Selective Aerobic Oxidation of P-Methoxytoluene by Co(II)-Promoted NHPI Incorporated into Cross-Linked Copolymer Structure

A wide series of copolymer materials with various contents of 4-vinyl-diisopropyl-phtalate ester (10–90 mol%), divinylbenzene (1–11 mol%) and styrene, as monomers, were obtained by radical copolymerization. In the last steps of the synthesis, diisopropyl ester functionalities were converted into the form of N-hydroxyphthalimide (NHPI) rings. The obtained materials with the NHPI groups immobilized in the copolymer structure were studied by various physicochemical techniques, including FT-IR, UV-Vis-DR, XPS, elemental analysis, and tested as catalysts in aerobic oxidation of p-methoxytoluene in the presence of Co(II) acetate co-catalyst. Conversion of the aromatic substrate was correlated with the NHPI content and cross-linking degree. The best catalytic performance (conversions higher than 23%) was achieved for the copolymer catalysts containing 60% and 30% of 4-vinyl-diisopropyl-phtalate ester. At too high concentrations of NHPI and DVB, some of the NHPI groups were transformed into inactive (C=O)-N=O species or not available due to embedding inside the copolymer structure. The mechanism of the process involving both NHPI centers, forming phthalimide N-oxyl (PINO) radicals, and Co(II) cations was discussed. Stability of the developed catalysts was also tested. The opening of imide rings took place during the catalytic process, resulting in the formation of carboxyl groups and the release of hydroxylamine molecules. The deactivated catalyst could be easily regenerated by repeating two last steps of closing imide ring.

DPD Study on the Interfacial Properties of PEO/PEO-PPO-PEO/PPO Ternary Blends: Effects of Pluronic Structure and Concentration

Using the method of dissipative particle dynamics (DPD) simulations, we investigated the interfacial properties of PEO/PEO-PPO-PEO/PPO ternary blends composed of the Pluronics L64(EO13PO30EO13), F68(EO76PO29EO76), F88(EO104PO39EO104), or F127(EO106PO70EO106) triblock copolymers. Our simulations show that: (i) The interfacial tensions (γ) of the ternary blends obey the relationship γF68 < γL64 < γF88 < γF127, which indicates that triblock copolymer F68 is most effective in reducing the interfacial tension, compared to L64, F88, and F127; (ii) For the blends of PEO/L64/PPO and the F64 copolymer concentration ranging from ccp = 0.2 to 0.4, the interface exhibits a saturation state, which results in the aggregation and micelle formation of F64 copolymers added to the blends, and a lowered efficiency of the L64 copolymers as a compatibilizer, thus, the interfacial tension decreases slightly; (iii) For the blends of PEO/F68/PPO, elevating the Pluronic copolymer concentration can promote Pluronic copolymer enrichment at the interfaces without forming the micelles, which reduces the interfacial tension significantly. The interfacial properties of the blends contained the PEO-PPO-PEO triblock copolymer compatibilizers are, thus, controlled by the triblock copolymer structure and the concentration. This work provides important insights into the use of the PEO-PPO-PEO triblock copolymer as compatibilizers in the PEO and PPO homopolymer blend systems.

Synthesis of Poly(l-lactide-co-ε-caprolactone) Copolymer: Structure, Toughness, and Elasticity

Biodegradable and bioabsorbable polymers have drawn considerable attention because of their mechanical properties that mimic human soft tissue. Poly(l-lactide-co-ε-caprolactone) (PLCL), the copolymer of L-lactic (LA) and ε-caprolactone (CL), has been applied in many tissue engineering and regenerative medicine fields. However, both the synthesis of PLCL and the structure-activity relationship of the copolymer need to be further investigated to allow tuning of different mechanical properties. The synthesis conditions of PLCL were optimized to increase the yield and improve the copolymer properties. The synthetic process was evaluated by while varying the molar ratio of the monomers and polymerization time. The mechanical properties of the copolymer were investigated from the macroscopic and microscopic perspectives. Changes in the polymerization time and feed ratio resulted in the difference in the LA and CL content, which, in turn, caused the PLCL to exhibit different properties. The PLCL obtained with a feed ratio of 1:1 (LA:CL) and a polymerization time of 30 h has the best toughness and elasticity. The developed PLCL may have applications in dynamic mechanical environment, such as vascular tissue engineering.

THE EFFECT OF METHYL METHACRYLATE ON THE PROPERTIES OF SYNTHESIZED ACRYLATE EMULSIONS

The effect of methyl methacrylate (MMA) addition on the properties of synthesized acrylate emulsions based on butyl acrylate (BA) and 2-ethylhexyl acrylate (EHA) was investigated. The samples were synthesized by addition of MMA in copolymer structure, ranging from 10 to 50 wt% of the total mass of BA and EHA. Fourier transformation infrared (FTIR) spectroscopy was used to analyze the molecular structure of synthesized acrylate emulsions and the results confirmed that a quantitative polymerization reaction occurred. The analysis of thermal properties showed that the addition of methyl methacrylate increases the glass transition temperature of the acrylate films obtained by drying the synthesized emulsions. The tensile strength and elongation at break increased proportionally with the increase of the content of MMA in the synthesized samples. Since the obtained acrylate materials can be used to improve the water impermeability of paper and other materials, the obtained emulsion was applied in a thin layer on a sheet of paper and the resistance of the paper to water and oil was investigated. The results showed that all emulsions were impermeable both to water and oil.

Coarse-grained simulation of the self-assembly of lipid vesicles concomitantly with novel block copolymers with multiple tails

We carried out a series of coarse-grained molecular dynamics liposome-copolymer simulations with varying extent of copolymer concentration in an attempt to understand the effect of copolymer structure and concentration on vesicle self-assembly and stability.

Features of Structure and Properties of pHEMA-gr-PVP Block Copolymers, Obtained in the Presence of Fe2+

This paper presents the research results of the copolymer structure and properties of 2-hydroxyethylmethacrylate (HEMA) with polyvinylpyrrolidone (PVP) and their hydrogels, obtained by block polymerization in the presence of iron sulfate (II). By the methods of chemical analysis, IR spectroscopy, Thermogravimetric (TG) and Differential Thermal Analysis (DTA), the course of grafted copolymerization of HEMA on PVP with the formation of a cross-linked copolymer was confirmed. The results received by scanning electron microscopy showed that due to the copolymerization of HEMA with PVP, macroporous hydrogels with a pore size of 10–30 μm were obtained. The peculiarities of the structure formation of the obtained copolymers depending on the initial composition formulation were established and their structural parameters were investigated: PVP grafting efficiency, PVP content in copolymer, molecular weight of internodal fragment of polymer network, crosslinking degree, and crosslinking density. The interrelation of sorption–diffusion, physical–mechanical and thermophysical properties along with the structure of the obtained materials was proved. It was shown that with the increasing PVP content in the original composition, the efficiency of its grafting and crosslinking density of the polymer network decreased, but the surface hardness, heat resistance, sorption capacity of copolymers in the dry state, as well as ion permeability and elasticity in the swollen state increased, while their tensile strength deteriorated. It is proved that by changing the original composition formulation it is possible to change the structure and hence the properties of the copolymers in the desired direction.

Rational Design of Amphiphilic Diblock Copolymer/MWCNT Surface Modifiers and Their Application for Direct Electrochemical Sensing of DNA

We demonstrate the application of amphiphilic ionic poly(n-butylmethacrylate)-block- poly(2-(dimethylamino)ethyl methacrylate) diblock copolymers (PnBMA40-b-PDMAEMA40, PnBMA40-b-PDMAEMA120, PnBMA70-b-PDMAEMA120) for dispersing multiwalled carbon nanotubes (MWCNTs) in aqueous media, a subsequent efficient surface modification of screen-printed electrodes (SPEs), and the application of the modified SPEs for DNA electrochemistry. Stable and fine aqueous dispersions of MWCNTs were obtained with PnBMAx-b-PDMAEMAy diblock copolymers, regardless of the structure of the copolymer and the amount of MWCNTs in the dispersions. The effect of the diblock copolymer structure was important when the dispersions of MWCNTs were deposited as modifying layers on surfaces of SPEs, resulting in considerable increases of the electroactive surface areas and great acceleration of the electron transfer rate. The SPE/(PnBMAx-b-PDMAEMAy + MWCNT) constructs were further exploited for direct electrochemical oxidation of the guanine (G) and adenine (A) residues in a model salmon sperm double-stranded DNA (dsDNA). Two well-defined irreversible oxidation peaks were observed at about +600 and +900 mV, corresponding to the electrochemical oxidation of G and A residues, respectively. A multi-parametric optimization of dsDNA electrochemistry enables one to get the limits of detection (LOD) as low as 5 μg/mL (0.25 μM) and 1 μg/mL (0.05 μM) for G and A residues, respectively. The achieved sensitivity of DNA assay enables quantification of the A and G residues of dsDNA in the presence of human serum and DNA in isolated human leukocytes.