Poly Ethylene Glycol Monomethacrylate Research Articles

PH-Responsive Water-Soluble Chitosan Amphiphilic Core–Shell Nanoparticles: Radiation-Assisted Green Synthesis and Drug-Controlled Release Studies

This work aims to apply water radiolysis-mediated green synthesis of amphiphilic core-shell water-soluble chitosan nanoparticles (WCS NPs) via free radical graft copolymerization in an aqueous solution using irradiation. Robust grafting poly(ethylene glycol) monomethacrylate (PEGMA) comb-like brushes were established onto WCS NPs modified with hydrophobic deoxycholic acid (DC) using two aqueous solution systems, i.e., pure water and water/ethanol. The degree of grafting (DG) of the robust grafted poly(PEGMA) segments was varied from 0 to ~250% by varying radiation-absorbed doses from 0 to 30 kGy. Using reactive WCS NPs as a water-soluble polymeric template, a high amount of DC conjugation and a high degree of poly(PEGMA) grafted segments brought about high moieties of hydrophobic DC and a high DG of the poly(PEGMA) hydrophilic functions; meanwhile, the water solubility and NP dispersion were also markedly improved. The DC-WCS-PG building block was excellently self-assembled into the core-shell nanoarchitecture. The DC-WCS-PG NPs efficiently encapsulated water-insoluble anticancer and antifungal drugs, i.e., paclitaxel (PTX) and berberine (BBR) (~360 mg/g). The DC-WCS-PG NPs met the role of controlled release with a pH-responsive function due to WCS compartments, and they showed a steady state for maintaining drugs for up to >10 days. The DC-WCS-PG NPs prolonged the inhibition capacity of BBR against the growth of S. ampelinum for 30 days. In vitro cytotoxicity results of the PTX-loaded DC-WCS-PG NPs with human breast cancer cells and human skin fibroblast cells proved the role of the DC-WCS-PG NPs as a promising nanoplatform for controlling drug release and reducing the side effects of the drugs on normal cells.

Protein Removal from Hydrogels through Repetitive Surface Degradation.

Suppression of protein adsorption is a necessary property for materials used in the living body. In this study, thermoresponsive and degradable hydrogels were prepared by the radical polymerization of 2-methylene-1,3-dioxepane, 2-hydroxyethyl acrylate (HEA), and poly(ethylene glycol) monomethacrylate (PEGMA). The prepared hydrogels re-exposed PEG-grafted chains to the interface through surface degradation, which was confirmed by the maintenance of the chemical composition of the hydrogel surfaces after hydrolysis. Notably, adsorbed proteins can be removed from the hydrogel surfaces through hydrogel surface degradation at least thrice.

A polymerizable Aggregation Induced Emission (AIE)-active dye with remarkable pH fluorescence switching based on benzothiazole and its application in biological imaging

In recent years, Aggregation Induced Emission (AIE)-active fluorescent materials have been attracting considerable attention because they play an important role in clinical medicine, photoelectricity, environmental science, biological imaging, and sensors. In this contribution, a novel tetraphenylethylene (TPE) derivative of 2-(4-(1,2,2-triphenylvinyl)benzene) benzothiazole methacrylate (TPBMA) monomer was synthesized by a Suzuki coupling and an acylation reaction using TPE and benzothiazole as structural units, whose maximum emission wavelength respectively appeared at 506 nm in neutral medium and 579 nm in acidic medium with excellent pH sensitivity, and it could change repeatedly at 500 nm and 579 nm under HCl/NH3 fuming, indicating the reversible fluorescence conversion property. As compared with the TPB dye, the emission wavelength of TPBMA spectra has an obvious red-shift, which is consistent with the transition energy level difference (△E) of highest occupied molecular orbital (HOMO) and lowest unoccupied orbital (LUMO) situation by quantum chemistry calculation. Subsequently, the copolymers PEG-TB were successfully prepared by RAFT polymerization of TPBMA and poly (ethylene glycol) monomethacrylate (PEGMA), and their molecular weight (Mw) was about 2.12 × 104 with a narrow polydispersity index (PDI). From the 1H NMR analysis, the actual fraction of TPBMA in the PEG-TB copolymers increased to 22.6% from 17.4% when the feed ratio of TBMTA changed to 25.0% from 20.0%. The obtained PEG-TB could self-assemble into fluorescent organic nanoparticles (FONs) with 100–150 nm diameter in aqueous solution, and their fluorescence intensity increased gradually with the increase of water fraction in the THF solution, indicating the obvious AIE behavior. Moreover, the as-prepared PEG-TB FONs exhibited the prospective potential in the field of biological imaging due to their low cytotoxicity, excellent biocompatibility and easy cells absorption.

Noncovalent Functionalized Graphene Nanocarriers from Graphite for Treating Thyroid Cancer Cells.

Here, biocompatible graphene (G) nanocarriers decorated with iron oxide nanoparticles (IONPs) were prepared using 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) and poly(ethylene glycol) monomethacrylate (PEGMA). For this, we report the use of graphite directly instead of graphene oxide or reduced graphene oxide. Graphene nanocarrier (in situ GIOPMPC) was prepared in one-pot by in situ copolymerization of MPC and PEGMA monomers in the presence of IONPs and G. GIOPMCP nanocarriers were prepared by sonication using PMPC-co-PEGMA copolymers in the presence of IONPs and G. The prepared graphene nanocarriers were thoroughly characterized by various techniques. The analyses confirmed the successful preparation of nanocarriers with even distributions of PMPC-co-PEGMA and IONPs on surface G. The IONPs were coordinated through the phosphate groups in PMPC. Excellent dispersibility of the graphene nanocarriers in water enabled drug delivery applications. The prepared nanocarriers did not show significant cytotoxicity to the thyroid cancer cells up to 8 mg/mL (IC50: 38.26 mg/mL). Thyroid cancer cells were stably transduced with a bioluminescent reporter to monitor cell cytotoxicity. Doxorubicin (DOX) was loaded onto in situ GIOPMPC nanocarriers at two different concentrations and was successfully delivered to thyroid cancer cells, resulting in strong cytotoxicity. Moreover, signaling mechanistic analyses showed apoptosis activation, inhibition of anti-apoptosis and proliferation, and increased DNA damage in the thyroid cancer cells.

Poly (Ethylene Oxide)-Based Block Copolymer Electrolytes Formed via Ligand-Free Iron-Mediated Atom Transfer Radical Polymerization.

The Br-terminated poly (ethylene oxide) (PEO-Br) is used as a green and efficient macroinitiator in bulk Fe-catalyzed atom transfer radical polymerization (ATRP) without the addition of any organic ligands. The polymerization rate is able to be mediated by PEO-Br with various molecular weights, and the decrease in redox potential of FeBr2 in cyclic voltammetry (CV) curves indicates that an increased coordination effect is deteriorated with the depressing reaction activity in the longer ethylene oxide (EO) chain in PEO-Br. In combination with the study of different catalysts and catalytic contents, the methyl metharylate (MMA) or poly (ethylene glycol) monomethacrylate (PEGMA) was successfully polymerized with PEO-Br as an initiator. This copolymer obtained from PEGMA polymerization can be further employed as a polymer matrix to form the polymer electrolyte (PE). The higher ionic conductivity of PE was obtained by using a high molecular weight of copolymer.

Resistance to Long-Term Bacterial Biofilm Formation Based on Hydrolysis-Induced Zwitterion Material with Biodegradable and Self-Healing Properties.

Long-term resistance of biomaterials to the bacterial biofilm formation without antibiotic or biocide is highly demanded for biomedical applications. In this work, a novel biodegradable biomaterial with excellent capability to prevent long-term bacterial biofilm formation is prepared by the following two steps. Ethylcarboxybetaine ester analogue methacrylate (ECBEMA), poly(ethylene glycol) monomethacrylate (PEGMA), and 3-methacryloxypropyletris(trimethylsiloxy)silane (TRIS) were copolymerized to obtain p(ECBEMA-PEGMA-TRIS) (PEPT). Then, PEPT was cross-linked by isocyanate-terminated polylactic acid (IPDI-PLA-IPDI) to obtain the final PEPTx-PLAy (x and y are the number-average molecular weights (Mn) of PEPT and PLA, respectively) with optimal mechanical strength and adjustable surface regeneration rate. Static contact angle measurement, protein adsorption measurement, and attenuated total reflectance infrared (ATR-IR) results show that the PEPT19800-PLA800 film surface can generate a zwitterionic layer to resist nonspecific protein adsorption after surface hydrolysis. Quartz crystal microbalance with dissipation (QCM-D) results indicates that the PEPT19800-PLA800 film can undergo gradual degradation of the surface layer at the lowest swelling rate. Particularly, this material can efficiently resist the bacterial biofilm formation of both Gram-positive bacteria and Gram-negative bacteria over 14 and 6 days, respectively. Moreover, the material also shows an ideal self-healing feature to adapt to harsh conditions. Thus, this nonfouling material shows great potential in biomedical applications and marine antifouling coatings without antibiotic or biocide.

Multitargeting Peptide-Functionalized Star-Shaped Copolymers with Comblike Structure and a POSS-Core To Effectively Transfect Endothelial Cells.

Gene therapy meets one serious bottleneck in clinical application, namely, lack of safe and efficient gene delivery systems. In order to solve this problem, we designed a lowly cytotoxic and highly efficient gene delivery system for the transfection of endothelial cells. Octa(3-ammoniumpropyl)octasilsesquioxane octachloride reacted with 2-bromoisobutyryl bromide under alkaline condition, and sequentially initiated 2-(dimethylamino)ethyl methacrylate (DMAEMA) and poly(ethylene glycol) monomethacrylate (PEGMA) via atom transfer radical polymerization (ATRP) to prepare the eight-arm copolymer with a biocompatible polyhedral oligomericsilsesquioxane (POSS). The side chain ends of the comblike PPEGMA were double-bonded to facilitate the attachment of CAGW or CAG-TAT-NLS functional peptide, thereby enabling the star-shaped copolymers with multifunction. The peptide-functionalized star-shaped copolymers were self-assembled into nanoparticles (NPs) and used to condense pEGFP-ZNF580 (pDNA) to prepare the NPs/pDNA complexes. These complexes had low toxicity as confirmed by MTT. The results of fluorescence microscopy and flow cytometry showed that these multitargeting functionalized gene complexes could effectively transfect endothelial cells. Their transfection efficiency is higher than the positive control PEI 25 kDa group. Moreover, the Western blot test, wound healing assay, and in vitro tube formation assay also demonstrated that the transfected cells showed high migration and enhanced angiogenesis. The pDNA was effective delivered and expressed in endothelial cells by these multitargeting functionalized gene complexes, and promoted cell migration and tube formation. These star-shaped copolymers with comblike structure and a POSS core are a potential gene carrier for gene therapy.

Modulation of functional pendant chains within poly(ethylene glycol) hydrogels for refined control of protein release

Hydrogels are highly attractive delivery vehicles for therapeutic proteins. Their innate biocompatibility, hydrophilicity and aqueous permeability allow stable encapsulation and release of proteins. The release rates also can be controlled simply by altering the crosslinking density of the polymeric network. However, the crosslinking density also influences the mechanical properties of hydrogels, generally opposite to the permeability. In addition, the release of larger proteins may be hindered below critically diminished porosity determined by the crosslinking density. Herein, the physical properties of the hydrogels are tuned by presenting functional pendant chains, independent of crosslinking density. Heterobifunctional poly(ethylene glycol) monomethacrylate (PEGMA) with various end functional groups is synthesized and copolymerized with PEG dimethacrylate (PEGDA) to engineer PEG hydrogels with pendant PEG chains. The pendant chains of the PEG hydrogels consisting of sulfonate, trimethylammonium chloride, and phenyl groups are utilized to provide negative charge, positive charge and hydrophobicity, respectively, to the hydrogels. The release rates of proteins with different isoelectric points are controlled in a wide range by the type and the density of functional pendant chains via electrostatic and hydrophobic interactions.

Co-delivery of Vorinostat and Etoposide Via Disulfide Cross-Linked Biodegradable Polymeric Nanogels: Synthesis, Characterization, Biodegradation, and Anticancer Activity.

Treatment regimens for cancer patients using single chemotherapeutic agents often lead to undesirable toxicity, drug resistance, reduced uptake etc. Combination of two or more drugs is therefore becoming an imperative strategy to overcome these limitations. A step forward can be taken through delivery of the drugs used in combination via nanoparticles. Co-administration of chemotherapeutic drugs encapsulated in nanoparticles has been shown to result in synergistic effects and enhanced therapeutic efficacy. In present study, we explored the combination treatment of histone deacetylase inhibitor vorinostat (VOR) and topoisomerase II inhibitor etoposide (ETOP). The concurrent combination treatment of VOR and ETOP resulted in synergistic effect on human cervical HeLa cancer cells. VOR and ETOP were encapsulated into poly(ethylene glycol) monomethacrylate (POEOMA)-based disulfide cross-linked nanogels. The nanogels were synthesized using atom transfer radical polymerization (ATRP) via cyclohexane/water inverse mini-emulsion and were degradable in presence of intracellular glutathione (GSH) concentration. Both the drugs were loaded into the nanogels by physical encapsulation method and characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), dynamic light scattering (DLS), and differential scanning calorimetry (DSC). Both VOR- and ETOP-loaded nanogels showed sustained release profile. Furthermore, combination treatment drugs encapsulated of POEOMA nanogel demonstrated enhanced synergistic cytotoxic effect compared with combination of free drugs. Enhanced synergistic cell killing efficiency of drug-loaded POEOMA nanogels was due to increased apoptosis via caspase 3/7 activation. Therefore, combination of VOR- and ETOP-loaded PEG-based biodegradable nanogels may provide a promising therapy with enhanced anticancer effect.

Synthesis of amphiphilic fluorescent copolymers with smart pH sensitivity via RAFT polymerization and their application in cell imaging

In this paper, a fluorescein methacryloyl monomer (named Flu-MA) was firstly fabricated by the esterification reaction of fluorescein and methacryloyl chloride; subsequently, a novel amphiphilic fluorescent copolymer (Flu-PEG) with smart pH sensitivity was successfully prepared by RAFT copolymerizing of Flu-MA and poly(ethylene glycol) monomethacrylate (PEGMA). The result of 1H NMR and FTIR implied that both Flu-MA and PEGMA monomers were successfully incorporated into Flu-PEG copolymers, the molecular weight (M n) of which was about 39,800 with polydispersity index (PDI) as about 1.30. In aqueous solution, Flu-PEG copolymers could self-assemble into fluorescent organic nanoparticles (FONs) with about 200 nm diameters due to high water dispersibility and good fluorescence, respectively, endowed by PEGMA and Flu-MA, the fluorescence intensity of which was high sensitive to pH value of solution. More importantly, due to their high water dispersibility, excellent biocompatibility and good fluorescence, the as-prepared Flu-PEG FONs were high attractive for the application in cell imaging. A novel amphiphilic fluorescent copolymer (Flu-PEG) with smart pH-sensitivity was successfully fabricated by RAFT copolymerizing of Flu-MA and PEGMA, which showed high water dispersibility, uniform size and excellent biocompatibility, making them be highly potential for bioimaging application.

Photopolymerization kinetics and molecular interactions in methacrylate-imidazolium based ionic liquid systems

Photopolymerization of poly(ethylene glycol) monomethacrylate (PEGMM) in two imidazo- lium based ionic liquids (ILs) differing with the anion size and H-bond accepting ability, i.e. 1-ethyl- -3-methylimidazolium tetrafluoroborate ((EMIm)(BF4)) and 1-ethyl-3-methylimidazolium trifluoroace- tate ((EMIm)(ATF)) was investigated to find the effect of the IL anion on propagation k p and termination rate k t b coefficients (by DSC) as well as molecular interactions in the system (on the basis of viscosity and FT-IR measurements). Polymerizations in bulk and in tricresyl phosphate (TCP) served as references. Both monomer/IL systems show strong viscosity synergism and viscosity deviations are positive indica- ting that viscosity of associates between the monomer and the ILs is relatively higher than that of pure components. The increase in k p values observed in ILs is higher for polymerization in (EMIm)(BF 4 ), which shows stronger Coulomb cation-anion attractions and lower H-bond accepting ability of the anion. The influence of the ionic liquids on the termination rate coefficient results from the viscosity of the mono- mer-IL system, taking account of viscosity synergism. On the basis of changes of imidazolium ring CH groups vibrations and carbonyl stretching vibrations (both in PEGMM and IL anion) two possible confi- gurations of monomer-IL interactions were proposed: between the monomer carbonyl and C(2)-H hydro- gen of the imidazolium cation in the case of (EMIm)(BF 4 ) and a configuration in which the monomer car- bonyl interacts with the imidazolium cation located on the top of the ring, in the case of (EMIm)(ATF).

Well-Defined Amphiphilic Polymer-Si(100) Hybrids via Surface-Initiated Atom Transfer Radical Polymerization

Well-defined amphiphilic graft polymer brushes containing fluoropolymer segments have been successfully prepared by (i) UV-induced coupling of 4-vinylbenzyl chloride (VBC) with the hydrogen-termined Si(100) (Si-VBC surface), (ii) surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethl methacrylate (HEMA) to produce the Si–VBC–g–P(HEMA) surface as the backbone of macroinitiator for further ATRPs, (iii) coupling of 2-bromoisobutyrl bromide with the HEMA polymer(P(HEMA)) by the esterification to produce the macroinitiators for the subsequent ATRP(Si–VBC–g–P(HEMA)-R3Br), (iv) surface-initiated ATRP of 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) to produce the Si–VBC–g–P(HEMA)–g–P(HFBA) surface, and (v) the active P(HFBA) chain ends being used as the initiator for the subsequent ATRP of poly(ethylene glycol) monomethacrylate (PEGMA) to produce the amphiphilic Si–VBC–g–P(HEMA)–g–P(HFBA)–b–P(PEGMA) brush surface. The chemical composition and functionality of the silicon surface were characterised by X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM) and ellipsometry.

Star Hydrophilic Polymer Brushed Nanoparticles Covalently Tethered on Si(100) Substrates via Surface-Initiated Atom Transfer Radical Polymerization (ATRP)

Covalently tethered well-defined new three-arm star hydrophilic poly(ethylene glycol) monomethacrylate (PEGMA) brushed nanoparticles on silicon surface have been successfully prepared by (i) synthesis a novel type of three-arm star-shaped preceding initiator, trifunctional hydroxy-based N-allyl-3,4,5-trihydroxybenzamide (NATHB), (ii) UV-induced hydrosilylation of NATHB with the hydrogen-termined Si(100) (Si-NATHB surface), (iii) coupling of 2-bromo isobutyrl bromide with the hydroxyl of NATHB by the esterification to provide the initiators (Si–NATHB–R3Br) for the subsequent ATRP, (iv) surface-initiated ATRP of PEGMA and 2-hydroxyethl methacrylate monomethacrylate (HEMA) to give the linear Si–NATHB–g–P(PEGMA) brushes and the Si–NATHB–g–P(HEMA) surface, (v) further coupling of 2-bromo isobutyrl bromide with the hydroxyl of P(HEMA) by the esterification to produce the macroinitiators (Si–NATHB–g–P(HEMA)-R3Br) and (vi) surface-initiated ATRP of PEGMA to give the comb-shaped Si–NATHB–g–P(HEMA)–g–P(PEGMA) brushes surface. Kinetics study indicated that the chain growth of P(PEGMA) and P(HEMA) from the functionalized silicon surfaces was consistent with a “controlled” or “living” process. The chemical composition and functionality of the silicon surface were tailored by the well-defined star linear and comb-shaped P(PEGMA) brushes, which provide with this type of surface structures formed in three brushes under conditions of spatial constraints imposed by their chemical connection to a single grafting site. XPS spectra testify that the linear and comb-shaped P(PEGMA) have been grafted on the Si-NATHB surface. AFM imaging of the hydrophilic polymer brushed nanoparticles imaged distinctive morphology when they were prepared into linear and comb-shaped brushes structure.

Preparation of a novel immunosensor for tumor biomarker detection based on ATRP technique.

A novel electrochemical immunosensor for sensitive detection of a tumor marker is reported. This protocol involves the surface-initiated atom transfer radical polymerization (SI-ATRP) of poly(ethylene glycol) monomethacrylate (PEGMA) on an indium tin oxide (ITO) electrode. Using carcinoembryonic antigen (CEA) as a model analyte, capture anti-CEA (Ab1) was conjugated to poly(poly(ethylene glycol) monomethacrylate) (P(PEGMA)) brushes, via activation of hydroxyl groups by succinic anhydride and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, and N-hydroxysulfosuccinimide sodium salt (NHS/EDC). After the sandwich immunoreaction, the horseradish peroxidase-labeled signal anti-CEA antibodies were used to conjugate gold nanoparticles (HRP-Ab2-AuNPs bioconjugates). Under optimized conditions, the proposed immunosensor showed a high sensitivity and a linear range from 5 × 10-2 to 20 ng mL-1 with a low detection limit of 1.09 × 10-3 ng mL-1. The assay results of clinical serum samples were in acceptable agreement with the reference values. The designed immunoassay system with ultrahigh sensitivity and being efficient and economical, might have potentially broad applications in protein diagnostics and bioassay.

Study on the biocomposites with poly(ethylene glycol) dimethacrylate and surfaced‐grafted hydroxyapatite nanoparticles

AbstractIn composites of hydroxyapatite (HA) nanoparticles with a polymer matrix, the aggregation of nanoparticles would induce structural defects. In order to improve the dispersibility of HA nanoparticles in poly(ethylene glycol) dimethacrylate (PEGDMA) matrix and enhance mechanical properties of the HA/PEGDMA composite as potential bone substitute material, surface‐grafted HA nanoparticles with poly(ethylene glycol) monomethacrylate (PEGMA) were prepared, and crosslinked with PEGDMA under UV light to form a composite. The structure of HA‐g‐PEGMA was characterized by X‐ray diffraction (XRD) and thermal gravimetric analysis (TGA). The dispersibility of HA‐g‐PEGMA nanoparticles in poly(PEGDMA) was evaluated by SEM. The mechanical properties of the composites were investigated by compressive test. The dispersibility of HA‐g‐PEGMA nanoparticles in poly(PEGDMA) matrix was better than the bare HA. At a 1 wt % content of loading, the strength of composites increased by 14%, and the modulus increased by 9%. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Using Mass Spectrometry to Investigate the Structural Features of Photocrosslinked Co-Networks based on Gelatin and Poly(ethylene glycol) Methacrylates

ABSTRACTGelatin was functionalized with glycidyl methacrylate and photocrosslinked in the presence of poly(ethylene glycol) dimethacrylate (PEGDMA) or poly(ethylene glycol) monomethacrylate (PEGMA) to create a biopolymer-based system with tailorable properties. These co-networks were hydrolyzed using 6 M HCl and the degradation products were analyzed and identified using matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry. This technique successfully identified gelatin-derived peptides such as FLPEPPE, SFLPEPPE, and SFLPEPPEE as well as an accompanying PEG-g-poly(methacrylic acid) component. No oligo- or polymethacrylates were monitored at any molecular weight range above m/z = 500, which indicated that they possessed lower molecular weights. An in vitro hydrolytic degradation experiment performed in pH 7.4 PBS buffer solution at 37 °C showed that these networks, which were prepared without the addition of a potentially toxic photoinitiator, exhibited mass loss of up to 50 wt% at 6 weeks of incubation time. These results provide valuable insight into how these functional gelatin-based co-network biomaterials will perform in a biological setting.

Using Mass Spectrometry to Investigate the Structural Features of Photocrosslinked Co-Networks based on Gelatin and Poly(ethylene glycol) Methacrylates – CORRIGENDUM

Gelatin was functionalized with glycidyl methacrylate and photocrosslinked in the presence of poly(ethylene glycol) dimethacrylate (PEGDMA) or poly(ethylene glycol) monomethacrylate (PEGMA) to create a biopolymer-based system with tailorable properties. These co-networks were hydrolyzed using 6 M HCl and the degradation products were analyzed and identified using matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry. This technique successfully identified gelatin-derived peptides such as FLPEPPE, SFLPEPPE, and SFLPEPPEE as well as an accompanying PEG-g-poly(methacrylic acid) component. No oligo- or polymethacrylates were monitored at any molecular weight range above m/z = 500, which indicated that they possessed lower molecular weights. An in vitro hydrolytic degradation experiment performed in pH 7.4 PBS buffer solution at 37 °C showed that these networks, which were prepared without the addition of a potentially toxic photoinitiator, exhibited mass loss of up to 50 wt% at 6 weeks of incubation time. These results provide valuable insight into how these functional gelatin-based co-network biomaterials will perform in a biological setting.

Synthesis and properties of Polycaprolactone‐graft‐poly(2‐(dimethylamino)ethyl methacrylate‐co‐methoxy polyethylene glycol monomethacrylate) as non‐viral gene vector

AbstractPolycaprolactone‐graft‐Poly(2‐(dimethylamino)ethyl methacrylate‐co‐methoxy polyethylene glycol monomethacrylate) (PCL‐graft‐P(DMAEMA‐co‐mPEGMMA)) was synthesized by combination of ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP). PCL‐graft‐P(DMAEMA‐co‐mPEGMMA) was characterized by FTIR, 1H NMR, and GPC. PCL‐graft‐P(DMAEMA‐co‐mPEGMMA) with expected composition and structure was achieved. pH‐ and thermo‐sensitive properties of the PCL‐graft‐P(DMAEMA‐co‐mPEGMMA) nanoparticles prepared by the nanoprecipitation method were investigated by TEM and DLS. With increase in the temperature, the size of PCL‐graft‐P(DMAEMA‐co‐mPEGMMA) nanoparticles is decreased under base environment. Furthermore, in vitro transfection and toxicity assays were tested in 293T cells. The results indicate that PCL‐graft‐P(DMAEMA‐co‐PEGMMA) has lower cytotoxicity at N/P ratios less than 10 with transfection efficiency concomitantly reducing at N/P ratios less than 20 compared to PCL‐graft‐PDMAEMA as the control. However, PCL‐graft‐P(DMAEMA‐co‐PEGMMA) presents higher transfection efficiency at N/P ratios more than 20 compared to PCL‐graft‐PDMAEMA. Copyright © 2010 John Wiley & Sons, Ltd.

Versatile functionalization of Fe 3O 4 nanoparticles via RAFT polymerization and click chemistry

Azide-functionalized chain transfer agent (CTA) was synthesized and subsequently employed to mediate the reversible addition fragmentation transfer (RAFT) polymerization of poly(ethylene glycol) monomethacrylate (PEGMA) on the alkyne-functionalized Fe 3O 4 nanoparticles surface together with click chemistry. In a single pot procedure, azide-functionalized CTA, alkyne-functionalized Fe 3O 4 and PEGMA were combined to produce the desired product. Fourier transformed infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) results showed that PEGMA chains were grafted to Fe 3O 4 nanoparticles using RAFT polymerization and click chemistry.

Integrative design of a poly(ethylene glycol)-poly(propylene glycol)-alginate hydrogel to control three dimensional biomineralization

A mineralized polymeric matrix has been extensively studied to understand biomineralization processes and to further regulate phenotypic functions of various cells involved in osteogenesis and physiological homeostasis. It has been often proposed that several matrix variables including charge density, hydrophobicity, and pore size play vital roles in modulating composition and morphology of minerals formed within a three dimensional (3D) matrix. However, the aspects have not yet been systematically examined because a tool enabling the independent control of the matrix variables is lacking. This study presents an advanced integrative strategy to control morphology and composition of biominerals with matrix properties, by using a hydrogel formulated to independently control charge density, hydrophobicity, and porosity. The hydrogel consists of poly(ethylene glycol) monomethacrylate (PEGmM), poly(propylene glycol) monomethacrylate (PPGmM), and methacrylic alginate (MA), so the charge density and hydrophobicity of the hydrogel can be separately controlled with mass fractions of MA and PPGmM. Also, hydrogels which present only nano-sized pores, termed nanoporous hydrogels, are lyophilized and rehydrated to prepare the hydrogels containing micro-sized pores, termed microporous hydrogels. We find that increasing the mass fractions of MA and PPGmM of the microporous hydrogel promotes the growth of apatite layers because of the increases in the charge density, hydrophobicity and pore size. In contrast, increasing mass fractions of MA and PPGmM of the nanoporous hydrogel enhances the formation of calcium carbonate minerals. The dependency of the mineralization on hydrogel variables is related to the change in supersaturation of mineral ions. Overall, the results of this study will be highly useful to better understand the interplay of matrix variables in biomineralization and to design a wide array of mineralized matrix potentially used in cell therapies and tissue engineering.