Search Results (21)

(1) Background: This study aimed to determine the optimum parameters for the treatment of Streptococcus mutans biofilm on clear dental aligners. (2) Methods: A 24-h-old S. mutans biofilm was grown on polyurethane (PU) and poly(ethylene terephthalate glycol) (PETG) aligners. These samples were treated with three chlorhexidine digluconate (CHX)-based antiseptic solutions, manual brushing, and a combination of both, with varying exposure times. The number of adhered bacteria was determined in both untreated and treated samples after sonication. Materials were analyzed with atomic force and scanning electron microscopy, and surface free energy (SFE) values were determined using three different models. (3) Results: Our findings indicated that control strategies do not depend on the type of material. PU and PETG surfaces exhibited similar SFE values (41–45 mJ/m²). Differences in surface roughness were insufficient to cause significant changes in S. mutans behavior. The highest efficacy of all three tested antiseptics was established for the exposure time of 1 min, with efficacy deteriorating just after 3 min. (4) Conclusions: The efficacy of CHX against S. mutans early biofilm is material-independent and time-dependent. The optimal exposure time of 1 min should be combined with brushing, with a general recommendation of the antiseptic-first approach. Full article

Polypyrrole (PPy) is cationic in its conducting form, requiring a charge-balancing counterion, or dopant. The release of bioactive dopants, driven by the reduction of PPy films, offers a route to controlled drug delivery. Thiol-terminated long chain poly (ethylene glycol) (PEG) reacts with a dodecylbenzene sulfonate (DBSA)-doped PPy, forming a dense overlayer and partially liberating DBSA via the chemical reduction of the film. The resulting PEG brush acts as a barrier to dopant diffusion from the film, but proteins have been shown to disrupt this layer, releasing the DBSA. The mechanism by which this disruption occurs has not been thoroughly investigated. In this study, dopant release from PEG-PPy composites was examined via systematic exposure to a variety of chemical stimuli, including macromolecules such as poly (ethylene imine), polyethylene glycol, and poloxamers, as well as small-molecular-weight alcohols, carboxylic acids, and amines. Dopant release was quantified by quartz crystal microbalance. Poly (ethylene imine) efficiently released DBSA, while anionic and uncharged macromolecules did not. All classes of small molecules triggered dopant release, with longer homologues magnifying the response. The mechanisms of dopant removal are dependent on the functional groups of the stimulating agent and include ion exchange and nucleophilic reduction of the polycationic backbone. Tosylate, salicylate, and penicillin dopants showed release behaviors similar to DBSA, demonstrating the generality of the PEG barrier. Full article

Seven pyrene-labeled poly(oligo(ethylene glycol) methyl ether methacrylate)s (PyEG₅-PEG_nMAs) were prepared with n = 0, 3, 4, 5, 7, 9, and 19 ethylene glycol units by copolymerizing a small amount of penta(ethylene glycol) 1-pyrenemethyl ether methacrylate with an EG_nMA monomer. The conformation of the PyEG₅-PEG_nMA polymers evolved from a random coil for PyEG₅-PEG₀MA or poly(methyl methacrylate) to a polymeric bottle brush (PBB) architecture with increasing side chain length. The fluorescence decays of the PyEG₅-PEG_nMA samples were fitted according to the fluorescence blob model (FBM) whose parameters were used, in combination with the Kratky–Porod equation, to calculate the persistence length of these polymers. The persistence lengths obtained from the PEF experiments were found to increase with the square of the number (N_S) of non-hydrogen atoms in the side chain as expected theoretically. The persistence lengths found with the PyEG₅-PEG_nMA samples in DMF also matched those found earlier for another series of PEG_nMA samples labeled with 1-pyrenebutanol. The good agreement found between the persistence lengths obtained with the PEG_nMA samples labeled with two different pyrene derivatives illustrates the robustness of the method and its applicability for measuring the unknown persistence length of polydisperse polymer samples. Full article

This work aims to apply water radiolysis-mediated green synthesis of amphiphilic core–shell water-soluble chitosan nanoparticles (WCS NPs) via free radical graft copolymerization in an aqueous solution using irradiation. Robust grafting poly(ethylene glycol) monomethacrylate (PEGMA) comb-like brushes were established onto WCS NPs modified with hydrophobic deoxycholic acid (DC) using two aqueous solution systems, i.e., pure water and water/ethanol. The degree of grafting (DG) of the robust grafted poly(PEGMA) segments was varied from 0 to ~250% by varying radiation-absorbed doses from 0 to 30 kGy. Using reactive WCS NPs as a water-soluble polymeric template, a high amount of DC conjugation and a high degree of poly(PEGMA) grafted segments brought about high moieties of hydrophobic DC and a high DG of the poly(PEGMA) hydrophilic functions; meanwhile, the water solubility and NP dispersion were also markedly improved. The DC-WCS-PG building block was excellently self-assembled into the core–shell nanoarchitecture. The DC-WCS-PG NPs efficiently encapsulated water-insoluble anticancer and antifungal drugs, i.e., paclitaxel (PTX) and berberine (BBR) (~360 mg/g). The DC-WCS-PG NPs met the role of controlled release with a pH-responsive function due to WCS compartments, and they showed a steady state for maintaining drugs for up to >10 days. The DC-WCS-PG NPs prolonged the inhibition capacity of BBR against the growth of S. ampelinum for 30 days. In vitro cytotoxicity results of the PTX-loaded DC-WCS-PG NPs with human breast cancer cells and human skin fibroblast cells proved the role of the DC-WCS-PG NPs as a promising nanoplatform for controlling drug release and reducing the side effects of the drugs on normal cells. Full article

The properties of polymer brushes based on three macromonomers were investigated in aqueous and organic solutions. Methacrylic monomers with different compositions of the oligo(oxyalkylene) substituents and arrangements of the oligo(ethylene glycol) and oligo(propylene glycol) blocks were used for the synthesis of polymers. There were methoxy [oligo(ethylene glycol)_10.3-block-oligo(propylene glycol)_4.7] methacrylate, methoxy [oligo(propylene glycol)_8.3-block-oligo(ethylene glycol)_6.6] methacrylate, and methoxy oligo(propylene glycol)_4.2 methacrylate. Molecular brushes were investigated by the methods of molecular hydrodynamics and optics in dilute solutions in acetonitrile, chloroform, and water. The peculiarities of behavior of poly[oligo(oxyalkylene) methacrylates] in aqueous solutions and water-toluene systems have been found; in particular, the solubility of the polymers in water and organic solvents, the polymers equilibrium distribution between the phases, and the surface activity in the water-toluene system have been established. The thermo-responsibility in aqueous solutions and values of a critical concentration of micelle formation were shown. Depending on the arrangement of blocks in the side chains of molecular brushes, they are characterized by different intramolecular density. Full article

Biofouling on surfaces, caused by the assimilation of proteins, peptides, lipids and microorganisms, leads to contamination, deterioration and failure of biomedical devices and causes implants rejection. To address these issues, various antifouling strategies have been extensively studied, including polyethylene glycol-based polymer brushes. Conducting polymers-based biointerfaces have emerged as advanced surfaces for interfacing biological tissues and organs with electronics. Antifouling of such biointerfaces is a challenge. In this study, we fabricated electrospun fibre mats from sulphonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (sSEBS), infused with conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) (sSEBS-PEDOT), to produce a conductive (2.06 ± 0.1 S/cm), highly porous, fibre mat that can be used as a biointerface in bioelectronic applications. To afford antifouling, here the poly(oligo (ethylene glycol) methyl ether methacrylate) (POEGMA) brushes were grafted onto the sSEBS-PEDOT conducting fibre mats via surface-initiated atom transfer radical polymerization technique (SI-ATRP). For that, a copolymer of EDOT and an EDOT derivative with SI-ATRP initiating sites, 3,4-ethylenedioxythiophene) methyl 2-bromopropanoate (EDOTBr), was firstly electropolymerized on the sSEBS-PEDOT fibre mat to provide sSEBS-PEDOT/P(EDOT-co-EDOTBr). The POEGMA brushes were grafted from the sSEBS-PEDOT/P(EDOT-co-EDOTBr) and the polymerization kinetics confirmed the successful growth of the brushes. Fibre mats with 10-mers and 30-mers POEGMA brushes were studied for antifouling using a BCA protein assay. The mats with 30-mers grafted brushes exhibited excellent antifouling efficiency, ~82% of proteins repelled, compared to the pristine sSEBS-PEDOT fibre mat. The grafted fibre mats exhibited cell viability >80%, comparable to the standard cell culture plate controls. Such conducting, porous biointerfaces with POEGMA grafted brushes are suitable for applications in various biomedical devices, including biosensors, liquid biopsy, wound healing substrates and drug delivery systems. Full article

In this study, a brush-like polymer with aggregation-induced emission (AIE) features was synthesized for drug delivery and intracellular drug tracking. The polymer consisting of tetraphenylethene (TPE) chain-end as well as oligo-poly (ethylene glycol) (PEG) and hydrazine functionalities was successfully synthesized through copper (0)-mediated reversible-deactivation radical polymerization (Cu⁰-mediated RDRP). Anticancer drug doxorubicin (DOX) was conjugated to the polymer and formed a prodrug named TPE-PEGA-Hyd-DOX, which contains 11% DOX. The hydrazone between DOX and polymer backbone is a pH-sensitive linkage that can control the release of DOX in slightly acidic conditions, which can precisely control the DOX release rate. The drug release of 10% after 96 h in normal cell environments compared with about 40% after 24 h in cancer cell environments confirmed the influence of the hydrazone bond. The ratiometric design of fluorescent intensities with peaks at 410 nm (emission due to AIE feature of TPE) and 600 nm (emission due to ACQ feature of DOX) provides an excellent opportunity for this product as a precise intracellular drug tracker. Cancer cells confocal microscopy showed negligible DOX solution uptake, but an intense green emission originated from prodrug uptake. Moreover, a severe red emission in the DOX channel confirmed a promising level of drug release from the prodrug in the cytoplasm. The merged images of cancer cells confirmed the high performance of the TPE-PEGA-Hyd-DOX compound in the viewpoints of cellular uptake and drug release. This polymer prodrug successfully demonstrates low cytotoxicity in healthy cells and high performance in killing cancer cells. Full article

Bottlebrush copolymers with different chemical structures and compositions as well as diverse architectures represent an important kind of material for various applications, such as biomedical devices. To our knowledge, zwitterionic conjugated bottlebrush copolymers integrating fluorescence imaging and tumor microenvironment-specific responsiveness for efficient intracellular drug release have been rarely reported, likely because of the lack of an efficient synthetic approach. For this purpose, in this study, we reported the successful preparation of well-defined theranostic zwitterionic bottlebrush copolymers with unique brush-on-brush architecture. Specifically, the bottlebrush copolymers were composed of a fluorescent backbone of polyfluorene derivate (PFONPN) possessing the fluorescence resonance energy transfer with doxorubicin (DOX), primary brushes of poly(2-hydroxyethyl methacrylate) (PHEMA), and secondary graft brushes of an enzyme-degradable polytyrosine (PTyr) block as well as a zwitterionic poly(oligo (ethylene glycol) monomethyl ether methacrylate-co-sulfobetaine methacrylate) (P(OEGMA-co-SBMA)) chain with super hydrophilicity and highly antifouling ability via elegant integration of Suzuki coupling, NCA ROP and ATRP techniques. Notably, the resulting bottlebrush copolymer, PFONPN₉-g-(PHEMA₁₅-g-(PTyr₁₆-b-P(OEGMA₆-co-SBMA₆)₂)) (P₂) with a lower MW ratio of the hydrophobic side chains of PTyr and hydrophilic side chains of P(OEGMA-co-SBMA) could self-assemble into stabilized unimolecular micelles in an aqueous phase. The resulting unimolecular micelles showed a fluorescence quantum yield of 3.9% that is mainly affected by the pendant phenol groups of PTyr side chains and a drug-loading content (DLC) of approximately 15.4% and entrapment efficiency (EE) of 90.6% for DOX, higher than the other micelle analogs, because of the efficient supramolecular interactions of π–π stacking between the PTyr blocks and drug molecules, as well as the moderate hydrophilic chain length. The fluorescence of the PFONPN backbone enables fluorescence resonance energy transfer (FRET) with DOX and visualization of intracellular trafficking of the theranostic micelles. Most importantly, the drug-loaded micelles showed accelerated drug release in the presence of proteinase K because of the enzyme-triggered degradation of PTyr blocks and subsequent deshielding of P(OEGMA-co-SBMA) corona for micelle destruction. Taken together, we developed an efficient approach for the synthesis of enzyme-responsive theranostic zwitterionic conjugated bottlebrush copolymers with a brush-on-brush architecture, and the resulting theranostic micelles with high DLC and tumor microenvironment-specific responsiveness represent a novel nanoplatform for simultaneous cell image and drug delivery. Full article

A platform technology based on inorganic/organic nanoparticles for carrying drugs could be of enormous potential benefit in treating cancer. Surface modification of the nanoparticles with pH-responsive and biocompatible polymers can improve the selectivity and targeting toward the tumor cells. Polyethylene glycol (PEG) and its derivatives being present on the surface could enhance the ability to tailor nanomaterial hydrophilicity and to resist the adhesion of proteins and/or cells. Herein, we report a new nanoplatform based on mesoporous silica nanoparticles (MSNs) conjugated with poly(2-(diethylamino) ethyl methacrylate) (PDEAEMA) brushes as a candidate for stimuli-responsive intracellular drug delivery system. Alkyl bromide functional initiators (end-functionalized PDEAEMA brushes) were derivatized to amine, followed by the reaction with ethylene sulfide and poly(oligo(ethylene glycol) methyl ether acrylate (POEGMEA). Using X-ray photoelectron spectroscopy (XPS) to examine the attachment of POEGMEA, it was found that the POEGMEA molecules in the outer surface of PDEAEMA brushes have been successfully reacted with thiol groups, as indicated by the increase in the peak intensity of the C–O group at 286.5 eV. Brush-modified silica hybrids have an average diameter of ca. 250 nm, as estimated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Rhodamine B dye was loaded into the brush-modified silica hybrids nanoparticles with loading capacity of ca. 74%. The accumulated dye released from brush-modified particles in acidic media was approximately 60%, whereas the dye amount release in basic media was less than 15% after 10 h exposure time. Alamar Blue assay was used to assess the cytotoxicity of MSNs–PDEAEMA, MSNs–PDEAEMA–SH, and MSNs–PDEAEMA–POEGMEA. The results show that all three nanosystems were non-toxic to hMSC with an increase in cell proliferation for MSNs–PDEAEMA–POEGMEA at 50 µg/mL after both 24 and 48 h of incubation. Full article

In the present work, we have successfully prepared and characterized novel nanocomposite material exhibiting temperature-dependent surface wettability changes, based on grafted brush coatings of non-fouling poly(di(ethylene glycol)methyl ether methacrylate) (POEGMA) with the embedded CaCO₃ nanoparticles. Grafted polymer brushes attached to the glass surface were prepared in a three-step process using atom transfer radical polymerization (ATRP). Subsequently, uniform CaCO₃ nanoparticles (NPs) embedded in POEGMA-grafted brush coatings were synthesized using biomineralized precipitation from solutions of CaCl₂ and Na₂CO₃. An impact of the low concentration of the embedded CaCO₃ NPs on cell adhesion and growth depends strongly on the type of studied cell line: keratinocytes (HaCaT), melanoma (WM35) and osteoblastic (MC3T3-e1). Based on the temperature-responsive properties of grafted brush coatings and CaCO₃ NPs acting as biologically active substrate, we hope that our research will lead to a new platform for tissue engineering with modified growth of the cells due to the release of biologically active substances from CaCO₃ NPs and the ability to detach the cells in a controlled manner using temperature-induced changes of the brush. Full article

In this paper, a new pH-responsive nanosystem based on mesoporous silica nanoparticles (MSNs) was developed for cancer therapy. Poly(2-(diethylamino) ethyl methacrylate) (PDEAEMA) was grafted on their outer surface and acts as a gatekeeper, followed by subsequent modification of the polymer by cysteine (MSN-PDEAEMA-Cys) and poly(oligo(ethylene glycol) methyl ether methacrylate) (MSN-PDEAEMA-Cys-POEGMEMA). The physicochemical properties of these nanocarriers were characterized using scanning and transmission electron microscopies (SEM and TEM), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and dynamic light scattering (DLS). The synthesized nanoparticles were well-dispersed with a diameter of ca. 200 nm. The obtained XPS results confirm the successful modification of MSN-PDEAEMA with Cys and POEGMEMA by increasing the peak intensity of C–O and C=O groups at 286.5 and 288.5 eV, respectively. An anti-cancer drug, doxorubicin (DOX), was encapsulated into the fabricated nanoplatform. The DOX release amount at physiological pH of 7.4 was limited (10%), while an accumulation drug release of ca. 35% was accomplished after 30 h in acidic media. The MTT cell line was used to assess the cytotoxicity of the unloaded and DOX-loaded fabricated nanoplatforms. Upon loading of DOX on these nanomaterials, they showed significant toxicity to human liver cancer cells. These results suggest that the prepared nano-structured materials showed good biocompatibility as well, and they can serve as nanocarriers for the delivery of anti-cancer drugs. Full article

A well-defined block copolymer brush poly(glycidyl methacrylate)-graft-(poly(methyl methacrylate)-block- poly(oligo(ethylene glycol) methyl ether methacrylate)) (PGMA-g-(PMMA-b-POEGMA)) is synthesized via grafting from an approach based on a combination of click chemistry and reversible addition-fragmentation chain transfer (RAFT) polymerization. The resulting block copolymer brushes were characterized by ¹H-NMR and size exclusion chromatography (SEC). The self-assembly of the block copolymer brush was then investigated under selective solvent conditions in three systems: THF/water, THF/CH₃OH, and DMSO/CHCl₃. PGMA-g-(PMMA-b-POEGMA) was found to self-assemble into spherical micelle structures as analyzed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The average size of the particles was much smaller in THF/CH₃OH and DMSO/CHCl₃ as compared with the THF/water system. Thin film of block copolymer brushes with tunable surface properties was then prepared by the spin-coating technique. The thickness of the thin film was confirmed by scanning electron microscopy (SEM). Atom force microscopy (AFM) analysis revealed a spherical morphology when the block copolymer brush was treated with poor solvents for the backbone and hydrophobic side chains. The contact angle measurements were used to confirm the surface rearrangements of the block copolymer brushes. Full article

Antifouling polymer layers containing extracellular matrix-derived peptide motifs offer promising new options for biomimetic surface engineering. In this contribution, we report the design of antifouling vascular grafts bearing biofunctional peptide motifs for tissue regeneration applications based on hierarchical polymer brushes. Hierarchical diblock poly(methyl ether oligo(ethylene glycol) methacrylate-block-glycidyl methacrylate) brushes bearing azide groups (poly(MeOEGMA-block-GMA-N₃)) were grown by surface-initiated atom transfer radical polymerization (SI-ATRP) and functionalized with biomimetic RGD peptide sequences. Varying the conditions of copper-catalyzed alkyne-azide “click” reaction allowed for the immobilization of RGD peptides in a wide surface concentration range. The synthesized hierarchical polymer brushes bearing peptide motifs were characterized in detail using various surface sensitive physicochemical methods. The hierarchical brushes presenting the RGD sequences provided excellent cell adhesion properties and at the same time remained resistant to fouling from blood plasma. The synthesis of anti-fouling hierarchical brushes bearing 1.2 × 10³ nmol/cm² RGD biomimetic sequences has been adapted for the surface modification of commercially available grafts of woven polyethylene terephthalate (PET) fibers. The fiber mesh was endowed with polymerization initiator groups via aminolysis and acylation reactions optimized for the material. The obtained bioactive antifouling vascular grafts promoted the specific adhesion and growth of endothelial cells, thus providing a potential avenue for endothelialization of artificial conduits. Full article

Cells are continuously sensing their microenvironment and subsequently respond to different physicochemical cues by the activation or inhibition of different signaling pathways. To study a very complex cellular response, it is necessary to diminish background environmental influences and highlight the particular event. However, surface-driven nonspecific interactions of the abundant biomolecules from the environment influence the targeted cell response significantly. Yes-associated protein (YAP) translocation may serve as a marker of human hepatocellular carcinoma (Huh7) cell responses to the extracellular matrix and surface-mediated stresses. Here, we propose a platform of tunable functionable antifouling poly(carboxybetain) (pCB)-based brushes to achieve a molecularly clean background for studying arginine, glycine, and aspartic acid (RGD)-induced YAP-connected mechanotransduction. Using two different sets of RGD-functionalized zwitterionic antifouling coatings with varying compositions of the antifouling layer, a clear correlation of YAP distribution with RGD functionalization concentrations was observed. On the other hand, commonly used surface passivation by the oligo(ethylene glycol)-based self-assembled monolayer (SAM) shows no potential to induce dependency of the YAP distribution on RGD concentrations. The results indicate that the antifouling background is a crucial component of surface-based cellular response studies, and pCB-based zwitterionic antifouling brush architectures may serve as a potential next-generation easily functionable surface platform for the monitoring and quantification of cellular processes. Full article

Urinary tract infections are one of the most common hospital-acquired infections, and they are often associated with biofilm formation in indwelling medical devices such as catheters and stents. This study aims to investigate the antibiofilm performance of a polymer brush—poly[oligo(ethylene glycol) methyl ether methacrylate], poly(MeOEGMA)—and evaluate its effect on the antimicrobial susceptibility of Escherichia coli biofilms formed on that surface. Biofilms were formed in a parallel plate flow chamber (PPFC) for 24 h under the hydrodynamic conditions prevailing in urinary catheters and stents and challenged with ampicillin. Results obtained with the brush were compared to those obtained with two control surfaces, polydimethylsiloxane (PDMS) and glass. The polymer brush reduced by 57% the surface area covered by E. coli after 24 h, as well as the number of total adhered cells. The antibiotic treatment potentiated cell death and removal, and the total cell number was reduced by 88%. Biofilms adapted their architecture, and cell morphology changed to a more elongated form during that period. This work suggests that the poly(MeOEGMA) brush has potential to prevent bacterial adhesion in urinary tract devices like ureteral stents and catheters, as well as in eradicating biofilms developed in these biomedical devices. Full article