DMAEMA Content Research Articles

Evidences for charged hydrogen bonds on surfaces bearing weakly basic pendants: The case of PMMA–ran–PDMAEMA polymeric films

Positively charging a solid surface usually confers on it a bactericidal action that increases with the charge density. The latter may be modulated by chemically specific interactions between surface groups such as charged hydrogen bonds. As this possibility has not yet been extensively investigated, we studied the surface electrolytic properties of PEG–b–(PMMA–ran–PDMAEMA)n plaques by means of contact angle titrations, ATR–FTIR spectroscopy, DFT electronic structure calculations, and Monte Carlo titration simulations. Contact angle titrations highlighted the impact that polymer composition and film preparation have on plaques surface energy upon changing the pH. Following the relative increase in IR N–H bending absorption due to ammonium formation via FTIR experiments suggested, instead, an increase of surface groups pKb compared to free DMAEMA monomers. Interestingly, the N–H bending absorption for polymers with high DMAEMA contents appeared one pH unit below than for the low DMAEMA content cases. Basing on electronic structure harmonic frequencies analysis and Monte Carlo simulations, we rationalize the difference in apparent pKb as related to a shift in N–H bending frequency (+120 cm−1) due to a more likely ammonium–amine dimerization. We predict that a sufficient density of free N–H groups ought to appear at lower pH values the higher is the DMAEMA contents.

PH-Triggered Drug Release of Monodispersed P(St-co-DMAEMA) Nanoparticles: Effects of Swelling, Polymer Chain Flexibility and Drug-Polymer Interactions

Monodispersed pH-sensitive poly(styrene-co-N,N′-dimethylaminoethyl methacrylate) (P(St-co- DMAEMA)) nanoparticles (NPs) were synthesized by emulsion polymerization for use in potential applications in targeted drug delivery to the tumor microenvironment. pH-Sensitive volume swelling and drug release of the NPs with varied St/DMAEMA molar ratios, crosslinking degrees and model drug coumarin-6 loading were explored in vitro to elucidate the pH-sensitive drug release mechanisms. The swelling of the NPs, which accounts for the electrostatic repulsion of protonated tertiary amine groups under acidic conditions, reaches maximum at low pH, low crosslinking density and high DMAEMA content. The NPs undergo a pH-triggered drug release, and under the condition of pH 5 and pH 2, the average release rate during 24 h is 1.5-fold and 3-fold higher than that at physiological pH, respectively. The pH-triggered drug release is related to pH-sensitive swelling, polymer chain flexibility and drug-polymer interaction, and is significantly impacted by the St/DMAEMA molar ratio, degree of crosslinking and drug loading.

Investigation of cationic soapless P(St-co-DMAEMA) latex and its electrostatic adsorption of laponite

Cationic poly(styrene-co-N,N-dimethylaminoethyl methacrylate) (P(St-co-DMAEMA)) latexes were prepared in the absence of surfactant by using 2,2’ -azobis (2-methylpropionamidine) dihydrochloride (AIBA) as the initiator. The effects of the AIBA concentration, HCl/DMAEMA molar ratio and DMAEMA amount on the emulsion polymerization and the latex properties were investigated. The particle morphology and size, the zeta potential and the amino distribution of the P(St-co-DMAEMA) latexes were characterized by transmission electron microscope (TEM), dynamic light scattering (DLS) and conductometric titration, respectively. Results showed that the emulsion polymerization performed smoothly with high monomer conversion and narrow particle size distribution under the optimized conditions with AIBA concentration of 1 wt%, HCl/DMAEMA molar ratio of 1.2 and DMAEMA content of 5 wt%. The diameter of the dried latex particles decreased and the density of amino groups on the particle surfaces increased with increasing the DMAEMA content. The zeta potential of the P(St-co-DMAEMA) latexes was pH-dependent and the zero point was around at pH 7.2. A facile method was developed to fabricate P(St-co-DMAEMA)/laponite hybrid nanoparticles via electrostatic adsorption, in which the loading capacity of laponite platelets reached 17.7 wt%, and the resultant hybrid nanoparticles showed good thermal stability.

Grafting of pH-sensitive poly (N,N-dimethylaminoethyl methacrylate-co-2-hydroxyethyl methacrylate) onto HNTS via surface-initiated atom transfer radical polymerization for controllable drug release

ABSTRACTCopolymer brushes composed of N,N-dimethylaminoethyl methacrylate (DMAEMA) and 2-hydroxyethyl methacrylate (HEMA) were tethered on the surface of HNTs (HNTs) through surface-initiated atom transfer radical polymerization (SI-ATRP). ATRP initiator was anchored to surface and copolymers were synthesized from surface with different compositions of monomers. Successful grafting of copolymer brushes was approved by FTIR, TGA, XPS, FE-SEM, TEM, and N2 adsorption-desorption.1H NMR was used to determine the composition of copolymers. pH-sensitive properties of copolymer-grafted nanotubes were investigated by UV-visible absorbance in different pH values. Finally, loading and in vitro drug release from neat and copolymer-grafted HNTs were investigated using diphenhydramine hydrochloride as a model drug. Incorporation of DMAEMA to structure of polymers led to pH sensitivity of grafted-copolymers and controlled release of drug upon varying the pH of release medium. pH-dependent drug release showed that drug release was increased by decreasing pH of release medium and increasing DMAEMA content.

Preparation and application in drug controlled delivery of pH‐sensitive P(CE‐co‐DMAEMA‐co‐MEG) hydrogel

ABSTRACTA pH‐sensitive hydrogel [P(CE‐co‐DMAEMA‐co‐MEG)] was synthesized by the free‐radical crosslinking polymerization of N,N‐dimethylaminoethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate(MPEG‐Mac) and methoxyl poly(ethylene glycol)‐poly(caprolactone)‐methacryloyl methchloride (PCE‐Mac). The effects of pH and monomer content on swelling property, swelling and deswelling kinetics of the hydrogels were examined and hydrogel microstructures were investigated by SEM. Sodium salicylate was chosen as a model drug and the controlled‐release properties of hydrogels were pilot studied. The results indicated that the swelling ratios of the gels in stimulated gastric fluids (SGF, pH = 1.4) were higher than those in stimulated intestinal fluids (SIF, pH = 7.4), and followed a non‐Fickian and a Fickian diffusion mechanism, respectively. In vitro release studies showed that its release rate depends on different swelling of the network as a function of the environmental pH and DMAEMA content. SEM micrographs showed homogenous pore structure of the hydrogel with open pores at pH 1.4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40737.

Assessment of new biocompatible Poly(N-(morpholino)ethyl methacrylate)-based copolymers by transfection of immortalized keratinocytes

Skin carcinomas are among the most commonly diagnosed tumors in the world. In this study, we investigated the transfection of immortalized keratinocytes, used as an in vitro model for skin carcinoma, using the antisense technology and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)-based copolymers. In order to improve the transfection efficiency of the classic PDMAEMA polymers, copolymers were synthesized including a poly(N-morpholino)ethylmethacrylate) (PMEMA) moiety for an improved proton-sponge effect, intended to favour the release of the oligonucleotide from the acidic endosome. These copolymers were synthesized either statistically (with alternating PDMAEMA and PMEMA fragments) or in blocks (one PDMAEMA block followed by one PMEMA block). MTT assays were performed using the PDMAEMA-PMEMA copolymers and revealed no significant cytotoxicity of these polymers at an N/P ratio of 7.3. Using fluorescent oligonucleotides and analyzing transfection efficiency by flow cytometry, we noticed no significant differences between the two kinds of copolymers. However copolymers with a higher DMAEMA content and a higher Mn were also those displaying the highest vectorization efficiency. Confocal microscopy showed that these copolymers induced a fine granular distribution of the transfected antisense oligonucleotides inside the cells. We also assessed the functionality of the transfected antisense oligonucleotide by transfecting immortalized GFP expressing keratinocytes with a GFP antisense oligonucleotide using these copolymers. A significant silencing was achieved with a PDMAEMA-PMEMA in block copolymer (Mn = 41 000, 89 % PDMAEMA). Together, these results suggest that PDMAEMA-PMEMA copolymers combining low toxicity, vectorization and proton sponge properties, can be efficiently used to transfect immortalized keratinocytes and so open new perspectives in the therapy of skin carcinomas as well as of other skin diseases of genetic or immunological origin.

Radiation synthesis of acrylamide/N,N-(dimethylamino) ethyl methacrylate grafted onto low density polyethylene films

Radiation-induced graft copolymerization of acrylamide/N,N-(dimethylamino) ethyl methacrylate (AAm/DMAEMA) onto low density polyethylene films was carried out. The effect of grafting conditions such as solvent type and comonomer composition were studied. Characterization of the prepared films was investigated by Fourier transform infrared. Some selected properties such as thermal stability and swelling behavior were determined. It was found that grafting efficiency, swelling behavior and thermal stability increased with increasing DMAEMA content. Scanning electron microscopy was used for predicting the change in surface morphology via the grafted films. The improvement in properties of the prepared films make it possible to use them in some practical applications.

Synthesis, Swelling and Drug-Release Behaviour of a Poly(N,N-diethylacrylamide-co-(2-dimethylamino) ethyl methacrylate) Hydrogel

In this study, poly(N,N-diethylacrylamide-co-(2-dimethylamino) ethyl methacrylate) (poly(DEA-co-DMAEMA)) hydrogels were synthesized by changing the initial DEA/DMAEMA mol ratio. The hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). In comparison with the PDEA hydrogel, the equilibrium swelling ratio (ESR) and lower critical solution temperature (LCST) of the hydrogels increase with the increase of DMAEMA content in the feed. The deswelling and reswelling kinetics and cytotoxicity of the different composition ratios of DEA to DMAEMA in the co-polymerized hydrogels were also investigated in detail. The absorption and release behaviour of the model drug, bovine serum albumin, were found to be dependent on hydrogel composition and environment temperature, which suggests that these materials have potential application as intelligent drug carriers.

Synthesis and Characterization of Novel Poly(N-isopropylacrylamide-co-N,N′-dimethylaminoethyl methacrylate sulfate) Hydrogels

Poly(N-isopropylacrylamide-co-N,N′-dimethylaminoethyl methacrylate sulfate) [P(NIPAM-co-DMAEMASA)] was prepared from N-isopropylacrylamide (NIPAM) and N,N-dimethylaminoethyl methacrylate sulfate (DMAEMASA) monomers, and its properties were compared with those of poly(N-isopropylacrylamide-co-N,N′-dimethylaminoethyl methacrylate) [P(NIPAM-co-DMAEMA)]. The copolymers were characterized by swelling measurements in distilled water (10−40 °C) and buffer solutions (I = 0.1 M, pH = 2.2−10.0), FTIR, DSC, and SEM methods. The ESV’s of the NIPAM-DMAEMASA copolymers in distilled water were 5 times higher than those of P(NIPAM-co-DMAEMA); they decreased with an increase in comonomer (DMAEMASA/DMAEMA) content for both copolymers. While NIPAM-DMAEMASA copolymers did not display any phase transition with temperature, the LCST of the NIPAM-DMAEMA copolymer was determined as 20 °C. Both copolymers displayed a phase transition at pH = 5.0, but the pH of the phase transition for NIPAM-DMAEMA gels shifted to 7.0 with increased DMAEMA content. Glass transition temperatures of NIPAM copolymers did not change with the type and content of comonomer.

End‐linked amphiphilic polymer conetworks: Synthesis by sequential atom transfer radical polymerization and swelling characterization

AbstractConetworks based on end‐linked homopolymers and amphiphilic gradient copolymers were synthesized by the atom transfer radical polymerization (ATRP) of 2‐(dimethylamino)ethyl methacrylate (DMAEMA, hydrophilic monomer), methyl methacrylate (MMA, hydrophobic monomer), and ethylene glycol dimethacrylate (EGDMA, hydrophobic cross‐linker). Sequential, rather than step‐wise polymerizations, were performed to enhance the livingness of the polymerization, particularly for the end‐linking step, and to ultimately obtain conetworks based on gradient rather than pure block copolymers. Amphiphilic conetworks based on end‐linked MMA‐DMAEMA‐MMA gradient copolymers of different compositions were successfully synthesized as confirmed by the narrow molecular weight distributions of the linear precursors, the rigidity of the amphiphilic conetwork products and the low sol‐fraction extracted from the conetworks. Similarly successful was the ATRP synthesis of an end‐linked conetwork based on a DMAEMA‐MMA statistical copolymer and of a randomly cross‐linked conetwork that resulted from the simultaneous terpolymerization of DMAEMA, MMA and EGDMA. An amphiphilic conetwork based on an end‐linked DMAEMA‐MMA‐DMAEMA gradient copolymer presented a less rigid, mucous‐like, texture. The degrees of swelling (DS) in tetrahydrofuran of all the conetworks were higher than those measured in pure water, whereas the aqueous DS values increased by lowering the pH and increasing the DMAEMA content of the conetworks. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1878–1886, 2010

Study on the Sensitive Property of Poly(AMPS-co-DMAEMA) Hydrogel under Electric Stimulation

Taking 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and 2-dimethylamino ethyl methacrylate (DMAEMA) as monomers, taking N,N’-methylenebis acrylamide as the cross linker, and taking the ammonium persulfate and sodium bisulfite as the redox initiators, we adopted the aqueous polymerization to prepare the Ploy(AMPS-co-DMAEMA) hydrogel and studied the shrinking and bending behaviors of hydrogel under exterior DC electric field stimulation. The result indicated that the DMAEMA monomer content and the pressure could significantly influence the electric sensitivity of hydrogel. With the increase of the DMAEMA content and the non-contract electric field, the Poly(AMPS-co-DMAEMA) hydrogel first bended toward the cathode and then bended toward the anode.

Temperature- and pH-Responsive Dense Copolymer Brushes Prepared by ATRP

Dual responsive molecular brushes consisting of statistical copolymers of di(ethylene glycol) methyl ether methacrylate (MEO2MA) and either methacrylic acid (MAA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) were synthesized by grafting from poly(2-(2-bromoisobutyroyloxy)ethyl methacrylate (PBIEM) macroinitiators using atom transfer radical polymerization (ATRP). Copolymer brushes with controlled composition and molecular weights ranging from Mn = 600 000 to 1 400 000 with polydispersity indexes (Mw/Mn) between 1.18 and 1.45 were obtained. The lower critical solution temperature (LCST) of MEO2MA-stat-MAA decreased with the increasing molar fraction of MAA in the copolymer in deionized water but increased in buffer solution at pH 7. At pH 9, the hydrophilicity of polymer increased with ionization of carboxylic acid to further raise the LCST. On the other hand, the LCST of MEO2MA-stat-DMAEMA copolymers increased with increasing DMAEMA content at pH 4, 7, and 9. A bottle-brush terpolymer prepared from all...

Synthesis and characterization of amphiphilic conetworks based on multiblock copolymers

Model amphiphilic conetworks based on cross-linked block copolymers of the hydrophilic ionizable 2-(dimethylamino)ethyl methacrylate (DMAEMA, 25 nominal units per block) and the hydrophobic n-butyl methacrylate (BuMA, 5 nominal units per block) bearing three, five, seven and nine blocks were synthesized using group transfer polymerization. 1,4-Bis(methoxytrimethylsiloxymethylene)cyclohexane and ethylene glycol dimethacrylate were used as the bifunctional initiator and the cross-linker, respectively. Network synthesis was performed by sequential monomer/cross-linker additions to the reaction flask, which was pre-loaded with tetrabutylammonium bibenzoate (polymerization catalyst), tetrahydrofuran (THF, solvent), and initiator. All linear conetwork precursors were characterized using gel permeation chromatography and proton nuclear magnetic resonance spectroscopy and found to have molecular weights (MWs) and compositions reasonably close to the theoretically expected values. All polymer conetworks were characterized in terms of their degree of swelling (DS) in THF, in neutral water, and in aqueous media as a function of the solution pH. It was found that the DSs were highest in acidic pH due to the repulsive forces and the osmotic pressure developed by the ionization of the DMAEMA units. Intermediate values of the DSs were observed in THF, whereas the lowest DSs were measured in neutral water. In THF, the DSs increased with the MWs of the (final) linear (co)polymer precursors, while in acidic water the DSs increased with the DMAEMA content in the (co)networks.

Synthesis and swelling behavior of poly(2‐dimethylaminoethyl methacrylate‐co‐N‐hydroxymethyl acrylamide) hydrogels

AbstractCrosslinked poly(2‐(N,N‐dimethylamino)ethyl methacrylate‐co‐N‐hydroxymethyl acrylamide) poly(DMAEMA‐co‐NHMAAM) copolymers were synthesized using ammonium persulfate (APS)/N,N,N′,N′‐tetramethyl ethylenediamine (TEMED) as initiator/accelerator system in the presence of tetraethyleneglycol diacrylate (TEGDA) as crosslinker in water at 60°C. The effects of comonomer composition in the feed, pH of the swelling medium, and the temperature on the equilibrium swelling (ES) values of hydrogels were investigated. While the initial total monomer concentration was kept constant at 0.5 or 1 mol/l, the contents of APS and TEGDA in the feed were 1 mol% of the total monomers. ES values of DMAEMA‐NHMAAM gels increased with the increase in DMAEMA content in the feed. Although DMAEMA‐NHMAAM hydrogels containing up to 30 mol% were transparent in appearance, the presence of 40% DMAEMA in the copolymer worsened its transparency. ES values of the copolymer gels with high DMAEMA contents increased with both temperature and the pH of swelling medium. Copyright © 2006 John Wiley & Sons, Ltd.

Binding of butyl orange by poly(2‐dimethylaminoethyl methacrylate) and copolymers of 2‐dimethylaminoethyl methacrylate and N‐vinyl‐2‐pyrrolidone: Peculiar temperature dependence of the binding

AbstractThe temperature dependence of the binding of butyl orange by a homopolymer of 2‐dimethylaminoethyl methacrylate (DMAEMA) and copolymers of DMAEMA and N‐vinyl‐2‐pyrrolidone (VPy) has been examined at various pH's. The binding is very much dependent upon the temperature of the system, the pH of the binding medium, and the DMAEMA content in the polymer. In this case maximal binding is obtained at approximately 15–25° in the temperature range measured, although in most cases which have been examined, the degree of binding increases steadily with increasing temperature. This peculiar temperature dependence of the binding becomes more pronounced as the pH and the DMAEMA content are increased. The appearance of the peculiarity is discussed in terms of the pH‐induced conformational changes of the polymer and the hydrophobicity of the polymer.