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  • Molecular Diversity Preservation International  (7)
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  • 1
    Publication Date: 2020-06-13
    Description: 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.
    Electronic ISSN: 1996-1944
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 2
    Publication Date: 2018-11-12
    Description: 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.
    Electronic ISSN: 2073-4360
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 3
    Publication Date: 2020-08-01
    Description: 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.
    Electronic ISSN: 1996-1944
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 4
    Publication Date: 2020-07-24
    Description: A series of copolymers of di(ethylene glycol) methyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) (P(D-co-A)) with variable ratios of comonomers were synthesized using atom transfer radical polymerization. Then, the amino groups of obtained copolymers were modified to clickable azide or prop-2-yn-1-yl carbamate groups. A thermoresponsive copolymers were obtained with the value of cloud point temperature (TCP) dependent on the type and number of functional groups in the copolymer and on the concentration of solutions. For P(D-co-A) copolymers, the TCP increased with increasing content of 2-aminoethyl methacrylate comonomer. The presence of azide and prop-2-yn-1-yl carbamate groups caused the changes of TCP of modified copolymers. All studied copolymers in dilute aqueous solutions aggregated above TCP to nanoparticles with sizes dependent on the solution concentration, heating procedures, and types and numbers of functional groups present in a copolymer chain. The presence of hydrophilic elements in the chain and the increase in the copolymer concentration led to the enlargement of the particle sizes. Aggregates were crosslinked using click reaction between an azide and prop-2-yn-1-yl carbamate groups that led to stable thermoresponsive nanogels. A systematic study of the behavior of copolymers allowed the determination of the chains useful for possible application in drug delivery.
    Electronic ISSN: 2073-4360
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 5
    Publication Date: 2020-02-02
    Description: Poly(2-oxazoline) (POx) matrices in the form of non-woven fibrous mats and three-dimensional moulds were obtained by electrospinning and fused deposition modelling (FDM), respectively. To obtain these materials, poly(2-isopropyl-2-oxazoline) (PiPrOx) and gradient copolymers of 2-isopropyl- with 2-n-propyl-2-oxazoline (P(iPrOx-nPrOx)), with relatively low molar masses and low dispersity values, were processed. The conditions for the electrospinning of POx were optimised for both water and the organic solvent. Also, the FDM conditions for the fabrication of POx multi-layer moulds of cylindrical or cubical shape were optimised. The properties of the POx after electrospinning and extrusion from melt were determined. The molar mass of all (co)poly(2-oxazoline)s did not change after electrospinning. Also, FDM did not influence the molar masses of the (co)polymers; however, the long processing of the material caused degradation and an increase in molar mass dispersity. The thermal properties changed significantly after processing of POx what was monitored by increase in enthalpy of exo- and endothermic peaks in differential scanning calorimetry (DSC) curve. The influence of the processing conditions on the structure and properties of the final material were evaluated having in a mind their potential application as scaffolds.
    Electronic ISSN: 2073-4360
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 6
    Publication Date: 2020-01-13
    Description: In this work, the self-assembly of a series of amphiphilic polystyrene-b-polyglycidol (PS-b-PGL) diblock copolymers in dioxane and dioxane/water mixtures is presented. The PS-b-PGL have an average degree of polymerization (DP) of PS block equal to 29 units and varied degrees of polymerization for the glycidol segments with DPs of 13, 42, 69 and 117. In dioxane, amphiphilic diblock copolymers form micelles with the hydrophilic PGL placed in the core. Critical micelle concentration (CMC) was determined based on the intensity of scattered light vs. concentration. The micelle size was measured by dynamic light scattering and transmission electron microscopy. Also, the behaviour of the copolymer was studied in water/dioxane solutions by following the changes of scattered light intensity with the addition of water to the system. Critical water content (CWC) of the studied systems decreased as the initial PS-b-PGL concentration in dioxane increased. This process was accompanied by a decrease in the size of aggregate formed. For a given initial copolymer concentration, the size of copolymer aggregates decreased linearly with increasing the length of the PGL block
    Electronic ISSN: 2073-4360
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 7
    Publication Date: 2020-12-28
    Description: Thermoresponsive polymers are a promising material for drug nanocarrier preparation, which makes the study of their aggregation in physiological conditions very important. In this paper, the thermal behaviour of the thermoresponsive polymers poly(N-isopropylacrylamide), poly(2-isopropyl-2-oxazoline-co-2-n-propyl-2-oxazoline) and poly[(2-hydroxyethyl methacrylate)-co-oligo(ethylene glycol) methyl ether methacrylate] were studied in phosphate buffer (PBS) and solutions of its salts in concentration as in PBS. The thermal response of the polymers was measured using UV-Vis and dynamic light scattering (DLS). The salts shifted the cloud point temperature (TCP) of the (co)polymers to higher values compared to the TCP of aqueous polymer solutions. In PBS and NaCl solutions, all polymers exhibited an unexpected and previously unreported transmittance profile. During heating, an additional aggregation of polymers appeared above the TCP accompanied by the formation of a precipitate. In monosodium phosphate solutions and pure water, the studied polymers showed lower critical solution temperature (LCST-type) behaviour. DLS measurements showed that a salt influenced the size of the resulting polymer particles. The sizes and stability of particles depended on the heating rate. In PBS and NaCl solutions, the size of particles in the dispersion decreased above 60 °C, and the precipitate appeared on the bottom of the cuvette. The additional aggregation of polymer and its falling out of solution may hinder the removal of carriers from the body and has to be taken into account when preparing nanocarriers.
    Electronic ISSN: 2073-4360
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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