Triethylene Glycol Methacrylate Research Articles

New Amphiphilic Terpolymers of N-Vinylpyrrolidone with Acrylic Acid and Triethylene Glycol Dimethacrylate as Promising Drug Delivery: Design, Synthesis and Biological Properties In Vitro.

The terpolymers of N-vinylpyrrolidone (VP) with acrylic acid and triethylene glycol methacrylate were synthesized with more than 90% yield by radical copolymerization in ethanol from monomeric mixtures of different molar composition (98:2:2, 95:5: 2 and 98:2:5) and their monomer composition, absolute molecular masses and hydrodynamic radii in aqueous media were determined. Using the MTT test, these terpolymers were established to be low toxic for non-tumor Vero cells and HeLa tumor cells. Polymer compositions of hydrophobic dye methyl pheophorbide a (MPP) based on studied terpolymers and linear polyvinylpyrrolidone (PVP) were obtained and characterized in water solution. Quantum-chemical modeling of the MPP-copolymer structures was conducted, and the possibility of hydrogen bond formation between terpolymer units and the MPP molecule was shown. Using fluorescence microscopy, the accumulation and distribution of polymer particles in non-tumor (FetMSC) and tumor (HeLa) cells was studied, and an increase in the accumulation of MPP with both types of particles was found.

Microfluidic Controlled Self-Assembly of Polylactide (PLA)-Based Linear and Graft Copolymers into Nanoparticles with Diverse Morphologies.

This study outlines the microfluidic (MF) controlled self-assembly of polylactide (PLA)-based linear and graft copolymers. The PLA-based copolymers (PLA-Cs) were synthesized through a convenient one-pot/one-step ROP/RAFT technique. Three distinct vinyl monomers-triethylene glycol methacrylate (TEGMA), 2-hydroxypropyl methacrylate (HPMA), and N-(2-hydroxypropyl) methacrylamide (HPMAA) were employed to prepare various copolymers: linear thermoresponsive polylactide-b-poly(triethylene glycol methacrylate) (PLA-b-PTEGMA), graft pseudothermoresponsive poly[N-(2-hydroxypropyl)] methacrylate-g-polylactide (PHPMA-g-PLA), and graft amphiphilic poly[N-(2-hydroxypropyl)] methacrylamide-g-polylactide (PHPMAA-g-PLA). The MF technology was utilized for the controlled self-assembly of these PLA-based BCs in a solution, resulting in a range of nanoparticle (NP) morphologies. The thermoresponsive PLA-b-PTEGMA diblock copolymer formed thermodynamically stable micelles (Ms) through kinetically controlled assemblies. Similarly, employing MF channels led to the self-assembly of PHPMA-g-PLA, yielding polymersomes (PSs) with adjustable sizes under the same solution conditions. Conversely, the PHPMAA-g-PLA copolymer generated worm-like particles (Ws). The analysis of resulting nano-objects involves techniques such as transmission electron microscopy, dynamic light scattering investigations (DLS), and small-angle X-ray scattering (SAXS). More specifically, the thermoresponsive behavior of PLA-b-PTEGMA and PHPMA-g-PLA nano-objects is validated through variable-temperature DLS, TEM, and SAXS methods. Furthermore, the study explored the specific interactions between the formed Ms, PSs, and/or Ws with proteins in human blood plasma, utilizing isothermal titration calorimetry.

Self-Assembled Amphiphilic Fluorinated Random Copolymers for the Encapsulation and Release of the Hydrophobic Combretastatin A-4 Drug.

Water-soluble amphiphilic random copolymers composed of tri(ethylene glycol) methacrylate (TEGMA) or poly(ethylene glycol) methyl ether methacrylate (PEGMA) and perfluorohexylethyl acrylate (FA) were synthesized by ARGET-ATRP, and their self-assembling and thermoresponsive behavior in water was studied by dynamic light scattering (DLS) and UV-vis spectroscopy. The copolymer ability to self-fold in single-chain nano-sized structures (unimer micelles) in aqueous solutions was exploited to encapsulate Combretastatin A-4 (CA-4), which is a very hydrophobic anticancer drug. The cloud point temperature (Tcp) was found to linearly decrease with increasing drug concentration in the drug/copolymer system. Moreover, while CA-4 was preferentially incorporated into the unimer micelles of TEGMA-ran-FA, the drug was found to induce multi-chain, submicro-sized aggregation of PEGMA-ran-FA. Anyway, the encapsulation efficiency was very high (≥81%) for both copolymers. The drug release was evaluated in PBS aqueous solutions both below and above Tcp for TEGMA-ran-FA copolymer and below Tcp, but at two different drug loadings, for PEGMA-ran-FA copolymer. In any case, the release kinetics presented similar profiles, characterized by linear trends up to ≈10–13 h and ≈7 h for TEGMA-ran-FA and PEGMA-ran-FA, respectively. Then, the release rate decreased, reaching a plateau. The release from TEGMA-ran-FA was moderately faster above Tcp than below Tcp, suggesting that copolymer thermoresponsiveness increased the release rate, which occurred anyway by diffusion below Tcp. Cytotoxicity tests were carried out on copolymer solutions in a wide concentration range (5–60 mg/mL) at 37 °C by using Balb/3T3 clone A31 cells. Interestingly, it was found that the concentration-dependent micro-sized aggregation of the amphiphilic random copolymers above Tcp caused a sort of “cellular asphyxiation” with a loss of cell viability clearly visible for TEGMA-ran-FA solutions (Tcp below 37 °C) with higher copolymer concentrations. On the other hand, cells in contact with the analogous PEGMA-ran-FA (Tcp above 37 °C) presented a very good viability (≥75%) with respect to the control at any given concentration.

Controlling the lectin recognition of glycopolymers via distance arrangement of sugar blocks.

The arrangement of sugars in glycopolymers contributes to their recognition. The molecular recognition of proteins was controlled by the living radical polymerization of glycopolymers. The glycopolymers were prepared by the copolymerization of propargyl methacrylate (Pr-MA) and triethyleneglycol methacrylate (TEG-MA) via living radical polymerization with a reversible addition-fragmentation glycopolymer chain transfer (RAFT) reagent and by subsequent sugar conjugation by click chemistry. The block copolymers were prepared by the polymerization of Pr-MA and TEG-MA. The molecular recognition of glycopolymers was analyzed using the fluorescence quenching of lectin and found to be dependent on the glycopolymer structures. Two-site binding of glycopolymers to concanavalin A (ConA) was attained by both the glycopolymer with a 105-mer and the tri-block glycopolymer with a 103-mer. Glycopolymers with either a 27- or 54-mer showed much weaker interaction because of one-site binding. The molecular recognition of the glycopolymer was controlled by the arrangement and size of the sugar cluster and not by the sugar density.

Well-defined podophyllotoxin polyprodrug brushes: preparation via RAFT polymerization and evaluation as drug carriers

Novel poly(triethylene glycol methacrylate)-b-poly(podophyllotoxin methacrylate) copolymers (PTP) with a well-defined structure were designed and synthesized by direct RAFT polymerization with the hydrophobic monomer derivative from the anticancer drug podophyllotoxin.

Dual-stimuli responsive polymeric micelles: preparation, characterization, and controlled drug release

The preparation of stimuli-responsive polymeric micelles sensitive to both temperature and UV irradiation is achieved through the self-assembly from a series of amphiphilic block copolymers, poly(triethylene glycol methacrylate)-b-poly(2-nitrobenzyl methacrylate) (PTEGMA-b-PNBMA). The block ratios of the hydrophilic and thermo-responsive PTEGMA block to the hydrophobic and photoclevable PNBMA block are manipulated in the range of 4:1 to 1:1. The nanostructure and stimuli-responsive properties of the micelles are well-correlated with the chemical structures of the copolymers. The thermal transition temperature of micelles is reduced to 38–41 °C and close to body temperature as compared to that of PTEGMA homopolymer around 52 °C. After UV irradiation, the enhanced hydrophilicity of micelle core causes swelling and increased size of micelles. The capabilities of these micelles for drug encapsulation are demonstrated by using doxorubicin as the model drug and the subsequent drug release could be triggered by elevated temperature and/or UV irradiation. Furthermore, the potential application of these micelles in controlled drug release is explored by studying the in vitro cytotoxicity of drug-loaded micelles as triggered by external stimuli.

Synthesis and self-assembly of temperature-responsive copolymers based on N-vinylpyrrolidone and triethylene glycol methacrylate.

Polyvinylpyrrolidone (PVP) is a biocompatible, water-soluble polymer with unique physicochemical properties and attractive biological features that has found widespread use in several industries. Owing to advances in controlled polymerisation techniques, PVP can be easily synthesised with robust control over its architecture. However, the synthesis of PVP copolymers, which can allow tailoring of its properties and expand the scope of this polymeric material, is challenging and rarely reported. Here, we demonstrate the synthesis of well-defined, temperature-responsive polyvinylpyrrolidone-co-poly(triethylene glycol methacrylate) (PVP-co-pTEGMA) block copolymers via successive Reversible Addition-Fragmentation chain Transfer (RAFT) and Activators ReGenerated by Electron Transfer Atom Transfer Radical Polymerisation (ARGET-ATRP) techniques. We show that PVP-co-pTEGMA block copolymers display temperature-responsive behaviour and self-assemble above their cloud point temperature (Tcp) to form spherical nanostructures of 100-200 nm in diameter. Finally, we demonstrate stabilisation of these assemblies below their Tcp by cross-linking through the PVP block.

Synthesis of an original fluorinated triethylene glycol methacrylate monomer and its radical copolymerisation with vinylidene fluoride. Its application as a gel polymer electrolyte for Li-ion batteries

The synthesis and characterisation of novel poly[VDF-g-oligo(EO)] graft copolymers are presented.

Ад’ювантні властивості полімеру на основі акрилової кислоти

Adjuvant properties of the polymer containing acrylic acid, glycidyl methacrylate, triethylene glycol methacrylate and butyl acrylate have been established. Antibodies to ovalbumin and bovine serum albumin in the blood of mice were revealed using dot blot analysis and immunoenzyme analysis when applying the investigated polymer as a carrier of these protein antigens. Adjuvant properties of the polymer were compared to aluminum hydroxide, which is a component of many traditional vaccines. Experimental polymer was a stronger adjuvant because it led to an increase of specific antibodies against ovalbumin and bovine serum albumin.

Shape-Shifting Micro- and Nanopatterns Controlled by Temperature

Herein, features that alter their shape to form a different pattern upon an external trigger are described. Electron-beam lithography was used to fabricate micrometer- and nanometer-sized surface immobilized poly(triethylene glycol methacrylate) (pTEGMA) that exhibits significant thermal responsivity; the resulting hydrogels collapsed by up to 95% of their height upon addition of heat. Multicomponent features composed of both the thermoresponsive polymer and nonresponsive poly(ethylene glycol) (PEG) were then prepared. Upon increase in temperature, only the thermally responsive component of the pattern collapsed, causing a significant and predictable alteration in the overall pattern. Reversible micrometer- and nanometer-sized square-to-triangles, squares-to-checkerboards, smiles-to-neutral face, and zeros-to-ones shapes were shown.

Synthesis of Silica Hybrid Nanoparticles and the Effect of Their Addition on the Hardness of the Dental Nanocomposites

The objective of this study is to investigate the effect of silica hybrid nanoparticles on the hardness of the dental nanocomposites. The silica hybrid nanoparticles were synthesized by sol-gel method. The powders were modified with 3-methacryloxy-propyltrimethoxy silane (γ-MPS) either by co-condensation method or one-pot method. The silanized silica were then mixed with a mixture of bisglycidyl methacrylate (BisGMA), triethylene glycol methacrylate (TEGDMA), camphorquinone (CQ) and dimethylaminoethyl methacrylate (DMAEMA) to form dental nanocomposites. The hardness of the nanocomposites were determined using vickers hardness. The results shown that hardness of the dental composites using silica hybrid nanoparticles synthesized via one-pot method was higher compared to the synthesized via co-condensation method. Transmission Electron Microscope (TEM), and Fourier Transform Infrared Spectroscopy (FTIR) were used for characterization.

The preparation and characterization of co-polymer microgels with transition temperature at or near physiological values

In this study, triethyleneglycol methacrylate (TREGMA) containing long functional hydrophilic side chains (viz., -(-OCH2CH2-)3-OH), was selected to copolymerize with N-isopropylacrylamide (NIPAM) for the first time to prepare temperature-sensitive microgels. The structure and morphology of the microgels obtained were investigated through 1H NMR, transmission electron microscopy (TEM). Experimental results show that TREGMA can copolymerize well with NIPAM to prepare microgels with regular spherical morphology. Investigation on the volume phase transition of the microgels through turbidimetric method, dynamic light scattering (DLS) and differential scanning calorimetry (DSC) reveals that incorporation of hydrophilic side chains -(-OCH2CH2-)3-OH has strong influence on the sizes, size distribution and the deswelling properties of the microgels. The microgels exhibit much larger deswelling ratios (α) than pure poly(N-isopropylacrylamide)(pNIPAM) microgels. Foremost, the volume-phase transition temperature (VPTT) of the microgels can be modulated to well close to the normal body temperature of human beings. The characteristic makes the microgels competitive candidates for biomaterials.

Flocculation behavior of temperature-sensitive poly( N-isopropylacrylamide) microgels containing polar side chains with [sbnd]OH groups

The flocculation behavior of poly( N-isopropylacrylamide) (pNIPAM) microgels containing polar ( OCH 2CH 2 ) 3 OH chains, incorporated by the copolymeric components (triethyleneglycol methacrylate, TREGMA), in aqueous NaCl solution was investigated. Determination of the critical flocculation temperatures (CFTs) and the critical flocculation concentrations (CFCs) of the microgels at 45 °C shows that polar ( OCH 2CH 2 ) 3 OH chains have different influence on the flocculation behavior of the microgels at temperatures below and above their volume phase transition temperatures (VPTTs). The flocculation of the microgels becomes more difficult with the increase of ( OCH 2CH 2 ) 3 OH chains below the VPTT. In contrast, the microgels flocculate more easily with more ( OCH 2CH 2 ) 3 OH chains above the VPTT. Preliminary investigation on the flocculation kinetics of the microgels further shows that ( OCH 2CH 2 ) 3 OH chains have different effects on the flocculation rate at temperatures below and above the VPTT. The flocculating rate of the microgels at 25 °C decreases with the increase of ( OCH 2CH 2 ) 3 OH chains. While the flocculation rate at 45 °C increases with the increase of ( OCH 2CH 2 ) 3 OH chains due to their enrichment on the surface of the microgels as a result of the temperature-induced volume-phase transition, which was verified by variable temperature 1H NMR spectroscopy. The polar ( OCH 2CH 2 ) 3 OH chains rich in the surface increase the attractive force between the microgels, promoting the flocculation.

Deswelling comparison of temperature‐sensitive poly(N‐isopropylacrylamide) microgels containing functional OH groups with different hydrophilic long side chains

AbstractTwo monomers containing functional OH groups with different hydrophilic long side chains (viz., triethyleneglycol methacrylate (TREGMA) and polyethyleneglycol methacrylate (PEGMA)) were selected to modify the swelling/deswelling behavior of poly(N‐isopropylacrylamide) (pNIPAM) microgels. Dynamic scattering technique, turbidimetric method, and differential scanning calorimetry (DSC) were employed to investigate the deswelling behavior of the microgels. Experimental results show that the two series of microgels are identical in that incorporation of hydrophilic chains containing OH groups causes the volume‐phase transition temperature (VPTT) of pNIPAM microgels to shift to higher temperature; the more hydrophilic the side chains, the more the VPTTs shift. Although PEGMA are more effective in elevating the VPTTs of pNIPAM microgels than TREGMA, p(NIPAM‐co‐TREGMA) microgels show better deswelling properties than p(NIPAM‐co‐PEGMA) microgels, i.e., they have much larger deswelling ratios (α) and display less continuous volume‐phase transition. The VPTTs of the modified microgels can be modulated to well close to the normal body temperature of human beings. These characteristics along with the functional OH groups they contain make the microgels competitive candidates for biomaterials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3575–3583, 2005

Monomer permeability of disposable dental gloves

Statement of problem Studies have suggested that monomers may be able to permeate dental gloves. Purpose This study examined the permeability of disposable dental gloves to 6 kinds of dental monomers. Material and methods The permeability of 6 kinds of dental monomers (methyl methacrylate [MMA], 2-hydroxyethyl methacrylate [HEMA], triethyleneglycol methacrylate [TEGDMA], ethyleneglycol dimethacrylate [EGDMA], urethane dimethacrylate [UDMA], and Bis-glycidyl methacrylate [Bis-GMA]) through 5 kinds of dental gloves (latex, powder-free latex, coated latex, polychloroprene, and polyvinyl chloride) was examined for up to 180 minutes at 37°C. The fingers of unused gloves without pin holes were cut and used in the experiments. Five specimens per test group were examined. One type of monomer was poured into each finger and dipped in ethanol. The ethanol for extraction was measured by a spectrophotometer at a wavelength of 210 nm, and the results were analyzed by analysis of variance and the Kruskal-Wallis test ( P<.05). Results Four of the monomers tested (MMA, HEMA, TEGDMA, and EGDMA) permeated the gloves tested, whereas 2 (UDMA and Bis-GMA) did not ( P>.01). The amount of monomers permeating the latex in 10 minutes was 0.8 ± 0.6, 0.6 ± 0.6, 0.07 ± 0.1, 0.07 ± 0.1, 0.1 ± 0.1 and 0.06 ± 0.1 μL/mL for MMA, HEMA, EGDMA, TEGDMA, UDMA, and Bis-GMA, respectively. The amount of permeated monomer was then increased in relation to the examination time, and in MMA and HEMA, permeation occurred rapidly during the initial 60 minutes at 3 times the 10-minute values, then continued gradually and linearly. The polyvinyl chloride glove showed the greatest monomer permeability. Two-way analysis of variance showed significant correlations between MMA, HEMA, EGDMA or TEGDMA and UDMA or Bis-GMA ( P<.01). Statistical significance was shown between polyvinyl chloride and latex, powder-free latex, coated latex or polychloroprene ( P<.01). However, there was no significant relation between any kind of dental monomer and any kind of dental glove. Conclusion Within the limitations of this study, 4 of the monomers tested permeated all of the gloves tested.

Surface Mobility of Grafted Hydrogels

Solid-supported hydrogels were prepared by ozone-induced graft polymerization of 2-hydroxyethyl methacrylate (HEMA), diethylene glycol methacrylate (DEGMA), and triethylene glycol methacrylate (TEGMA) onto polypropylene substrates. Angle-dependent ESCA showed a gradient in chemical composition in the near-surface region (thickness 55 A). The various shapes of the C 1s peaks collected at a takeoff angle of 45° corresponded to what could be expected from the chemical composition of polyHEMA, polyDEGMA, and polyTEGMA, respectively. At a takeoff angle of 15°, all grafted polymers showed a more hydrophobic character with respect to the shape of the C 1s peak. During dynamic contact angle measurements, HEMA-grafted fibers showed the largest contact angle hysteresis, with an advancing contact angle of about 90° and receding contact angle close to zero. A less pronounced contact angle hysteresis for both DEGMA and TEGMA-grafted fibers was explained by a hindered reorientation as a consequence of an increased side chain length of the grafted polymers. A suppressed contact angle hysteresis was also obtained for fibers grafted in a HEMA monomer mixture containing 5% cross-linker (EDMA). Such surfaces also showed good reproducibility when sequential wetting cycles were performed during the dynamic contact angle measurements.

Polyfunctional polymer sorbents

The gas chromatographic properties of polyfunctional polymer sorbents, particularly those based on triethylene glycol methacrylate and butyl methacrylate and N-vinyl-3(5)-methylpyrazole and ethylene glycol dimethacrylate copoymers have been studied. The thermodynamic characteristics of sorption on these polymer sorbents have been investigated. The correlation betweenchanges in the sorption energy and entropy has been determined. It has been shown that in the system sorbate—polymer sorbent, the mechanism of interaction depends on the chemical nature, physical state and structural characteristics of the sorbent and chemical nature and molecular size of the sorbate.

Study of the chromatographic capability of butyl methacrylate gels

Suspension polymerization was used to synthesize hydrophobic gels based on butyl methacrylate and triethylene glycol methacrylate in the presence and absence of n-heptane. The resulting gels were subjected to gel chromatographic analysis to determine their permeability limits, distribution coefficients and separating power. The gels were found suitable for use in the liquid (sieve) chromatography of oligomers.