adsorption capacity, rapid synthesis process, and easy separation from solution, it could be an effective sorbent for the removal of other pollutants such as potentially toxic anionic elements (e.g., arsenate and chromate ions) from water and wastewater.

Caging Cationic Polymer Brush-Coated Plasmonic Nanostructures for Traceable Selective Antimicrobial Activities.

Cationic polymers are under intense research to achieve prominent antimicrobial activity. However, the cellular and in vivo toxicity caused by nonspecific electrostatic interaction has become a major challenge for their practical applications. Here, the development of a "caging" strategy based on the use of a block copolymer consisting of a stealth block and an anionic block that undergoes degradation in presence of enzymes secreted by selective bacterial pathogens of interest is reported. The results have shown that antimicrobial cationic polymer brushes-coated gold nanorods (AuNRs) can be caged by the block polymer of poly(ethylene glycol) and anionic, lipase-degradable block of ε-caprolactone and methacrylic acid copolymer to afford neutrally charged surfaces. The caged AuNRs are activated by lipase released by bacteria of interest to endow an excellent bactericidal effect but show minimal binding and toxicity against mammalian cells and nonspecific bacteria that do not produce lipase. In this design, AuNRs play multifunctional roles as the scaffolds for polymer brushes, photothermal transducers, and imaging probes for traceable delivery of the activation and delivery of bactericidal cationic polymer brushes. The caging strategy opens new opportunities for the safe delivery of antimicrobial materials for the treatment of bacterial infections.

Critical In-Plane Density of Polyelectrolyte Brush for the Ordered Hydrogen-Bonded Structure of Incorporated Water.

A polymer electrolyte brush is a reasonable platform to confine water molecules within a nanoscopic area to study their role in the function of interacting media because of their adjustable nanospace and charge by changing the in-plane density and side chains of the brush. Here, we demonstrate how the in-plane spacing of cationic polymer brush chains, poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMTAC), affects the hydrogen bond configuration of incorporated water using soft X-ray emission spectroscopy. At the critical in-plane density σ = 0.30 chains/nm2 of PMTAC, tetrahedrally coordinated water molecules started to melt into distorted or broken hydrogen-bonded configurations. Considering the charge on the quaternary ammonium cations, the electric field required to form a tetrahedrally coordinated hydrogen-bonded configuration was estimated as ∼500 kV cm-1 and is effective up to ∼1 nm from the surface of the polymer chain. These findings are useful for designing specific interface properties and the resultant surface function of polyelectrolyte-based materials.

Cationic Polymer Brush-Modified Carbon Nanotube-Meditated eRNA LINC02569 Silencing Attenuates Nucleus Pulposus Degeneration by Blocking NF-κB Signaling Pathway and Alleviate Cell Senescence.

Enhancer RNAs (eRNAs) are noncoding RNAs that synthesized at active enhancers. eRNAs have important regulatory characteristics and appear to be significant for maintenance of cell identity and information processing. Series of functional eRNAs have been identified as potential therapeutic targets for multiple diseases. Nevertheless, the role of eRNAs on intervertebral disc degeneration (IDD) is still unknown yet. Herein, we utilized the nucleus pulposus samples of patients and identified a key eRNA (LINC02569) with the Arraystar eRNA Microarray. LINC02569 mostly locates in nucleus and plays an important role in the progress of IDD by activating nuclear factor kappa-B (NF-κB) signaling pathway. We used a cationic polymer brush coated carbon nanotube (oCNT-pb)-based siRNA delivery platform that we previously designed, to transport LINC02569 siRNA (si-02569) to nucleus pulposus cells. The siRNA loaded oCNT-pb accumulated in nucleus pulposus cells with lower toxicity and higher transfection efficiency, compared with the traditional siRNA delivery system. Moreover, the results showed that the delivery of si-02569 significantly alleviated the inflammatory response in the nucleus pulposus cells via inhibiting P65 phosphorylation and preventing its transfer into the nucleus, and meanwhile alleviated cell senescence by decreasing the expression of P21. Altogether, our results highlight that eRNA (LINC02569) plays important role in the progression of IDD and could be a potential therapeutic target for alleviation of IDD.

Cationic polymer brush-coated bioglass nanoparticles for the design of bioresorbable RNA delivery vectors

Cationic polymer brushes are attractive coatings for the development of gene delivery vectors, owing to the simplicity via which they enable the control of a broad range of design parameters independently of each other. Indeed, brush chemistry, grafting density, thickness and nanoparticle cores (chemistry, size and shape) can be designed and controlled separately. Although some of these parameters have been investigated in the case of poly(dimethylaminoethyl methacrylate) (PDMAEMA) brushes, including grafting density and thickness, the main core studied to date with such systems has remained silica nanoparticles that display low resorption potential. In this work, we propose to make use of bioresorbable mesoporous silica nanoparticles (MSN) for the design of brush-based gene delivery systems. We synthesise a range of MSNs with varying calcium doping levels, enabling to regulate resorption. We demonstrate the growth of PDMAEMA brushes from these bioglass nanoparticles and study some of their physico-chemical properties. We demonstrate the control of brush release from these nanomaterials, through their calcium content and surface erosion. Finally, we quantify their efficacy in a siRNA knock down model. Therefore, these systems demonstrate the feasibility of designing bioresorbable brush-based gene delivery vectors.

Ultrathin Polydopamine-Graphene Oxide Hybrid Coatings on Polymer Filters with Improved Filtration Performance and Functionalities.

Thin polymer fiber mats, in particular those made of nonwoven polypropylene (PP) fibers, are extensively used for medical and industrial filtration. The recent pandemic has increased the demand for the fabrication of protective masks. The nonwoven PP filter has limitations in filtration efficiency and lacks advanced functionalities. Here, we propose a simple, effective, and low-cost method to functionalize PP filters and endow antimicrobial and photothermal properties. Our approach is based on the deposition of an ultrathin hybrid coating composed of graphene oxide (GO) and polydopamine on the surface of PP filters by spray-coating. The complementary properties and synergic effects of GO and polydopamine in the ultrathin coating improved the filtration efficiency of the PP filter by 20% with little change in pressure drop. Single component coatings did not result in similar improvements in performance. The ultrathin coating also makes the surface of the filter more hydrophilic with negative charges. The photothermal property of GO enables a rapid temperature increase of the surface-coated filter upon light irradiation for easy sterilization. Furthermore, cationic polymer brushes can be grafted to the ultrathin hybrid coating, which adds the highly desired antimicrobial property to the PP filters for their more effective protection against microorganisms.

Infection resistant polymer brush coating on the surface of biodegradable polyester.

Biomaterials with anti-infective coatings are usually found to suffer from low cyto-compatibility and therefore, development of a stable, effective polymeric anti-bacterial substrate without compromising the biocompatibility is still an unmet challenge. Addressing this, a simple strategy for developing non-leaching antibacterial coating on a biodegradable substrate is reported here. The strategy can be utilized for mitigating serious biomedical implant related complications arising from generation of biocide resistant bacterial strains, losing antibacterial activity over time etc. without significantly compromising the cytocompatibility of the biomaterials. To develop the infection resistant yet cytocompatible biomaterials comprised of tartaric acid based biodegradable aliphatic polyester, we have primarily focussed on attaching anti-infective polymer brushes such as poly (2-hydroxyethyl methacrylate) (PHEMA), poly (poly (ethylene glycol) methacrylate) (PPEGMA) and poly[(2-methacryloyloxyethyl] trimethyl ammonium chloride) (PMETA) on hydroxyl functionalized polyester substrate via surface initiated atom transfer radical polymerization (SIATRP). The brushes were thoroughly characterized for reaction kinetics, grafting yield, surface density, topography and hydrophilicity. Among the various brushes, cationic polymer brush (PMETA) was found to exhibit highest antibacterial activity, with only ~3% and ~4% adherence of E. coli (Escherichia coli) and S. aureus (Staphylococcus aureus), respectively. In order to show its widespread use and also to vary initiator density, polylactic acid (PLA) was blended with this tartaric acid based aliphatic polyester and a 3D (three-dimensional) scaffold was fabricated by 3D printing using the blend. Finally, PMETA brush was grown onto the scaffold surface for various time periods and the evaluation of antibacterial activity (using gram positive and gram-negative bacteria) and cytocompatibility (using mammalian osteoblast cells) were carried out on the brush modified scaffold. A balance between antibacterial activity and cytocompatibility was found at optimum brush length achieved after 18h of SIATRP suggesting that this composition offers a stable, non-leaching, anti-infective, but cytocompatible coating on biodegradable polymeric implant surface for addressing several biomaterials associated infections.

Poly(2-aminoethyl methacrylate)-based polyampholyte brush surface with carboxylic groups to improve blood compatibility

Zwitterionic material-based polymer brush significantly prevents protein adsorption and cell adhesion, which leads to the blood compatibility. However, zwitterionic polymer itself is difficult to be modified further, for the blood compatibility since the charged balance is impaired after the modification. In this research, chemically modifiable mixed charge polymer brush is designed, without impairing its characteristics. Condensed mixed charge polymer brush will work like zwitterionic material because neighbouring opposite charge is reported to be important in the zwitterionic material. Cationic polymer brush with primary amine group, which is based on 2-aminoethyl methacrylate (AEMA), was prepared and modified by succinic anhydride to obtain carboxylic group induced poly(AEMA). The ratio of primary amine group and carboxylic group was optimized to obtain the polyampholyte brush. The blood compatibility was evaluated by measuring coagulation/complement activation, protein adsorption and cell adhesion induced by the polymer. Our designed cationic-based polyampholyte brush prevented coagulation/complement activation comparable to poly(2-methacryloyloxyethyl phosphorylcholine) brush, based on intra-monomer interaction, because condensed mix charge works like zwitterion.

Accessible and sustainable Cu(0)-mediated radical polymerisation for the functionalisation of surfaces

Towards use of environmentally benign solvents and ambient conditions for surface functionalisation by controlled growth of thick cationic polymer brushes.

Single-Step Metal-Free Grafting of Cationic Polymer Brushes on Fluorescent Nanodiamonds.

Cationic polymers are often employed in conjugation with nanomaterials, and the resultant hybrids are useful for various bioapplications. Here, a single-step metal-free method for the synthesis of fluorescent nanodiamonds (FNDs) conjugated with cationic polymer brushes is reported. Distinct from the common methods such as atom transfer radical polymerization and reversible addition fragmentation chain transfer, our ring-opening-polymerization-based method is simple and less time consuming and hazardous. Infrared spectroscopy, thermogravimetric analysis, zeta potential, and dynamic light scattering confirmed the synthesis. The produced FND-polymer brushes showed markedly higher cell labeling and internalization efficiency without noticeable cytotoxicity. Our method is general and applicable to other nanoparticles as well for uses in diverse research areas.

Highly Stable RNA Capture by Dense Cationic Polymer Brushes for the Design of Cytocompatible, Serum-Stable SiRNA Delivery Vectors.

The high density of polymer brushes confers to these coatings unique physicochemical properties, in particular for the regulation of biomolecular interaction and the design of highly selective coatings for biosensors and protein patterning. Here, we show that high density poly(dimethylaminoethyl methacrylate) cationic polymer brushes enable the stable uptake of high levels of oligonucleotides. This is proposed to result from the high degree of crowding and associated increase in entropic driving force for the binding of polyelectrolytes such as nucleic acid molecules. We further demonstrate the ease with which such coatings allow the design of highly structured nanomaterials for siRNA delivery using block copolymer-brush-based nanoparticles that allow the protection of oligonucleotides by a protein-resistant outer block. In particular, these nanomaterials display a high serum stability and low cytotoxicity while retaining excellent knock down efficiencies. Polymer brush-based nanomaterials therefore appear particularly attractive for the rational design of a new generation of high performance theranostics and RNA delivery probes.

Surface modification of electrospun cellulose acetate nanofibers via RAFT polymerization for DNA adsorption

We report on a facile and robust method by which surface of electrospun cellulose acetate (CA) nanofibers can be chemically modified with cationic polymer brushes for DNA adsorption. The surface of CA nanofibers was functionalized by growing poly[(ar-vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes through a multi-step chemical sequence that ensures retention of mechanically robust nanofibers. Initially, the surface of the CA nanofibers was modified with RAFT chain transfer agent. Poly(VBTAC) brushes were then prepared via RAFT-mediated polymerization from the nanofiber surface. DNA adsorption capacity of CA nanofibrous web surface functionalized with cationic poly(VBTAC) brushes was demonstrated. The reusability of these webs was investigated by measuring the adsorption capacity for target DNA in a cyclic manner. In brief, CA nanofibers surface-modified with cationic polymer brushes can be suitable as membrane materials for filtration, purification, and/or separation processes for DNA.

Stimuli response of cationic polymer brush prepared by ATRP: Application in peptide fractionation

Random cationic copolymer brushes composed of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and N-isopropylacrylamide (NIPAAm) were synthesized using the atom transfer radical polymerization (ATRP) method. The effects of varying the monomer feed ratios (30:70 and 70:30 DMAEMA:NIPAAm) and polymerization times on the film height, morphology and stimuli response to pH of the brush were evaluated. While the polymerization time was found to have little influence on the properties of the brushes, the monomer feed ratios had a great impact. The 70% DMAEMA polymer brush had similar height as the 30% DMAEMA brush after 45 min; however, it had a greater response to pH and morphological change compared to the 30% DMAEMA. The 70% DMAEMA brush was used to demonstrate an efficient approach to alleviate the ion suppression effect in MALDI analysis of complex mixtures by effectively fractionating a binary mixture of peptides prior to MALDI-MS analysis.

Nanostructure of Cationic Polymer Brush at the Air/Water Interface

Cationic amphiphilic diblock copolymers were synthesized by RAFT polymerization and the nanostructure of their monolayers was investigated by π-A isotherm and X-ray reflectivity. Carpet layer (dense hydrophilic block layer) formation under the hydrophobic layer was confirmed and a “brush” layer was found beneath the carpet layer. However, the thickness of brush layer was much thinner than that of the fully-stretched chain length. The critical salt concentration was found to be 0.01 M NaCl, which is much lower than that of the previous strongly anionic brush. These differences were probably caused by the low effective charge on the brush chains due to the hydrophobic nature of the quarternized ammonium cation.

Peptide/Protein Separation with Cationic Polymer Brush Nanosponges for MALDI-MS Analysis

A cationic polymer nanobrush was synthesized, attached to a MALDI target, and used for the fractionation of peptides and proteins based on their pI, prior to analysis by MALDI-MS. The cationic polymer nanobrush was synthesized on a gold substrate by AIBN photoinitiated polymerization, using a 70:30 ratio of 2-aminoethyl methacrylate hydrochloride (AEMA):N-isopropylacrylamide (NIPAAM). This brush showed selectivity for adsorption of acidic peptides and proteins and allowed fractionation of simple two-component mixtures to be completed in less than 10 min. The brush-adsorbed biomolecules were recovered by treating the nanobrush with ammonium hydroxide, which effectively collapsed the brush, thereby releasing the trapped compounds for MALDI MS analysis. These results demonstrate that nanobrush can serve as a convenient platform for rapid fractionation of biomolecules prior to analysis by MALDI-MS.

Cationic polymer brush grafted-nanodiamond via atom transfer radical polymerization for enhanced gene delivery and bioimaging

A novel cationic nanodiamond-polymer brush was synthesized by 2-bromoisobutyrate-modified nanodiamond (ND) surface-initiated atomic transfer radical polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA). Elemental analysis, FTIR, HRTEM, TGA and zeta potential analysis were used to confirm the successful synthesis of ND-polymer brushes. It was shown that the ND-brushes were capable of condensing plasmid DNA into stable nanoparticles, protecting DNA from enzyme degradation. Transfection studies demonstrated that the ND-brushes could not only efficiently deliver plasmids into COS-7 cells, but also mediate higher expression than PEI25k with lower cytotoxicity. The green fluorescence of ND-brushes could also be detected by laser scanning confocal microscopy, making the nanodiamond-polymer brushes an excellent multifunctional gene vector with not only high transfection efficiency but allowing for bioimaging.

AFM study of cationically charged polymer brushes: switching between soft and hard matter.

AFM studies on cationic polymer brushes in water (a good solvent) show that brushes in an extended conformation can be easily deformed or indented by an AFM tip. Experiments on polymer brushes in a more collapsed conformation, using methanol-water as a 'poor solvent' environment, show similar properties. Conversely, this 'soft' behaviour is dramatically different in the presence of electrolytes containing anions that are strongly coordinated to cationic groups of the polymer brush. Our initial studies in electrolyte solutions at different concentrations show that these brushes become so rigid that they cannot be indented or deformed by the AFM tip, even at high loads.