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751 result(s) for "polymer brushes"
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Dually-functional riboflavin macromolecule as a supramolecular initiator and reducing agent in temporally-controlled low ppm ATRP
A novel supramolecular riboflavin-inspired macroinitiator was prepared for the first time by transesterification methodology and used as the multifunctional vitamin-B2 core to synthesize PBA brushes using different low ppm atom transfer radical polymerization (ATRP) approaches. Firstly the macromolecular initiator was successfully applied as a dually-functional structure, which simultaneously acts as a reducing agent in activator regeneration by electron transfer (ARGET) ATRP. Subsequently simplified electrochemically mediated ATRP of BA with different conditions was carried out for the preparation of well-defined riboflavin-based polymer brushes. Polymerizations were characterized in a well-controlled manner, affording polymers with a narrow dispersity (Ð = 1.22-1.25). Four-arms polymers were also received by an approach never described before - temporally-controlled multi-step seATRP under constant current conditions, giving precisely-defined polymer brushes (Ð = 1.26) with preserved chain-end functionality (DCF< 1%), despite stopping and restarting the polymerization. The solvolysis results indicate that all chains grow to equal lengths (Ð< 1.17), which shows the precisely controlled characteristic of seATRP. 1H NMR analysis confirms the formation of new vitamin B2-inspired polymers. In connection with the preserved riboflavin functionality and additional functional chains, these innovative macromolecules may find applications, e.g. as drug delivery systems.
Modification of Silica Nanoparticles with Miktoarm Polymer Brushes via ATRP
Silica nanoparticles were successfully modified with miktoarm brushes via atom transfer radical polymerization (ATRP) using three different approaches. In the first approach: “graft onto and from”, a poly( tert -butyl acrylate) (PtBA) macroinitiator was grafted onto the surface of a monomer-modified silica nanoparticle. Then, polystyrene (PSt) brush was grafted from the surface-tethered reactive chain end. In the second approach: “two-step reverse ATRP”, the PtBA and poly( n -butyl acrylate) (PBA) brushes were consecutively grafted from initiator-modified silica particles via ATRP. The polymerization was initiated from the silica surface via a two-step controlled thermal decomposition of surface-tethered diazo initiator moieties. In the third method: “diblock first”, a diblock copolymer of poly( tert -butyl acrylate) and poly(glycidyl methacrylate) (PtBA-b-PGMA) was grafted onto amine-modified silica particles. The diblock copolymer was covalently attached to the silica surface via interaction between surface-tethered amine groups and the short reactive block containing glycidyl groups. Next, the polystyrene brushes were grafted from surface-tethered reactive chain end. The materials prepared by three different approaches were characterized using gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). The PtBA brushes were hydrolyzed under acidic conditions to form poly(acrylic acid) (PAA) brushes. The resulting materials were imaged using atomic force microscopy (AFM) and transmission electron microscopy (TEM).
Low Friction, Lubricity, and Durability of Polymer Brush Coatings, Characterized Using the Relaxation Tribometer Technique
Among the possible solutions for achieving low friction, polymer brushes that are grafted onto surfaces are good candidates. The tribological characterization of such layers becomes more difficult when the friction is lower: the signal-to-noise ratio of the friction force that is measured with conventional tribometers impedes the precise quantification. Therefore, we have applied a new technique that has been developed at the Laboratory of Tribology and System Dynamics (LTDS), called the ‘oscillating relaxation tribometer’. The advantage of this original technique is that it characterizes low friction with unequalled sensitivity. The lower the friction, the better the precision, and it permits obtaining the ‘friction law’ directly from robust and rapid experimental tests. In this study, the samples that have been used are the ionic liquid-type polymer brushes (ILPBs) with different thicknesses, which have been grafted onto silicon wafers and steel coupons. The counter-face is a mirror-polished steel ball. We show that (i) a thick ILPB layer on silicon is very resistant to high contact pressure, up to 555 MPa; (ii) the friction behavior that is obtained is close to that of a Newtonian viscous one, even under maximum normal loads; (iii) poorer results are obtained for the thinner sample; and (iv) the repetition, up to 5000 oscillations on the same surface, does not affect the friction damping of the contact, which demonstrates that this film provides a favorable resistance to friction under severe contact conditions. In addition, the feasibility of grafting onto steel surfaces is demonstrated. The results are then discussed, with respect to friction and dissipation.
Concentrated polymer brushes do not induce the expression of inflammatory and angiogeneic genes in human umbilical vein endothelial cells
OBJECTIVE: When polymer brushes are applied as the inner coating for artificial blood vessels, they may induce unwanted responses in vascular endothelial cells continuously exposed to the polymer surface. Accordingly, we have examined the in vitro effect of non-biofouling concentrated polymer brushes (CPBs) on pro-inflammatory and angiogenic responses of human umbilical vein endothelial cells (HUVECs). RESULTS: Micro-patterned CPBs were prepared on silicon wafers using biocompatible polymers, poly(poly(ethylene glycol)methyl ether methacrylate) (PPEGMA) and poly(2-hydroxyethyl methacrylate) (PHEMA). HUVECs were cultured on PPEGMA-CPBs and PHEMA-CPBs with different channel widths (20, 50, and 80 µm) and analyzed for mRNA expression of the pro-inflammatory cytokines IL-6 and IL-8 and angiogeneic vascular endothelial growth factor (VEGF). Irrespective of channel width, PHEMA-CPBs reduced the expression of all target genes, whereas PPEGMA-CPBs reduced VEGF and did not affect IL-6 and IL-8 levels. CONCLUSION: Micro-patterned CPBs, irrespective of chemical structure or adhesion area, do not induce the expression of important pro-inflammatory and angiogenic mediators in endothelial cells.
Mixed Polymer Brushes for “Smart” Surfaces
Mixed polymer brushes (MPBs) are composed of two or more disparate polymers covalently tethered to a substrate. The resulting phase segregated morphologies have been extensively studied as responsive “smart” materials, as they can be reversible tuned and switched by external stimuli. Both computational and experimental work has attempted to establish an understanding of the resulting nanostructures that vary as a function of many factors. This contribution highlights state-of-the-art MPBs studies, covering synthetic approaches, phase behavior, responsiveness to external stimuli as well as novel applications of MPBs. Current limitations are recognized and possible directions for future studies are identified.
Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization
In situ emulsion polymerization was employed for synthesizing carbon nanotube (CNT) composites in a colloidal system with poly(styrene) or PS to form nanostructured brush. CNTs were initially functionalized with oleic acid, followed by silanization with (3-aminopropyl) triethoxysilane to impart cross-linking properties. Styrene monomers were efficiently grafted to surface modified CNT via emulsion polymerization with variable CNT concentrations. FTIR analyses of the functionalized CNT and PS/CNT composites confirmed the bond formation and effectiveness of the developed experimental method. X-ray photoelectron spectroscopy confirmed the presence of the desired bonds and the composition of the composites. Structural properties of the composites characterized by TEM confirmed excellent deagglomeration and dispersion of CNTs in PS/CNT composite. Thermal characteristics from TGA and DSC data showed enhanced properties for the nanocomposites as a function of the CNT content. BET measurements indicated significant improvements in surface area and pore volume with enhancements in gas sorption for the polymer nanocomposites.
Stability of Immobilized Chemosensor‐Filled Vesicles on Anti‐Fouling Polymer Brush Surfaces (Adv. Mater. Interfaces 21/2024)
Vesicle Immobilization Vesicles filled with chemosensors are immobilized into regular arrays on a polymer brush antifouling surface. Analytes entering the vesicle can turn off the chemosensor fluorescence. In article 2400200, Michael Hirtz and co‐workers investigate the stability of these systems and their potential for membrane permeability assays.
The Bioanalytical and Biomedical Applications of Polymer Modified Substrates
Polymers with different structures and morphology have been extensively used to construct functionalized surfaces for a wide range of applications because the physicochemical properties of polymers can be finely adjusted by their molecular weights, polydispersity and configurations, as well as the chemical structures and natures of monomers. In particular, the specific functions of polymers can be easily achieved at post-synthesis by the attachment of different kinds of active molecules such as recognition ligand, peptides, aptamers and antibodies. In this review, the recent advances in the bioanalytical and biomedical applications of polymer modified substrates were summarized with subsections on functionalization using branched polymers, polymer brushes and polymer hydrogels. The review focuses on their applications as biosensors with excellent analytical performance and/or as nonfouling surfaces with efficient antibacterial activity. Finally, we discuss the perspectives and future directions of polymer modified substrates in the development of biodevices for the diagnosis, treatment and prevention of diseases.
Folic Acid-Terminated Poly(2-Diethyl Amino Ethyl Methacrylate) Brush-Gated Magnetic Mesoporous Nanoparticles as a Smart Drug Delivery System
Currently, chemotherapy is an important method for the treatment of various cancers. Nevertheless, it has many limitations, such as poor tumour selectivity and multi-drug resistance. It is necessary to improve this treatment method by incorporating a targeted drug delivery system aimed to reduce side effects and drug resistance. The present work aims to develop pH-sensitive nanocarriers containing magnetic mesoporous silica nanoparticles (MMSNs) coated with pH-responsive polymers for tumour-targeted drug delivery via the folate receptor. 2-Diethyl amino ethyl methacrylate (DEAEMA) was successfully grafted on MMSNs via surface initiated ARGET atom transfer radical polymerization (ATRP), with an average particle size of 180 nm. The end groups of poly (2-(diethylamino)ethyl methacrylate) (PDEAEMA) brushes were converted to amines, followed by a covalent bond with folic acid (FA) as a targeting agent. FA conjugated to the nanoparticle surface was confirmed by X-ray photoelectron spectroscopy (XPS). pH-Responsive behavior of PDEAEMA brushes was investigated by Dynamic Light Scattering (DLS). The nanoparticles average diameters ranged from ca. 350 nm in basic media to ca. 650 in acidic solution. Multifunctional pH-sensitive magnetic mesoporous nanoparticles were loaded with an anti-cancer drug (Doxorubicin) to investigate their capacity and long-circulation time. In a cumulative release pattern, doxorubicin (DOX) release from nano-systems was ca. 20% when the particle exposed to acidic media, compared to ca. 5% in basic media. The nano-systems have excellent biocompatibility and are minimally toxic when exposed to MCF-7, and -MCF-7 ADR cells.
Super‐Slippery Poly(Dimethylsiloxane) Brush Surfaces: From Fabrication to Practical Application
Superwetting surfaces with special slippery performances have been the focus of practical applications and basic research for decades. Compared to superhydrophobic/superoleophobic and slippery liquid‐infused porous surfaces (SLIPS), liquid‐like covalently attached poly(dimethylsiloxane) (PDMS) brush surfaces have no trouble in constructing the micro/nanostructure and the loss of infused lubricant, meanwhile, it can also provide lots of new advantages, such as smooth, transparent, pressure‐ and temperature‐resistant, and low contact angle hysteresis (CAH) to diverse liquids. This paper focuses on the relationship between the wetting performance and practical functional application of PDMS brush surfaces. Recent progress of the preparation of PDMS brush surfaces and their super‐slippery performances, with a special focus on diverse functional applications were summarized. Finally, perspectives on future research directions are also discussed. Superwetting surfaces with special slippery performances have been the focus of practical applications and basic research for decades. Liquid‐like covalently attached poly(dimethylsiloxane) (PDMS) brush surfaces enable smooth, transparent, pressure‐ and temperature‐resistant, and low adhesion to diverse liquids. This paper focuses on the relationship between the wetting performance and practical functional application of PDMS brush surfaces.