Aminoethyl Methacrylate Research Articles

Reversible Stimuli-Dependent Aggregation-Induced Emission from a "Nonfluorescent" Amphiphilic PVDF Graft Copolymer.

A poly(vinylidine fluoride) graft random copolymer of t-butyl aminoethyl methacrylate (tBAEMA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA, Mn = 300) [PVDF-g-P(tBAEMA-ran-OEGMA), PVBO] is synthesized by atom transfer radical polymerization (ATRP), and PVBO is fractionated to get a highly water-soluble fraction (PVBO-1) showing a reversible on/off fluorescence behavior with gradual increase and decrease in pH, respectively, achieving a maximum quantum yield of 0.18 at pH = 12. PVBO-1 dissolved in water shows large multimicellar aggregates (MMcA), but at pH 12, crumbling of larger aggregates to much smaller micelles occurs, forming nonconjugated polymer dots (NCPDs), as supported by transmission electron microscopy and dynamic light scattering study. The reversible fluorescence on/off behavior also occurs with the decrease and increase of temperature. Theoretical study indicates that, at high pH, most of the amino groups become neutral and exhibit a strong tendency to form aggregates from crowding of a large number of carbonyl and amine groups, minimizing the HOMO-LUMO gap, showing an absorption peak at the visible region, and generating aggregation-induced emission.

Equilibrium Swelling of Biocompatible Thermo-Responsive Copolymer Gels.

Biomedical applications of thermo-responsive (TR) hydrogels require these materials to be biocompatible, non-cytotoxic, and non-immunogenic. Due to serious concerns regarding potential toxicity of poly(N-isopropylacrylamide) (PNIPAm), design of alternative homo- and copolymer gels with controllable swelling properties has recently become a hot topic. This study focuses on equilibrium swelling of five potential candidates to replace PNIPAm in biomedical and biotechnological applications: poly(N-vinylcaprolactam), poly(vinyl methyl ether), poly(-dimethyl amino ethyl methacrylate), and two families of poly(2-oxazoline)s, and poly(oligo(ethylene glycol) methacrylates). To evaluate their water uptake properties and to compare them with those of substituted acrylamide gels, a unified model is developed for equilibrium swelling of TR copolymer gels with various types of swelling diagrams. Depending on the strength of hydrophobic interactions (high, intermediate, and low), the (co)polymers under consideration are split into three groups that reveal different responses at and above the volume phase transition temperature.

PH-Sensitive Polycations for siRNA Delivery: Effect of Asymmetric Structures of Tertiary Amine Groups.

pH-sensitive polyelectrolytes provide enormous opportunity for siRNA delivery. Especially, their tertiary amine structures can not only bind genes but also act as pH-sensitive hydrophobic structure to control genes release. However, the influence of molecular structures on siRNA delivery still remains elusive, especially for the asymmetric alkyl substituents of the tertiary amine groups. Herein, a library of N-methyl-N-alkyl aminoethyl methacrylate monomers (MsAM) with asymmetric alkyl substituents on the tertiary amine group is synthesized and used to prepare a series of tri-block polycationic copolymers poly(aminoethyl methacrylate)-block-poly (N-methyl-N-alkyl aminoethyl methacrylate)-block-poly(ethylene glycol methacrylate) (PAMA-PMsMA-PEG). And the properties of these polycations and their self-assembled micelles are characterized, including molecular structure, proton buffering capacity, pH-sensitivity, size, and zeta potential. With the length increase of one alkyl substituent, the proton buffering capacity of both monomers and polycations is demonstrated to be narrowed down. The siRNA delivery efficiency and cytotoxicity of these micelles are also evaluated on HepG2 cells. In particular, poly(aminoethyl methacrylate)-block-poly(N-methyl-N-ethyl aminoethyl methacrylate)-block-poly(ethylene glycol methacrylate) (PAMA-PMEMA-PEG) elicited the best luciferase knockdown efficiency and low cytotoxicity. Besides, PAMA-PMEMA-PEG/siRRM2 also induced significant anti-tumor activity in vitro. These results indicated PAMA-PMEMA-PEG has potential for further use in the design of gene vehicles with the improved efficiency of siRNA delivery.

Three-dimensional composite electrospun nanofibrous membrane by multi-jet electrospinning with sheath gas for high-efficiency antibiosis air filtration

Three-dimensional (3D) composite polyvinylidene fluoride (PVDF)/polyacrylonitrile (PAN) electrospun nanofibrous membranes combining both thick and thin nanofibers have been fabricated by the method of multi-jet electrospinning with sheath gas to realize high-efficiency air filtration under a low pressure drop. The thin PAN nanofibers form a dense membrane, with a strong capturing ability on the ultra-fine particles, while the thick PVDF nanofibers play a 3D supporting effect on the thin PAN nanofibers. In this case, the combination results in a fluffy membrane with higher porosity, which could achieve the airflow passing through the membrane without the air pressure drop. The effects of the composite manner of thick nanofibers and thin nanofibers are investigated, in order to optimize the air filtration performance of the 3D composite nanofibrous membrane. As a result, the maximum quality factor for air filtration could reach up to 0.398 Pa−1. The particle-fiber interaction model was used to simulate the air filtration process as well, and the simulation results were fairly consistent with the experimental results, providing a guidance method for the optimization of composite nanofibrous membrane for high-efficiency air filtration. More interestingly, a cationic poly[2-(N,N-dimethyl amino) ethyl methacrylate] (PDMAEMA) was added in the PVDF solution to obtain a composite air filtration membrane with excellent antibiosis performance, which achieved the highest inhibition rate of approximately 90%. In short, this work provides an effective way to promote antibiosis air filtration performance by using an electrospun nanofibrous membrane, and might also effectively accelerate the biological protection application of current air filtration membranes.

Gamma radiation-induced grafting of poly(2-aminoethyl methacrylate) onto chitosan: A comprehensive study of a polyurethane scaffold intended for skin tissue engineering

A novel brush-like poly(2-aminoethyl methacrylate) (PAEMA) was grafted onto chitosan (CS) through gamma radiation-induced polymerization. The copolymer (CS-g-PAEMA) was used to prepare a sodium acetate leached poly(urethane-urea) scaffold. The above derivatives were developed, synthesized, and characterized to meet the specific characteristics of biomaterials. The results revealed that this method is an easy and successful route for grafting PAEMA onto CS. The feasibility of preparing a CS-g-PAEMA polyurethane foam was confirmed by mechanical, morphometric, spectroscopic, and cytotoxic studies. The scaffold showed high biocompatibility both in vitro and in vivo. The first experiment proved that CS-based polyurethane efficiently allows the dynamic culturing of human fibroblast cells. Additionally, an in vivo study in a murine model indicated a complete integration of the scaffold to surrounding subcutaneous tissue as supported by the histological and histochemical assessments. The aforementioned results support the use of CS-g-PAEMA poly(saccharide-urethane) as a model of in vitro-engineered skin.

Synthesis of molecularly imprinted polymers based on boronate affinity for diol-containing macrolide antibiotics with hydrophobicity-balanced and pH-responsive cavities

In this research, in order to separate and purify diol-containing macrolide antibiotics, like tylosin, from complex biological samples, molecularly imprinted polymer (MIP) based on boronate affinity for tylosin was synthesized by using precipitation polymerization method with 4-vinylphenylboronic acid (VPBA) and dimethyl aminoethyl methacrylate (DMAEMA) as pH-responsive functional monomers, and N,N'-methylene bisacrylamide (MBAA)/ ethylene glycol dimethacrylate (EGDMA) as the co-crosslinkers that balance the hydrophobicity of the MIP. The synthesized tylosin-MIP had the advantages of high adsorption capacity (120 mg/g), fast pH-responsiveness responsible for the accessibility of imprinted cavities, and high selectivity coefficient towards tylosin versus its analogues (2.8 versus spiramycin, 7.3 versus desmycosin) in an aqueous environment. The mechanism of boronate affinity between tylosin and VPBA in the form of charged hydrogen bonding was analyzed via density functional theory (DFT). MIPs were used to successfully separate diol-containing macrolides through molecularly imprinted solid phase extraction (MISPE). The results show that MIPs prepared in this method have a good application prospect in the separation and purification of the diol-containing macrolide antibiotics.

Conjugation of Polysulfobetaine via Poly(pyrogallol) Coatings for Improving the Antifouling Efficacy of Biomaterials.

Antifouling treatment is critical to certain biomedical devices for their functions and patients’ life. Facial, versatile, and universal coating methods to conjugate antifouling materials on a wide variety of biomaterials are beneficial for the fabrication of low-fouling biomedical devices. We developed a simple one-step coating method for surface conjugation of zwitterionic poly(sulfobetaine) via deposition of self-polymerized pyrogallol (PG). Poly(pyrogallol) could deposit copolymers of sulfobetaine methacrylate and aminoethyl methacrylate (pSBAE) on various biomaterials. pSBAE coatings inhibited as high as 99.8% of the adhesion of L929 cells and reduced protein adsorption significantly. The resistance against L929 cell adhesion was increased with increasing coating time and was positively correlated with the surface hydrophilicity and film thickness. Such a coating was robust to resist harsh sterilization conditions and stable for long-term storage in phosphate-buffered saline. We expect that the simple low-fouling pSBAE coating is applicable to the manufacture of medical devices.

Glucose-Responsive Gene Delivery at Physiological pH through Tertiary-Amine Stabilized Boronate-PVA Particles Synthesized by One-Pot Reaction

We report a physiologically stable and cytocompatible glucose-responsive nonviral gene delivery system made up of boronate functionalized polymeric material. Herein, we utilize boronate cis-diol interactions to develop a glucose-responsive submicron particle (SMP) system. The stability of the boronate interaction at a physiological pH was achieved by copolymerization of dimethyl aminoethyl methacrylate (DMAEMA) with acrylamidophenylboronic acid (AAPBA) and the formation of a complex with polyvinylalcohol (PVA) which is governed by cis-diol interactions. The shift in hydrodynamic diameter of SMPs was observed and correlated with increasing glucose concentrations at a physiological pH. Optimal transfection was observed for a 5 µg dose of the gaussia luciferase reporter gene in NIH3T3 cells without any adverse effect on cellular viability. The destabilization of the AAPBA–PVA complex by interacting with glucose allowed the release of encapsulated bovine serum albumin (BSA) in a glucose-responsive manner. In total, 95% of BSA was released from SMPs at a 50 mM glucose concentration after 72 h. A two-fold increase in transfection was observed in 50 mM glucose compared to that of 10 mM glucose.

Highly Selective Recovery of Perfluorooctanoic Acid from Semiconductor Wastewater Via Adsorption on PH-Stimulated Poly(Dimethyl Amino)Ethyl Methacrylate Microgels

Highly Selective Recovery of Perfluorooctanoic Acid from Semiconductor Wastewater Via Adsorption on PH-Stimulated Poly(Dimethyl Amino)Ethyl Methacrylate Microgels

Preparation and Characterization of Sodium Alginate- Eudragit E100 Based Systems with Prospective Pharmaceutical Delivery to Application

Regarding the preparation of a local drug delivery system, the possibility of incorporating an active substance in a matrix system was investigated to prolong the drug release. A complex between sodium alginate and a triple copolymer of dimethyl aminoethyl methacrylate was prepared in the presence of a cross-linking agent- malic acid. The formation of a polyelectrolyte complex was proven by turbidimetry, determining the specific viscosity of the diluted solutions of sodium alginate, EE 100, malic acid with IR spectroscopy.

Protein adsorption to poly(2-aminoethyl methacrylate)-grafted Sepharose gel: Effects of chain length and charge density

Grafting functional polymer chains onto porous resins has been found to drastically increase both adsorption capacity and uptake rate in protein chromatography. In this work, 2-aminoethyl methacrylate (AEM) was used for grafting onto Sepharose FF gel, and six anion-exchangers of different polyAEM (pAEM) chain lengths (ionic capacities, ICs), FF-pAEM, were obtained for protein adsorption and chromatography. It was found that protein adsorption capacity (qm) increased with increasing pAEM chain length, but the uptake rate, represented by the ratio of effective pore diffusivity to the free solution diffusivity (De/D0), showed an up-down trend, reaching a peak value (De/D0=0.55) at an IC of 313 mmol/L. Partial charge neutralization of the AEM-grafted resin of the highest IC (513 mmol/L) by reaction with sodium acetate produced three charge-reduced resins, FF-pAEM513-R. With reducing the charge density, the adsorption capacity kept unchanged and then decreased, but the uptake rate monotonically increased, reaching a maximum (about 2-fold increase) at a residual IC of 263 mmol/L. It is notable that, at the same IC, the charge-reduced resin (FF-pAEM513-R) presented similar or even higher values of qm and De/D0 than its FF-pAEM counterpart. Particularly, at the same IC of 263 mmol/L, a ~50% enhancement of De/D0 was observed. Both adsorption capacity and uptake rate in the charge-reduced resin with a residual IC of 339 mmo/L (FF-pAEM513-R339) decreased more sharply with increasing NaCl concentration by comparison with FF-pAEM513, indicating its increased salt-sensitivity than FF-pAEM513. That is, charge reduction on the AEM-grafted resin could accelerate protein uptake at 0 mmol/L NaCl but decrease salt tolerance. Column breakthrough experiments showed that FF-pAEM513-R339 was favorable for high flow rate protein chromatography at low NaCl concentration (0 mmol/L), whereas FF-pAEM513 was a good choice in a wide range of salt concentrations at low flow rate. This research proved the excellent protein chromatography performance of the AEM-based anion-exchangers.

A pH-responsive polyelectrolyte multilayer film with tunable interfacial properties

We report a facile and versatile approach to fabricate polyelectrolyte multilayer (PEM) films with a chemically modifiable outer surface. A PEM film was prepared by layer-by-layer assembly of poly (2-aminoethyl methacrylate) (PAMA) and polymethacrylic acid (PMAA), terminated with a partially tert-butyloxycarbonyl (Boc)-protected random copolymer (PAMA-co-PBocAMA) as the final layer. The obtained PEM film was then cross-linked and the free amino groups in the PEM film were quenched using EDC/NHS chemistry. The outer layer of the film was then treated via a deprotection reaction, affording free amino groups selectively located at the film surface. As a proof of concept study, these functional groups were used to modify the film surface with two model hydrophilic and hydrophobic compounds, which tuned the wettability of the PEM.

Folic Acid-Terminated Poly(2-Diethyl Amino Ethyl Methacrylate) Brush-Gated Magnetic Mesoporous Nanoparticles as a Smart Drug Delivery System.

Currently, chemotherapy is an important method for the treatment of various cancers. Nevertheless, it has many limitations, such as poor tumour selectivity and multi-drug resistance. It is necessary to improve this treatment method by incorporating a targeted drug delivery system aimed to reduce side effects and drug resistance. The present work aims to develop pH-sensitive nanocarriers containing magnetic mesoporous silica nanoparticles (MMSNs) coated with pH-responsive polymers for tumour-targeted drug delivery via the folate receptor. 2-Diethyl amino ethyl methacrylate (DEAEMA) was successfully grafted on MMSNs via surface initiated ARGET atom transfer radical polymerization (ATRP), with an average particle size of 180 nm. The end groups of poly (2-(diethylamino)ethyl methacrylate) (PDEAEMA) brushes were converted to amines, followed by a covalent bond with folic acid (FA) as a targeting agent. FA conjugated to the nanoparticle surface was confirmed by X-ray photoelectron spectroscopy (XPS). pH-Responsive behavior of PDEAEMA brushes was investigated by Dynamic Light Scattering (DLS). The nanoparticles average diameters ranged from ca. 350 nm in basic media to ca. 650 in acidic solution. Multifunctional pH-sensitive magnetic mesoporous nanoparticles were loaded with an anti-cancer drug (Doxorubicin) to investigate their capacity and long-circulation time. In a cumulative release pattern, doxorubicin (DOX) release from nano-systems was ca. 20% when the particle exposed to acidic media, compared to ca. 5% in basic media. The nano-systems have excellent biocompatibility and are minimally toxic when exposed to MCF-7, and -MCF-7 ADR cells.

Preparation of switchable polymer latexes under elevated CO2 pressure by using 4,4'-(diazene-1,2-diyl) bis(N-(3-(dimethylamino)propyl)-4-methylpentanamide) as a novel CO2-switchable inistab

Switchable polystyrene (PS) latexes were prepared by using newly synthesized CO2-responsive inistab (initiator + colloidal stabilizer), 4,4'-(diazene-1,2-diyl) bis(N-(3-(dimethylamino)propyl)-4-methylpentanamide) (DABPA) through surfactant-free emulsion polymerization (SFEP) under elevated CO2 pressure. The synthesized latexes can be easily aggregated by adding NaOH or N2 and heat, and readily redispersed by introducing CO2 with 10 min of sonication. The redispersed latexes had almost similar zeta potential, particle size and polydispersity (PDI) as the original latexes. The influence of elevated CO2 pressure along with adding CO2-switchable comonomer, 2-(diethyl)amino ethyl methacrylate (DEAEMA) on the stability and solid content of PS latexes were studied. The results showed that by increasing CO2 pressure up to 60 bar, solid content of latex could be enhanced to 30% by employing 0.25 mol% (with respect to the styrene monomer) of inistab, DABPA and 0.54 mol% of DEAEMA. The obtained polymer particles, ranging in diameter from 230 to 525 nm, are spherical as established by SEM and DLS. This method of using inistab at elevated CO2 pressure yields relatively high solid content and less amount of required stabilizer during the emulsion polymerization.

Electrical Conductivity of Chitosan/Dimethyl Amino Ethyl Methacrylate/Metal Composite Prepared by Gamma Radiation

Dimethyl amino ethyl methacrylate was grafted onto chitosan using gamma irradiation technique. The grafting (%) was increased with irradiation dose increment. The presences of Cu+2 and Ag+ with different concentrations (1 and 2%) in the properties of composites were examined. The prepared copolymers composites were characterized by FTIR, TGA, SEM, XRD and the electrical conductivity. The TGA indicates improvement of thermal stability for chitosan-g-PDMAEMA/metals ions composite. Crystallinity and swelling (%) of the grafted samples decreased with increasing the grafting level. Also the electrical conductivity chitosan-g-PDMAEMA/Ag+ (2%) composite have enhanced properties than original chitosan-g-PDMAEMA and chitosan-g-PDMAEMA/Cu+2 copolymers composite.

Influence of the Structure of a Surface Layer of Methyl Methacrylate-Based Cationic Particles on Adsorption of Biomolecules

Crosslinked cationic particles 200–600 nm in diameter have been synthesized via emulsifier-free copolymerization of methyl methacrylate and 2-aminoethyl methacrylate hydrochloride in the presence of cross-linking agents (N,N'-methylenebisacrylamide, triethylene glycol dimethacrylate, and diethylene glycol dimethacrylate). It has been shown that polymer particles with a maximum concentration of surface functional groups (1.42 µmol/m2) and a stable structure of a surface layer are formed only in the presence of ethanol (20 vol %). The synthesized particles efficiently adsorb biologically active substances, and their dispersions are stable against aggregation in buffer solutions at pH 7.0.

Imine bonding self-repair hydrogels after periodate-triggered breakage of their cross-links

The development of new materials with smart properties is currently expanding the development of new technologies. Therefore, the design of materials with novel sensitivities and smart behavior is important for the development of smart systems with automated responsivity. We have recently reported the synthesis of hydrogels, cross-linked by N,N'-diallyltartardiamide (DAT). The covalent DAT-crosslinking points have vicinal diols which can be easily cleaved with periodate, generating changes in the hydrogel properties, as well as generating valuable α-oxo-aldehyde functional groups useful for further chemical modification. Based on those findings, we envisioned that a self-healable hydrogel could be obtained by incorporation of primary amino functional groups, from 2-aminoethyl methacrylate hydrochloride (AEMA), coexisting with DAT into the same network. Herein, α-oxo-aldehyde groups generated after the reaction with periodate would arise in the immediate environment of amine groups to form imine cross-links. For this purpose, DAT-crosslinked hydrogels were synthesized and carefully characterized. The cleavage of DAT-crosslinks with periodate promoted changes in the mechanical and swelling properties of the materials. As expected, a self-healing behavior was observed, based on the spontaneous formation of imine covalent bonds. In addition, we surprisingly found a combination of fast vicinal diols cleavage and a low speed self-crosslinking reaction by imine formation. Consequently, it was found a time-window in which a periodate-treated polymer was obtained in a transient liquid state, which can be exploited to choose the final shape of the material, before automated gelling. The singular properties attained on these hydrogels could be useful for developing sensors, actuators, among other smart systems.

Electrochemical sensing of methylmalonic acid based on molecularly imprinted polymer modified with graphene oxide and gold nanoparticles

Molecularly imprinted allyl trimethoxysilane –grafted- graphene oxide/gold nano particle co polymerised with -allyl amine (AA) /2-aminoethyl methacrylate hydrochloride (AEMA) polymer (GO/AuNP-g-ATMS-co-AEMA/AA) was synthesised by bulk imprinting method. The synthesised product was tested for sensing and quantifying methylmalonic acid (MMA) in blood samples in selective manner. Electrochemical studies performed with the developed sensor. The effective pH for the response of the sensor material was found to be 7.4. The response time, limit of detection (LOD) and limit of quantification (LOQ) of the electrode was found to be ~2 min, 0.2095 μM and 0.2935 μM respectively. The constructed sensor exhibits great selectivity and is useful for the rapid determination of MMA in human serum. The designed electrode is long lasting, reproducible and no pre-treatment of biological samples required during clinical analysis which makes it advantageous. The feasibility of the developed sensor was ensured by comparing it with the HP GC/MSD method practiced in diagnostic laboratory (correlation coefficient of 0.967). These results clearly indicate that the sensor developed through molecularly imprinting technique is valid for real sample analysis.

Thermoresponsive Nanogels of Modified Poly((di(ethylene glycol) methyl ether methacrylate)-co-(2-aminoethyl methacrylate))s

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.

Real-time imaging of polymersome nanoparticles in zebrafish embryos engrafted with melanoma cancer cells: Localization, toxicity and treatment analysis.

BackgroundThe developing zebrafish is an emerging tool in nanomedicine, allowing non-invasive live imaging of the whole animal at higher resolution than is possible in the more commonly used mouse models. In addition, several transgenic fish lines are available endowed with selected cell types expressing fluorescent proteins; this allows nanoparticles to be visualized together with host cells.MethodsHere, we introduce the zebrafish neural tube as a robust injection site for cancer cells, excellently suited for high resolution imaging. We use light and electron microscopy to evaluate cancer growth and to follow the fate of intravenously injected nanoparticles.FindingsFluorescently labelled mouse melanoma B16 cells, when injected into this structure proliferated rapidly and stimulated angiogenesis of new vessels. In addition, macrophages, but not neutrophils, selectively accumulated in the tumour region. When injected intravenously, nanoparticles made of Cy5-labelled poly(ethylene glycol)-block-poly(2-(diisopropyl amino) ethyl methacrylate) (PEG-PDPA) selectively accumulated in the neural tube cancer region and were seen in individual cancer cells and tumour associated macrophages. Moreover, when doxorubicin was released from PEG-PDPA, in a pH dependant manner, these nanoparticles could strongly reduce toxicity and improve the treatment outcome compared to the free drug in zebrafish xenotransplanted with mouse melanoma B16 or human derived melanoma cells.InterpretationThe zebrafish has the potential of becoming an important intermediate step, before the mouse model, for testing nanomedicines against patient-derived cancer cells.FundingWe received funding from the Norwegian research council and the Norwegian cancer society