Interactions between Nanoclay, CTAB and Linear/Star Shaped Polymers.

The influence of star-shaped (PAA-SS) and linear polyacrylic acid (PAA) with different molecular weights (high-PAA-HMW and low-PAA-LMW) on the structure of the adsorption layer, adsorption amount, electrokinetic and stabilizing properties of the PAA/CTAB/nanoclay suspensions was studied. The properties of the systems containing one of these polymers, the cationic surfactant-hexadecyltrimethylammonium bromide (CTAB) and the surface-modified nanoclay (N-SM) were analyzed using the following techniques: BET, CHN, FT-IR, ED-XRF, XRD, HRTEM, UV-Vis, tensiometry and zeta potential measurements. It was proved that PAA could be used as an effective stabilizer of N-SM. Moreover, the addition of CTAB caused a significant increase in the stability of the systems but decreased the adsorption of PAA on the N-SM surface and changed the structure of the adsorption layers. The largest stability was observed in the PAA-HMW/CTAB system. The PAA polymers and PAA/CTAB complexes adsorbed, especially on the clay surface, influenced the primary distribution of the layered sheets but kept the same basal d-spacing. The adsorption of PAA and the PAA/CTAB complexes took place mainly at the plate edges and on the contact space between the sheets. The obtained results will be used for the preparation of the PAA/CTAB/nanoclay composite for water purification.

Alternative to Poly(2-isopropyl-2-oxazoline) with a Reduced Ability to Crystallize and Physiological LCST.

In this work, we sought to examine whether the presence of alkyl substituents randomly distributed within the main chain of a 2-isopropyl-2-oxazoline-based copolymer will decrease its ability to crystallize when compared to its homopolymer. At the same time, we aimed to ensure an appropriate hydrophilic/lipophilic balance in the copolymer and maintain the phase transition in the vicinity of the human body temperature. For this reason, copolymers of 2-ethyl-4-methyl-2-oxazoline and 2-isopropyl-2-oxazoline were synthesized. The thermoresponsive behavior of the copolymers in water, the influence of salt on the cloud point, the presence of hysteresis of the phase transition and the crystallization ability in a water solution under long-term heating conditions were studied by turbidimetry. The ability of the copolymers to crystallize in the solid state, and their thermal properties, were analyzed by differential scanning calorimetry and X-ray diffractometry. A cytotoxicity assay was used to estimate the viability of human fibroblasts in the presence of the obtained polymers. The results allowed us to demonstrate a nontoxic alternative to poly(2-isopropyl-2-oxazoline) (PiPrOx) with a physiological phase transition temperature (LCST) and a greatly reduced tendency to crystallize. The synthesis of 2-oxazoline polymers with such well-defined properties is important for future biomedical applications.

Nonviral Plasmid DNA Carriers Based on N,N'-Dimethylaminoethyl Methacrylate and Di(ethylene glycol) Methyl Ether Methacrylate Star Copolymers.

Star polymers with random and block copolymer arms made of cationic N,N'-dimethylaminoethyl methacrylate (DMAEMA) and nonionic di(ethylene glycol) methyl ether methacrylate (DEGMA) were synthesized via atom transfer radical polymerization (ATRP) and used for the delivery of plasmid DNA in gene therapy. All stars were able to form polyplexes with plasmid DNA. The structure and size of the polyplexes were precisely determined using light scattering and cryo-TEM microscopy. The hydrodynamic radius of a complex of DNA with star was dependent on the architecture of the star arms, the DEGMA content and the number of amino groups in the star compared to the number of phosphate groups of the nucleic acid (N/P ratio). The smallest polyplexes (Rh90°âˆ¼50 nm) with positive zeta potentials (∼15 mV) were formed of stars with N/P=6. The introduction of DEGMA into the star structure caused a decrease of polyplex cytotoxicity in comparison to DMAEMA homopolymer stars. The overall transfection efficiency using HT-1080 cells showed that the studied systems are prospective gene delivery agents. The most promising results were obtained for stars with random copolymer arms of high DEGMA content.

Controlling the Crystallinity of Thermoresponsive Poly(2-oxazoline)-Based Nanolayers to Cell Adhesion and Detachment.

Semicrystalline, thermoresponsive poly(2-isopropyl-2-oxazoline) (PIPOx) layers covalently bonded to glass or silica wafers were obtained via the surface-termination of the living polymer chains. Polymer solutions in acetonitrile were exposed to 50 °C for various time periods and were poured onto the functionalized solid wafers. Fibrillar crystallites formed in polymerization solutions settled down onto the wafers next to the amorphous polymer. The amount of crystallites adsorbed on thermoresponsive polymer layers depended on the annealing time of the PIPOx solution. The wettability of PIPOx layers decreased with the increasing amount of crystallites. The higher content of crystallites weakened the temperature response of the layer, as evidenced by the philicity and thickness measurements. Semicrystalline thermoresponsive PIPOx layers were used as biomaterials for human dermal fibroblasts (HDFs) culture and detachment. The presence of crystallites on the PIPOx layers promoted the proliferation of HDFs. Changes in the physicochemical properties of the layer, caused by the temperature response of the polymer, led to the change in the cells shape from a spindle-like to an ellipsoidal shape, which resulted in their detachment. A supporting membrane was used to assist the detachment of the cells from PIPOx biosurfaces and to prevent the rolling of the sheet.

Quaternized Poly(N,N'-dimethylaminoethyl methacrylate) Star Nanostructures in the Solution and on the Surface.

Antibacterial polymeric materials are promising in the fight against resistant bacteria strains. Amongst them, cationic macromolecules with quaternary ammonium groups are one of intensively studied, as they interact with the bacterial membranes causing cell death. In this work, we propose to use nanostructures composed of polycations with star topology for the preparation of antibacterial materials. First, star polymers of N,N'-dimethylaminoethyl methacrylate and hydroxyl-bearing oligo(ethylene glycol) methacrylate P(DMAEMA-co-OEGMA-OH) were quaternized with various bromoalkanes and their solution behavior was studied. It was shown that in water two modes of star nanoparticles were observed, of diameters about 30 nm and up to 125 nm, independently of the quaternizing agent. Separately layers of P(DMAEMA-co-OEGMA-OH) stars were obtained. In this case, the chemical grafting of polymers to the silicon wafers modified with imidazole derivatives was applied, followed by the quaternization of the amino groups of polycations. A comparison of the quaternary reaction in solution and on the surface showed that in the solution it is influenced by the alkyl chain length of the quaternary agent, while on the surface such relationship is not observed. After physico-chemical characterization of the obtained nanolayers, their biocidal activity was tested against two strains of bacteria E. coli and B. subtilis. The best antibacterial properties exhibited layers quaternized with shorter alkyl bromide, where 100% growth inhibition of E. coli and B. subtilis after 24 h of contact was observed.

Effects of cationic polymers on the viability of microbial biofilms.

INTRODUCTION: The number of published biofilm studies and novel ways for studying them has risen dramatically in recent years, ow-ing to the broad application of biofilms in medicine. Some bacteria develop biofilms that are highly resistant to antimicrobial agents, resulting in persistent infections. This necessitates the development of alternative methods for combating biofilms. In this regard, the application of cationic polymers is a good candidate for realization of this strategy. AIM: The aim of our study was to investigate the potential of a newly synthesized covalently attached star copolymer of N,N'-dimeth-ylaminoethyl methacrylate and hydroxyl-bearing oligo(ethylene glycol) methacrylate [P(DMAEMA-co-HOEGMA)] to silica surfaces and its quaternized version [P(QDMAEMA-co-HOEGMA)] for destruction of biofilms formed by Bacillus subtilis or Pseudomonas aeruginosa. MATERIALS AND METHODS: Model strains representing different genera and taxonomic groups were selected for the study. The anti-biofilm activities of two different newly synthesized cationic polymers were investigated by observation (live/dead staining) of the viability of bacterial cells within the biofilm. RESULTS: The results obtained by the live/dead labeling of bacterial biofilms show a substantial decrease in the viability of population in the presence of cationic polymers, better expressed at B. subtilis. CONCLUSIONS: The studied two immobilized on silica wafers newly synthesized star copolymers exhibited potential for anti-biofilm effects. The results demonstrated combined potential for reducing the viability of bacterial cells within the biofilms and probably for loosening the biofilm matrix. The effect was better expressed in B. subtilis.

Gene-repaired iPS cells as novel approach for patient with osteogenesis imperfecta.

Introduction: The benefits of patient's specific cell/gene therapy have been reported in relation to numerous genetic related disorders including osteogenesis imperfecta (OI). In osteogenesis imperfecta particularly also a drug therapy based on the administration of bisphosphonates partially helped to ease the symptoms. Methods: In this controlled trial, fibroblasts derived from patient diagnosed with OI type II have been successfully reprogrammed into induced Pluripotent Stem cells (iPSCs) using Yamanaka factors. Those cells were subjected to repair mutations found in the COL1A1 gene using homologous recombination (HR) approach facilitated with star polymer (STAR) as a carrier of the genetic material. Results: Delivery of the correct linear DNA fragment to the osteogenesis imperfecta patient's cells resulted in the repair of the DNA mutation with an 84% success rate. IPSCs showed 87% viability after STAR treatment and 82% with its polyplex. Discussion: The use of novel polymer Poly[N,N-Dimethylaminoethyl Methacrylate-co-Hydroxyl-Bearing Oligo(Ethylene Glycol) Methacrylate] Arms (P(DMAEMA-co-OEGMA-OH) with star-like structure has been shown as an efficient tool for nucleic acids delivery into cells (Funded by National Science Centre, Contract No. UMO-2020/37/N/NZ2/01125).

Hybrid nanolayers of star polymers and silver nanoparticles with antibacterial activity.

The aim of this study was to obtain stable star polymer layers with incorporated silver nanoparticles (AgNPs) and to study the antimicrobial activity of these hybrid materials. In this work, a novel approach regarding the synthesis of AgNPs directly by the star polymer layer is presented. Nanolayers of poly(N,N'-dimethylaminoethyl methacrylate) and hydroxyl-bearing poly[oligo(ethylene glycol) methacrylate] (P(DMAEMA-co-OEGMA-OH)) stars, covalently bound with solid supports, were obtained through chemical reaction of hydroxyl groups in the star arms with substrate modified with imidazole derivative. Quantitative chemical composition analysis and tracking of the changes in the morphology and wettability after every step of surface modification confirmed the covalent attachment of stars with the support. In the next step, the polymer nanolayers were modified with AgNPs formed in situ using only amine groups of the star arms and followed by the crystal quartz microbalance (QCM). The analysis of the layer thickness and affinity to water, both with the shape, size and amount of silver incorporated into the layer, confirmed the efficacy of AgNPs formation. The amount of silver incorporated into layers was correlated with the molar masses of the grafted stars, and a possible location of AgNPs within layers was shown. The antibacterial activity tests of prepared nanolayers showed that obtained hybrid materials were highly effective against both gram-positive and gram-negative bacteria strains. This study shows that the obtained layers are promising as stable coatings for antibacterial applications.

Star Polymers as Non-Viral Carriers for Apoptosis Induction.

Apoptosis is a widely controlled, programmed cell death, defects in which are the source of various diseases such as neurodegenerative diseases as well as cancer. The use of apoptosis in the therapy of various human diseases is of increasing interest, and the analysis of the factors involved in its regulation is valuable in designing specific carriers capable of targeting cell death. Highly efficient and precisely controlled delivery of genetic material by low-toxic carriers is one of the most important challenges of apoptosis-based gene therapy. In this work, we investigate the effect of the star polymer with 28 poly(N,N'-dimethylaminoethyl methacrylate) arms (STAR) on human cells, according to its concentration and structure. We show that star polymer cytotoxicity increases within its concentration and time of cells treatment. Except for cytotoxic effect, we observe morphological changes such as a shrinkage, loss of shape and begin to detach. We also prove DNA condensation after star polymer treatment, one of the most characteristic feature of apoptosis. The results indicate that the use of STAR triggers apoptosis in cancer cells compared to various normal cells, what makes these nanoparticles a promising drug in therapeutic strategy, which targets apoptosis. We demonstrate highlighting potential of star polymers as an innovative tool for anti-cancer therapy.

The Role of Polymer Structure in Formation of Various Nano- and Microstructural Materials: 30 Years of Research in the Laboratory of Nano- and Microstructural Materials at the Centre of Polymer and Carbon Materials PAS.

The review summarizes the research carried out in the Laboratory of Nano- and Microstructural Materials at the Centre of Polymer and Carbon Materials, Polish Academy of Sciences (CMPW PAS). Studies carried out for many years under the guidance of Professor Andrzej Dworak led to the development and exploration of the mechanisms of oxirane and cyclic imine polymerization and controlled radical polymerization of methacrylate monomers. Based on that knowledge, within the last three decades, macromolecules with the desired composition, molar mass and topology were obtained and investigated. The ability to control the structure of the synthesized polymers turned out to be important, as it provided a way to tailor the physiochemical properties of the materials to their specific uses. Many linear polymers and copolymers as well as macromolecules with branched, star, dendritic and hyperbranched architectures were synthesized. Thanks to the applied controlled polymerization techniques, it was possible to obtain hydrophilic, hydrophobic, amphiphilic and stimulus-sensitive polymers. These tailor-made polymers with controlled properties were used for the construction of various types of materials, primarily on the micro- and nanoscales, with a wide range of possible applications, mainly in biomedicine. The diverse topology of polymers, and thus their properties, made it possible to obtain various types of polymeric nanostructures and use them as nanocarriers by encapsulation of biologically active substances. Additionally, polymer layers were obtained with features useful in medicine, particularly regenerative medicine and tissue engineering.

An Overview of Methods and Tools for Transfection of Eukaryotic Cells in vitro.

Transfection is a powerful analytical tool enabling studies of gene products and functions in eukaryotic cells. Successful delivery of genetic material into cells depends on DNA quantity and quality, incubation time and ratio of transfection reagent to DNA, the origin, type and the passage of transfected cells, and the presence or absence of serum in the cell culture. So far a number of transfection methods that use viruses, non-viral particles or physical factors as the nucleic acids carriers have been developed. Among non-viral carriers, the cationic polymers are proposed as the most attractive ones due to the possibility of their chemical structure modification, low toxicity and immunogenicity. In this review the delivery systems as well as physical, biological and chemical methods used for eukaryotic cells transfection are described and discussed.

Selective Partial Hydrolysis of 2-isopropyl-2-oxazoline Copolymers towards Decreasing the Ability to Crystallize.

Poly(2-isopropyl-2-oxazoline) (PiPrOx) is readily prone to crystallization both in solid and from solutions. This feature is detrimental for certain applications. Here, we examine whether the presence of unsubstituted ethyleneimine (EI) units, a gradient distributed within a polymer chain composed of 2-isopropyl-2-oxazoline (iPrOx) and 2-methyl-2-oxazoline (MOx) units, decreases the ability to crystallize the copolymer and affects thermal properties compared to the homopolymer of iPrOx. We assumed that the separation of stiff iPrOx units by the more flexible EI will affect the spatial arrangements of the ordered chains, slightly plasticize and, as a result, decrease their ability to crystallize. The selective hydrolysis of gradient iPrOx and 2-methyl-2-oxazoline (MOx) copolymers, carried out under mild conditions, led to iPrOx/MOx/EI copolymers. To the best of our knowledge, the selective hydrolysis of these copolymers has never been carried out before. Their thermal properties and crystallization abilities, both in a solid state and from an aqueous solution, were analyzed. Based on the analysis of polymer charge and cytotoxicity studies, the potential use of the copolymers obtained was indicated in some biological systems.

Antimicrobial Activity of Hybrid Nanomaterials Based on Star and Linear Polymers of N,N'-Dimethylaminoethyl Methacrylate with In Situ Produced Silver Nanoparticles.

Well-defined linear and multi-arm star polymer structures were used as the templates for in situ synthesis and stabilization of silver nanoparticles (AgNPs). This approach led to hybrid nanomaterials with high stability and antibacterial activity to both Gram-positive and Gram-negative bacterial strains. The ecologically friendly so called "green" synthesis of nanomaterials was performed through AgNPs preparation in the aqueous solutions of star and linear poly(N,N'-dimethylaminoethyl methacrylate)s (PDMAEMAs); the process was followed with time. The size, shape, and zeta potential of the obtained hybrids were determined. To our knowledge, this is the first time that the antibacterial activity of PDMAEMA hybrid nanomaterial against Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa was investigated and assessed by minimum inhibitory concentration (MIC) and minimum biocidal concentration (MBC). Completely quaternized with ethyl bromide, star and linear PDMAEMAs were used in comparative biological tests. The modification of the polymers with in situ-formed AgNPs increased the antibacterial properties against all studied strains of bacteria by several times in comparison to non-modified polymers and quaternized polymers. These results yield novel nanohybrid materials that can be useful for applications in medicine and biology.

Star polymer-based nanolayers with immobilized complexes of polycationic stars and DNA for deposition gene delivery and recovery of intact transfected cells.

We designed a novel thermoresponsive system of nanolayers composed of star poly[oligo(ethylene glycol) methacrylate]s (S-POEGMA) covalently bonded to a solid support and covered with polyplexes of cationic star polymers and plasmid DNA (pDNA). S-POEGMA stars were attached to the solid support via a UV-mediated "grafting to" method. To the best of our knowledge, for the first time, the conformational changes of obtained star nanolayers, occurring with changes in temperature, were studied using a quartz crystal microbalance technique. Next, the polyplexes of star poly[N,N'-dimethylaminoethyl methacrylate-ran-di(ethylene glycol) methacrylate] (S-P(DMAEMA-DEGMA)) with pDNA, exhibiting a phase transition temperature (TCP) in culture medium DMEM, were deposited on S-POEGMA layers when the temperature increased above the TCP of polyplex. The thermoresponsivity of the system was then the main mechanism for controlling the adhesion, proliferation, transfection and detachment of HT-1080 cells. The nanolayers promoted the effective cell culture and delivered nucleic acids into cells, with a transfection efficiency several times higher than that of the control. The detachment of the transfected cells was regulated only by the change of temperature. The studies demonstrated that we obtained a novel and effective system, based on a star polymer architecture, useful for gene delivery and tissue engineering applications.

Nanolayers of Poly(N,N'-Dimethylaminoethyl Methacrylate) with a Star Topology and Their Antibacterial Activity.

In this paper, we focus on the synthesis and characterization of novel stable nanolayers made of star methacrylate polymers. The effect of nanolayer modification on its antibacterial properties was also studied. A covalent immobilization of star poly(N,N'-dimethylaminoethyl methacrylate) (PDMAEMA) to benzophenone functionalized glass or silicon supports was carried out via a "grafting to" approach using UV irradiation. To date, star polymer UV immobilization has never been used for this purpose. The thickness of the resulting nanolayers increased from 30 to 120 nm with the molar mass of the immobilized stars. The successful bonding of star PDMAEMA to the supports was confirmed by surface sensitive quantitative spectroscopic methods. Next, amino groups in the polymer layer were quaternized with bromoethane, and the influence of this modification on the antibacterial properties of the obtained materials was analyzed using a selected reference strain of bacteria. The resulting star nanolayer surfaces exhibited higher antimicrobial activity against Bacillus subtilis ATCC 6633 compared to that of the linear PDMAEMA analogues grafted onto a support. These promising results and the knowledge about the influence of the topology and modification of PDMAEMA layers on their properties may help in searching for new materials for antimicrobial applications in medicine.

Poly(2-oxazoline) Matrices with Temperature-Dependent Solubility-Interactions with Water and Use for Cell Culture.

In this work, we studied the stability of matrices with temperature-dependent solubility and their interactions with water at physiological temperature for their application in cell culture in vitro. Gradient copolymers of 2-isopropyl- with 2-n-propyl-2-oxazoline (P(iPrOx-nPrOx)) were used to prepare the matrices. The comonomer ratio during polymerization was chosen such that the cloud point temperature (TCP) of the copolymer was below 37 °C while the glass transition (Tg) was above 37 °C. The role of the support for matrices in the context of their stability in aqueous solution was examined. Therefore, matrices in the form of both self-supported bulk polymer materials (fibrillar mats and molds) and polymer films supported on the silica slides were examined. All of the matrices remained undissolved when incubated in water at a temperature above TCP. For the self-supported mats and molds, we observed the loss of shape stability, but, in the case of films supported on silica slides, only slight changes in morphology were observed. For a more in-depth investigation of the origin of the shape deformation of self-supported matrices, we analyzed the wettability, thickness, and water uptake of films on silica support because the matrices remained undeformed under these conditions. It was found that, above the TCP of P(iPrOx-nPrOx), the wettability of the films decreased, but at the same time the films absorbed water and swelled. We examined how this specific behavior of the supported films influenced the culture of fibroblasts. The temperature-dependent solubility of the matrices and the possibility of noninvasive cell separation were also examined.

Fibroblast and keratinocyte crosstalk: the effect of a poly(tri[ethylene glycol] ethyl ether methacrylate) thermoresponsive surface on short-term co-culture.

The treatment of difficult-to-treat wounds can be challenging. Although a number of approaches have been investigated, the healing process may be slow and unsatisfactory. An alternative approach is the use of a continuous sheet of skin cells applied over a wound which may improve cell implantation and patient recovery. To analyse the gene expression profile of fibroblast/keratinocyte co-culture on poly(tri[ethylene glycol] ethyl ether methacrylate) (P[TEGMA-EE]), a thermoresponsive biocompatible surface. Cultures were grown for 72 hours as a continuous layer on P(TEGMA-EE). Assays for genotoxicity, cell morphology, and fluorescence-assisted flow cytometry were performed to exclude adverse effects. A gene expression profile related to the extracellular matrix was investigated by microarray analysis. For fibroblast monocultures and fibroblast/keratinocyte co-cultures maintained for 72 hours on P(TEGMA-EE), no change in morphology or specific surface markers, or DNA damage (comet assay) was observed, relative to control surface. Moreover, no detrimental impact was ascertained based on microarray analysis. In response to lowered temperature, the detachment of a continuous cell layer sheet from the thermoresponsive surface was observed. When gene expression was compared between fibroblasts cultured alone and co-cultured with keratinocytes on P(TEGMA-EE), 10 genes were shown to be differentially expressed. Of these genes, six were significantly differentially expressed between cultures grown on P(TEGMA-EE) and human skin samples. Our results indicate that P(TEGMA-EE) is fully biocompatible and is therefore a suitable surface for successful preparation and recovery of two-layered fibroblast/keratinocyte co-culture as a continuous sheet of cells.

Photocrosslinking of Polyglycidol and Its Derivative: Route to Thermoresponsive Hydrogels.

Hydrogels of biologically well-tolerated, high-molar-mass polyglycidol (PGl) and its thermoresponsive derivative poly(glycidol-co-ethyl glycidyl carbamate) have been obtained by direct UV crosslinking in the solid state. Polymers with molar masses up to 1.45 × 106 g mol-1 were crosslinked in the presence of benzophenone or (4-benzoylbenzyl)trimethylammonium chloride as photosensitizers. The photosensitizer concentration was varied from 2 to 10 wt%. The influence of polymer composition and photosensitizer type and amount on the crosslinking efficiency, swelling and temperature behavior of the obtained hydrogels was investigated. The photocrosslinking of PGl and poly(glycidol-co-ethyl glycidyl carbamate) led to hydrogels with swelling degrees up to 1700%. The swelling degrees of the hydrogels decreased with the increase of the environmental temperature indicating the thermoresponsive nature of gels. The swelling of obtained gels can be controlled by varying the composition of the copolymer precursor and by the network density.

Synthesis, Characterization and Cytotoxicity of Novel Thermoresponsive Star Copolymers of N,N'-Dimethylaminoethyl Methacrylate and Hydroxyl-Bearing Oligo(Ethylene Glycol) Methacrylate.

Novel, nontoxic star copolymers of N,N-dimethylaminoethyl methacrylate (DMAEMA) and hydroxyl-bearing oligo(ethylene glycol) methacrylate (OEGMA-OH) were synthesized via atom transfer radical polymerization (ATRP) using hyperbranched poly(arylene oxindole) as the macroinitiator. Stars with molar masses from 100,000 g/mol to 257,000 g/mol and with various amounts of OEGMA-OH in the arms were prepared. As these polymers can find applications, e.g., as carriers of nucleic acids, drugs or antibacterial or antifouling agents, in this work, much attention has been devoted to exploring their solution behavior and their stimuli-responsive properties. The behavior of the stars was studied in aqueous solutions under various pH and temperature conditions, as well as in PBS buffer, in Dulbecco's modified Eagle's medium (DMEM) and in organic solvents for comparison. The results indicated that increasing the content of hydrophilic OEGMA-OH units in the arms up to 10 mol% increased the cloud point temperature. For the stars with an OEGMA-OH content of 10 mol%, the thermo- and pH-responsivity was switched off. Since cytotoxicity experiments have shown that the obtained stars are less toxic than homopolymer DMAEMA stars, the presented studies confirmed that the prepared polymers are great candidates for the design of various nanosystems for biomedical applications.

Stable star polymer nanolayers and their thermoresponsiveness as a tool for controlled culture and detachment of fibroblast sheets.

In this study, we describe novel thermoresponsive star copolymer surfaces used for the first time for the culture of fibroblast sheets, followed by their detachment, controlled by a change in temperature. To date, no star polymers, or their layers, have been used for this purpose. A "grafting to" strategy was applied to obtain poly[oligo(ethylene glycol) methacrylate] star layers on functionalized solid supports. Atom transfer radical polymerization of oligo(ethylene glycol) methacrylates and glycidyl methacrylate initiated with modified poly(arylene oxindole) yielded stars with molar masses up to Mn = 380 000 g mol-1. Stars were attached to a glass substrate via the reaction between the functional epoxy groups of the stars with the amine groups of the functionalized substrate. The thickness of the layer was related to the dimensions of isolated stars in solution, which showed that multilayers were obtained. Above the phase transition temperature, polymer nanolayers were hydrophobic, thus enabling the growth of fibroblasts on their surfaces and the formation of a cell sheet. Decreasing the temperature below the phase transition temperature made the star surfaces hydrophilic. This eliminated the affinity of the surface for cells and led to detachment of the intact fibroblast sheet. These observations have shown for the first time that the star polymer architecture favors the detachment of cell sheets as compared to linear polymer analogues grafted onto supports, thus reducing the time of this process. Knowledge of the influence of the polymer topology on layer properties and cell growth and detachment can aid in the development of polymeric materials for tissue culture applications.