Glycol Methacrylate Phosphate Research Articles

Exploring the Effect of Drug Loading on the Biological Fate of Polymer-Coated Solid Nanoparticles

Polymer-coated inorganic nanoparticles (NPs) have attracted great attention in drug delivery fields due to their unique magnetic, optical, and thermal properties. Recent studies have shown that the surface physicochemical properties of these NPs, including the size, shape, shell hydration, protein corona, and so forth, affect their biological fate. However, there has been less attention on the effect of the drug loading amount on the biological activity of inorganic NPs. Here, we used upconverting NPs (UCNPs) as an inorganic nanocarrier model, coated them with a triblock terpolymer poly(poly(ethylene glycol) methyl ether methacrylate)-block-polymethacrylic acid-block-ethylene glycol methacrylate phosphate (PPEGMEMA-b-PMAA-b-PEGMP), and loaded them with different amounts of anticancer drug doxorubicin (DOX) by electrostatic interactions. Our results show that the UCNPs with the lowest DOX loading amount (1.32%) have the best biological behavior. We find that the effect of DOX loading on the biological behavior of UCNPs is dominated by polymer shell hydration and the protein corona. The lowest drug-loading UCNPs are more hydrated and have more albumin coronas around, which leads to an increasing effect on the association with cancer cells and drug accumulation in the mouse tumor area. Our findings highlight the importance of optimizing the drug loading amounts in polymer-coated inorganic drug delivery systems as the amount and type of drug will alter the physical properties of the polymer shell.

Controlling the Biological Behaviors of Polymer-Coated Upconverting Nanoparticles by Adjusting the Linker Length of Estrone Ligands.

The estrone ligand is used for modifying nanoparticle surfaces to improve their targeting effect on cancer cell lines. However, to date, there is no common agreement on the ideal linker length to be used for the optimum targeting performance. In this study, we aimed to investigate the impact of poly(poly ethylene glycol methyl ether methacrylate) (PPEGMEMA) linker length on the cellular uptake behavior of polymer-coated upconverting nanoparticles (UCNPs). Different triblock terpolymers, poly(poly (ethylene glycol) methyl ether methacrylate)-block-polymethacrylic acid-block-polyethylene glycol methacrylate phosphate (PPEGMEMAx-b-PMAAy-b-PEGMP3: x = 7, 15, 33, and 80; y = 16, 20, 18, and 18), were synthesized with different polymer linker chain lengths between the surface and the targeting ligand by reversible addition-fragmentation chain transfer polymerization. The estrone ligand was attached to the polymer via specific terminal conjugation. The cellular association of polymer-coated UCNPs with linker chain lengths was evaluated in MCF-7 cells by flow cytometry. Our results showed that the bioactivity of ligand modification is dependent on the length of the polymer linker. The shortest polymer PPEGMEMA7-b-PMAA16-b-PEGMP3 with estrone at the end of the polymer chain was found to have the best cellular association behavior in the estrogen receptor (ER)α-positive expression cell line MCF-7. Additionally, the anticancer drug doxorubicin•HCl was encapsulated in the nanocarrier to evaluate the 2D and 3D cytotoxicity. The results showed that estrone modification could efficiently improve the cellular uptake in ERα-positive expression cell lines and in 3D spheroid models.

In vivo study of dose-dependent antioxidant efficacy of functionalized core\u2013shell yttrium oxide nanoparticles

Herein, we assess the dose-dependent antioxidant efficacy of ultrafine spherical functionalized core–shell yttrium oxide nanoparticles (YNPs) with a mean size of 7–8 nm and modified with poly EGMP (ethylene glycol methacrylate phosphate) and N-Fluorescein Acrylamide. The antioxidant properties of these nanoparticles were investigated in three groups of Sprague–Dawley rats (10 per group) exposed to environmental stress daily for 1 week and one control group. Groups 2 and 3 were intravenously injected twice a week with YNPs at 0.3 and 0.5 mg at 2nd and 5th day of environmental stress exposure respectively. Different samples of blood and serum were collected from all experimental groups at end of the experiment to measure oxidative biomarkers such as total antioxidant capacity (TAC), hydroxyl radical antioxidant capacity (HORAC), oxygen radical antioxidant capacity (ORAC), malondialdehyde (MDA), and oxidants concentration as hydrogen peroxide (H2O2). The liver, brain, and spleen tissues were collected for fluorescence imaging and histopathological examination in addition to brain tissue examination by transmission electron microscope (TEM). Inductively coupled plasma-mass spectrometry (ICP-MS) was used to estimate YNPs translocation and concentration in tissues which is consecutively dependent on the dose of administration. Depending on all results, poly EGMP YNPs (poly EGMP yttrium oxide nanoparticles) can act as a potent direct antioxidant in a dose-dependent manner with good permeability through blood–brain barrier (BBB). Also, the neuroprotective effect of YNPs opening the door to a new therapeutic approach for modulating oxidative stress–related neural disorders.Highlights• The dose-dependent antioxidant efficacy of ultrafine spherical functionalized core–shell yttrium oxide nanoparticles (YNPs) with a mean size of 7–8 nm and modified with poly EGMP (ethylene glycol methacrylate phosphate) and N-Fluorescein Acrylamide was assessed.• The dose of administration directly affecting the brain, liver, and spleen tissues distribution, retention, and uptake of YNPs and direct correlation between the absorbed amount and higher dose administered.• YNPs can act as a potent direct antioxidant in a dose-dependent manner with good permeability through blood–brain barrier (BBB).Graphical abstract

In-vitro adhesive and interfacial analysis of a phosphorylated resin polyalkenoate cement bonded to dental hard tissues.

ObjectivesTo assess the performance of a novel resin-modified glass-ionomer cement (pRMGIC) bonded to various tooth tissues after two-time intervals. Methods192 sound human molars were randomly assigned to 3 groups (n = 64): sound enamel, demineralised enamel, sound dentine. Sixty-four teeth with natural carious lesions including caries-affected dentine (CAD) were selected. All substrates were prepared, conditioned and restored with pRMGIC (30% ethylene glycol methacrylate phosphate (EGMP, experimental), Fuji II LC (control), Fuji IX, and Filtek™ Supreme with Scotchbond ™ Universal Adhesive. Shear bond strength (SBS) was determined after 24 h and three months storage in SBF at 37 °C. The debonded surfaces were examined using stereomicroscopy and scanning electron microscopy (SEM). Multivariate Analysis of Variance (MANOVA), Bonferroni post hoc tests (alpha=0.05) and independent T-tests were used for multifactorial data analysis. ResultsThe hydrophilicity and functionality of EGMP enhanced the bond strength of the pRMGIC to different substrates after 24 h and 3 months as compared to F2LC (p<0.05). Adhesive failures were found to decrease with pRMGIC and integration into exposed enamel prisms and dentine tubules was observed with SEM. Ageing enhanced bond strength of pRMGIC to all substrates but was statistically significantly only in sound dentine. The SBS of pRMGIC was higher with sound vs. demineralised enamel at both time periods (p<0.001), while it was higher to CAD initially and to sound dentine post-storage (p = 0.004). ConclusionspRMGIC exhibited enhanced bonding performance to various tooth tissues with an ability to seal exposed enamel prisms and dentine tubules. Clinical significancepRMGIC is a promising material exhibiting long-lasting bonded-tooth interfaces, for its use in minimally invasive reparative techniques.

Membranes for the Capture and Screening of Waterborne Plutonium Based on a Novel Pu-Extractive Copolymer Additive.

This contribution describes the fabrication of plutonium-adsorptive membranes by non-solvent induced phase separation. The dope solution comprised poly(vinylidene fluoride) (PVDF) and a Pu-extractive copolymer additive of PVDF-g-poly(ethylene glycol methacrylate phosphate) (EGMP) in dimethylformamide (DMF). The effects of casting conditions on membrane permeability were determined for PVDF membranes prepared with 10 wt% PVDF-g-EGMP. Direct-flow filtration and alpha spectrometry showed that membranes containing the graft copolymer could recover Pu up to 59.9 ± 3.0% from deionized water and 19.3 ± 3.5% from synthetic seawater after filtering 10 mL of 0.5 Bq/mL 238Pu. SEM-EDS analysis indicated that the graft copolymer was distributed evenly throughout the entire depth of the copolymer membranes, likely attributing to the tailing observed in the alpha spectra for 238Pu. Despite the reduction in resolution, the membranes exhibited high Pu uptake at the conditions tested, and new membrane designs that promote copolymer surface migration are expected to improve alpha spectrometry peak energy resolutions. Findings from this study also can be used to guide the development of extractive membranes for chromatographic separation of actinides from contaminated groundwater sources.

Extractive thin-film composite membranes for the isotopic screening of plutonium in water

Isotopic determination of trace-level Pu in water requires time-consuming concentration and sample preparation steps, and the samples routinely must be prepared off-site from the contamination source. An analytical method that combines on-site Pu concentration with spectroscopic screening would be a valuable tool for environmental monitoring and nuclear forensics. This contribution describes the development of extractive polymer thin-film composite (e-TFC) membranes for the rapid concentration and isotopic determination of Pu from water. The e-TFC membranes were prepared by spin coating Pu-extractive copolymers on the surface of an ultrafiltration membrane. The copolymers were synthesized from methyl methacrylate or 4-methylstyrene and a Pu-reactive monomer. Three Pu-reactive monomers were evaluated for their ability to create copolymers that were suitable for casting and capable of extracting Pu from water at trace levels. Copolymers containing 5% (w/w) ethylene glycol methacrylate phosphate (EGMP) had distribution coefficients of 92.7 ± 18.5 L/kg for 242Pu at pH 6.8. e-TFC membranes prepared with an EGMP-based copolymer active layer were effective for concentrating 242Pu from a 4.53 Bq/mL (1.26 × 10−8 M) solution at pH 6.8. The resulting alpha spectra of Pu-loaded e-TFC membranes achieved energy resolutions (full-width at half-maximum, FWHM) of 71.7 ± 8.7 keV, allowing for the isotopic discrimination of 242Pu from 238Pu/241Am also present in the solution.

Optimizing the Polymer Cloak for Upconverting Nanoparticles: An Evaluation of Bioactivity and Optical Performance.

The ability of upconversion nanoparticles (UCNPs) to convert low-energy near-infrared (NIR) light into high-energy visible-ultraviolet light has resulted in their development as novel contrast agents for biomedical imaging. However, UCNPs often succumb to poor colloidal stability in aqueous media, which can be conquered by decorating the nanoparticle surface with polymers. The polymer cloak, therefore, plays an instrumental role in ensuring good stability in biological media. This study aims to understand the relationship between the length and grafting density of the polymer shell on the physicochemical and biological properties of these core-shell UCNPs. Poly(ethylene glycol) methyl ether methacrylate block ethylene glycol methacrylate phosphate (PPEGMEMAn-b-PEGMP3) with different numbers of PEGMEMA repeating units (26, 38, and 80) was prepared and attached to the UCNPs via the phosphate ligand of the poly(ethylene glycol methacrylate phosphate) (PEGMP) block at different polymer densities. The in vitro and in vivo protein corona, cellular uptake in two-dimensional (2D) monolayer and three-dimensional (3D) multicellular tumor spheroid (MCTS) models, and in vivo biodistribution in mice were evaluated. Furthermore, the photoluminescence of single-polymer-coated UCNPs was compared in solid state and cancer cells using laser scanning confocal microscopy (LSCM). Our results showed that the bioactivity and luminescence properties are chain length and grafting density dependent. The UCNPs coated with the longest PPEGMEMA chain, grafted at low brush density, were able to reduce the formation of the protein corona in vitro and in vivo, while these UCNPs also showed the brightest upconversion luminescence in the solid state. Moreover, these particular polymer-coated UCNPs showed enhanced cellular uptake, extended in vivo blood circulation time, and more accumulation in the liver, brain, and heart.

Thermal characteristics and flame retardance behavior of phosphoric acid-containing poly(methacrylates) synthesized by RAFT polymerization

The RAFT polymerization of strongly acidic, cross-linkable ethylene glycol methacrylate phosphate (EGMP) is described without protecting the acidic groups, with applications towards fire retardant polymers. After achieving the optimized polymerization conditions, we synthesized organo-soluble phosphoric acid-containing copolymers with methyl methacrylate (MMA) and bio-based isobornyl methacrylate (IBMA) with Mn in the range of 7.2−9.5 kg mol−1 and relatively low dispersities of 1.40−1.55. Additionally, we showed that it was possible to reinitiate RAFT polymerization from a P(EGMP)-rich macro-chain transfer agent with MMA and IBMA. DSC revealed Tg depression of copolymers as a function of EGMP concentration, which shows the plasticizing effect of EGMP. Rheology revealed cross-liking behavior of HEMAP-rich samples at 120 ℃. Thermogravimetric analysis (TGA) showed a one-step decomposition for PMMA and a two-step decomposition for PIBMA copolymers. In addition, the incorporation of 28 mol% EGMP slowed down the decomposition rate, improved the decomposition temperature (Td) by 41 ℃, and notably increased the limiting oxygen index (LOI) from ∼17.6 to over 24. Among all samples, the EGMP-rich polymer (FEGMP = 0.71, FMMA = 0.29) exhibited prominent flame retardancy with the highest LOI value of 34. This result is invariably due to the strong acidity of phosphoric acid groups which notably leads to interesting flame retardancy properties.

On-line enrichment of N-glycans by immobilized metal-affinity monolith for capillary electrophoresis analysis

A novel N-glycan enrichment strategy is presented using unexpected but strong interactions between the sulfonate groups brought by the fluorescent dye of glycans and the Zr4+ modified poly(ethylene glycol methacrylate phosphate (EGMP)-co-acrylamide (AM)-co-bis-acrylamide (BAA)) monolith. The poly (EGMP-co-AM-co-BAA) monolith was synthesized via ultraviolet (UV) irradiation and then functionalized with Zr4+. The obtained monolith was characterized with scanning electron microscopy and mercury intrusion porosimetry. Large through-pores and a continuous skeleton with high permeability were observed. The N-glycans were labeled with the 1-aminopyrene-3, 6, 8-trisulfonic acid (APTS) and enriched by the Zr4+ modified monolith through IMAC interaction. This enrichment step was then coupled off-line to capillary electrophoresis (CE) separation with laser induced fluorescence (LIF) detection. Successful preconcentration of the APTS labeled maltooligosaccharide ladder was achieved under optimized conditions. Enrichment factors obtained for the maltooligosaccharides ranged from 9 to 24 with RSDs from 2.0% to 9.2% (n = 3). Moreover, very good repeatabilities (<6.7%) were obtained for glucose oligomers (4–15 glucose units) corresponding to sizes expected for N-glycans, demonstrating the great potential of this Zr4+ modified monolith to enrich APTS labeled glycans from N-glycoproteins. The proposed method was then successfully applied for the enrichment of N-glycans released from Ribonuclease B, in which case all five expected oligomannose glycans (Man 5 to Man 9) were successfully enriched. Thanks to the advantage of the method to enrich selectively APTS-glycans compared to the commercial SPE columns composed of HILIC or PGC materials, the first proof of concept of on-line enrichment coupled to CE-LIF separation was demonstrated for maltooligosaccharides as well.

Photo-crosslinked alginate nano-hydroxyapatite paste for bone tissue engineering

In this study, methacrylation of alginate was carried out by reacting sodium alginate with methacrylic anhydride in the presence of sodium hydroxide. Separately synthesized nano-hydroxyapatite (nano-HAp) powder was surface functionalized using mercaptopropionic acid and ethylene glycol methacrylate phosphate (EGMP) in the presence of azobisisobutyronitrile benzene as a free radical initiator in a nitrogen atmosphere. Methacrylated alginate solution was mixed with the required amount of surface-functionalized HAp nanoparticles in the presence of 0.05% Irgacure 2959 as a photoinitiator and was placed at the centre of a 8 kW UV light source (265 nm) to prepare photo-crosslinked bone paste. X-ray diffraction analysis indicated that surface functionalization did not alter phase purity of HAp nanopowder in the prepared paste. The graft polymerization of EGMP on the surface of HAp was confirmed by the presence of the 1732 cm−1 band, which belongs to C=-O stretching of EGMP, in addition to the characteristic peaks of nano-HAp and alginate in the composite paste. The storage and loss moduli of all the prepared pastes increased non-linearly with time up to 100 s, demonstrating their pseudo plastic behaviour. The rate of release of bone morphogenetic protein 2 (BMP-2) was significantly faster in the first few days, and the release curve gradually levelled off prior to slowing down up to 22 d. Mesenchymal stem cell adhesion studies revealed that cells could attach to the paste material and stretch over the surface of the material after 14 d of incubation. MTT assay showed that prepared paste materials were conducive to attachment and proliferation of mesenchymal stem cells. Immunocytochemical analysis revealed that the addition of surface-functionalized nano-HAp and BMP-2 to alginate hydrogel enhanced the osteogenic potential of the prepared paste. The results indicate that the newly developed photo-crosslinked paste may be physically and biologically suitable for application as a bone filler.

Functionalized Core-Shell Yttrium Oxide Nanoparticles as Antioxidants Agents in Heat Stressed Rats.

Herein, we assess the antioxidant potential of core-shell yttrium oxide nanoparticles functionalized with ethylene glycol methacrylate phosphate (EGMP). The antioxidant properties of these nanoparticles were investigated in heat stressed models of 21 rats (heat stressed group, group B). Different samples of blood, serum, and tissue homogenate were collected at different time intervals in order to measure oxidative biomarkers such as enzymatic antioxidants (SODs, GPX, GST, GR, and TAC) and oxidative byproducts (MDA, PC, and 8-OHdG). Liver specimens of prophylactic group and heat stressed ones were also histopathologically examined 2h post NPs injection. The measurements of oxidative biomarkers were complementary with histopathological findings and confirmed the antioxidant properties of poly EGMP yttrium oxide NPs.

An integrated multifunctional hybrid cement (pRMGIC) for dental applications

ObjectiveGlass-ionomer and resin-modified glass-ionomer cements are versatile materials with the ability to form a direct bond with tooth tissues. The aim of this study was to formulate a novel class of dental bio-interactive restorative material (pRMGIC) based on resin-modified glass-ionomer cements via the inclusion of an organophosphorus monomer, ethylene glycol methacrylate phosphate, with a potential to improve the mechanical properties and also function as a reparative restorative material. MethodspRMGIC was formulated with modification of the resin phase by forming mixes of ethylene glycol methacrylate phosphate (EGMP; 0–40%wt) and 2-hydroxyethyl methacrylate monomer into the liquid phase of a RMGIC (Fuji II LC, GC Corp.). The physical properties of the cements were determined including setting characteristics, compressive strength and modulus (CS &CM), microhardness (MH) and biaxial flexural strength (BFS). Fluid uptake and fluoride release were assessed up to 60 days storage. Adhesion to sound dentine was measured using micro-tensile bond strength and surface integrity was analysed using SEM coupled with EDX. Statistical analysis was performed using ANOVA and Bonferroni post-hoc tests. ResultsThe pRMGIC cements exhibited an increase in working time with increasing EGMP concentration however were within the limits of standard clinical requirements. Although the compressive strength of pRMGIC cements were comparable to control cements in the early stages of maturation, the higher EGMP-containing cements (EGMP30 and 40) exhibited significantly greater values (p < 0.05) after 4 weeks storage (141.0 ± 9 and 140.4 ± 8 MPa, respectively), in comparison to EGMP0 (128.8 ± 7 MPa). A dramatic two fold increase in biaxial flexural strength (p < 0.001) was observed for the pRMGIC’s. Furthermore, the ability to decalcify tooth apatite resulted in enhanced interfacial adhesion due to chelation with calcium ions of tooth apatite. The inclusion of EGMP encouraged formation of reinforcing complexes within the RMGIC, thus improving physical properties, decreasing solubility and lower fluoride release. A dense microstructure was observed with increasing EGMP content. SignificanceA novel universal bio-interactive adhesive repair material will enable clinicians to offer more effective repair of the tooth-restoration complex, thus future treatments will benefit both patient and a severely constrained healthcare budget.

Phosphonic acid and alkyl phosphate-derivatized resins for the simultaneous concentration and detection of uranium in environmental waters

The objective of this study was to synthesize extractive scintillating resins for the direct, real-time analysis of uranium in neutral pH environmental waters. In the first synthetic approach, a methyl phosphonic acid-derivatized resin was prepared by suspension polymerization to create a matrix containing a covalently bound fluorophore and 4-vinylbenzyl chloride, followed by phosphorylation and hydrolysis to add phosphonic acid functionality. In the second approach, methyl phosphate-derivatized resin was synthesized in a one-step suspension polymerization, resulting in matrix containing a covalently bound fluorophore and ethylene glycol methacrylate phosphate ligand. Uranium binding capacity and detection efficiency of the resins were evaluated in pH 4, 6 and 8 simulated ground water and compared. The ability of both resins to detect uranium from neutral pH simulated ground water was evaluated through a Shewart-3σ control statistic applied to real-time data collected in a flow-cell detector. Resins exhibited similar binding capacities (0.18 mmol g−1) and detection efficiencies; however, the methyl phosphate resin concentrated uranium more rapidly from simulated ground water than the phosphonic acid resin. The pH dependence on the volume to detection was interpreted through changes in uranium speciation and binding mechanism supported by computational simulations.

Biocompatibility and biodistribution of surface-modified yttrium oxide nanoparticles for potential theranostic applications.

The surface of ultrafine yttrium oxide nanoparticles (NPs) with mean size of 7-8nm was modified with a functional polymer layer to improve their dispersion and impart fluorescent properties for imaging purposes. Surface functionalization was achieved by silanization of yttrium oxide NPs with 3-trimethoxysilylpropyl methacrylate followed by grafting of a co-polymer made of acrylic acid (AA) and ethylene glycol methacrylate phosphate (EGMP). The polymer shell decreases the surface energy of NPs, enhances their polarity, and, as a result, improves their colloidal stability. The synthesized NPs are capable of scavenging free radicals and for this reason have therapeutic potential that warrants further investigations. Furthermore, these stabilized core-shell NPs showed a very low cytotoxicity, confirming that the polymer shell sensibly improves the biocompatibility of bare yttrium oxide NPs, which are otherwise toxic on their own. Poly-EGMP yttrium NPs proved to be safe up to 0.1mg/g body weight in 1month old Sprague-Dawley rats, showing also the ability to cross the blood-brain barrier short time after tail injection. The surface modification of yttrium NPs here described allows these NPs to be potentially used in theranostics to reduce neurodegenerative damage due to the heat stress.

Poly(ethylene glycol methacrylate phosphate) grafting on silica shell formed on magnetite nanoparticles: applications to selective sequestration of f-element ions

The silica layer protected magnetite (Fe3O4) NPs were functionalized with phosphate group bearing monomer ethylene glycol methacrylate phosphate (EGMP) and its polymer (poly(EGMP) having affinity toward f-element ions. The polymerizable double bonds of EGMP anchored on silica coated magnetite NPs were used to grow poly(EGMP) chains by γ-rays induced polymerization. It was observed in the extraction studies that Pu4+ ions sorbed preferentially in Fe3O4@SiO2-EGMP NPs over UO22+ ions from 3 mol L−1 HNO3. Contrary to this, Fe3O4@SiO2-poly(EGMP) NPs did not exhibit significant selectivity toward UO22+ and Pu4+ ions under similar chemical conditions. Indicating a multiple ligating groups coordination requirement for the binding of UO22+ ions with phosphate groups.

Palladium Nanoparticles Hosted in Poly(ethylenimine) and Poly(ethylene glycol methacrylate phosphate) Anchored Membranes for Catalyzing Uranyl Ions Reduction and Mizoroki–Heck Coupling Reaction

The poly(ethylenimine) (PEI) and poly(ethylene glycol methacrylate phosphate) (poly(EGMP)) functionalized microporous poly(propylene) membrane have been developed to host the palladium (Pd) nanoparticles (NPs) for catalyzing the inorganic and organic reactions. These functionalized membranes are characterized for their porosities and pore-size distributions. Field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-rays spectrometry (EDX) attached to FE-SEM, and small-angle X-rays scattering (SAXS) have been used to study the Pd NPs size distributions and homogeneous distributions in the membrane matrixes. The average size of Pd NPs has been found to be ≈2 nm in all the membranes by SAXS experiments, and elemental mappings by EDX suggest uniform distributions of Pd NPs. However, a very small number of bigger particles have been formed in the membrane having lowered pore-filling due to lower network elasticity in some region that allowed agglomeration to some extent. The in situ generated H...

A new approach in modifying ethylene glycol methacrylate phosphate coating formulation by adding sodium montmorillonite to increase corrosion resistance properties

In this work, the corrosion inhibition property of the ethylene glycol methacrylate phosphate (EGMAP) and the polymerized EGMAP also incorporated with sodium montmorillonite (Na+Mt) has been studied. The corrosion inhibition of carbon steel in 1.0 M HCl solution was investigated using electrochemical impedance spectroscopy (EIS) measurements. Data obtained were analyzed to be modeled through appropriate equivalent circuit models. EGMAP is used as the corrosion inhibitor in acidic media, even at very low concentration, the inhibition efficiency increases with concentration and can reach a limiting value (82%) with a concentration of 1.0 × 10−2 mol L−1 of the inhibitor after 48 h of immersion time.The adsorption of EGMAP on the carbon steel surface obeys to the Langmuir's adsorption isotherm. The calculated ΔG°ads value show that the corrosion inhibition of the carbon steel in 1.0 M HCl is mainly controlled by a physisorption process.The polymerization kinetics of EGMAP is favorised under UV-light, by creating highly crosslinked polymerized chains leading to complete conversion degree of the C═C bonds to C─C reached 95% in 45 min. The protective power of this inhibitor also increases in the case of polymerized inhibitor by 80%. The addition of clay in the coating formulation lead to a significant improvement, reaching an inhibitory value of 98%, explained by the adsorption of clay on the surface of the steel. Both formulations present a very advantageous stability of adsorbed layers.

A Rapid One-Pot Synthesis of Novel High-Purity Methacrylic Phosphonic Acid (PA)-Based Polyhedral Oligomeric Silsesquioxane (POSS) Frameworks via Thiol-Ene Click Reaction.

Herein, we demonstrate a facile methodology to synthesis a novel methacrylic phosphonic acid (PA)-functionalized polyhedral oligomeric silsesquioxanes (POSSs) via thiol-ene click reaction using octamercapto thiol-POSS and ethylene glycol methacrylate phosphate (EGMP) monomer. The presence of phosphonic acid moieties and POSS-cage structure in POSS-S-PA was confirmed by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (1H, 29Si and 31P-NMR) analyses. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrum of POSS-S-PA acquired in a dithranol matrix, which has specifically designed for intractable polymeric materials. The observed characterization results signposted that novel organo-inorganic hybrid POSS-S-PA would be an efficacious material for fuel cells as a proton exchange membrane and high-temperature applications due to its thermal stability of 380 °C.

Titanium alloy modified with anti-biofouling zwitterionic polymer to facilitate formation of bio-mineral layer

The surface of a titanium (Ti) alloy was modified with a self-assembled monolayer of poly(ethylene glycol) methacrylate phosphate (Phosmer PE). A zwitterionic monomer (carboxymethyl betaine, CMB) could be copolymerized with the surface-bound Phosmer PE due to a flexible linker between the Ti alloy surface and a methacryloyl group of Phosmer PE. The poly(CMB) (PCMB)-modified Ti alloy plate exhibited strong suppression of protein adsorption and cell adhesion, and induced approximately twice the amount of calcium (Ca2+) deposition as compared to the unmodified Ti alloy plate. The zwitterionic polymer-modified surfaces not only showed enhanced mineralization clusters creation and growth, but they were also highly non-responsive to biologically derived materials such as proteins and cells. Therefore, it is possible to easily form highly pure and rigid hydroxyapatite layers on Ti alloy surfaces without the incorporation of organic molecules such as proteins. The present surface modification technique and strategy can be applied to implantable orthopedic materials as a means of encouraging integration with host tissues, such as the thigh bone.

Microscope-assisted UV-initiated preparation of well-defined porous polymer monolithic plugs in glass microchips for peptide preconcentration.

Herein, highly defined monolithic beds were prepared in glass microchips by photopolymerization of ethylene glycol methacrylate phosphate (EGMP), acrylamide, and N,N'-methylenebisacrylamide (BAA) using an epifluorescence microscope as UV-irradiation source. Such a fast and easy method allowed precise control of (i) the edge shape, (ii) the location along the microchannel, and (iii) the length of the monolithic plugs within glass microchips. The addition of hydroquinone, a polymerization inhibitor, to the prepolymerization mixture was beneficial for achieving local and robust incorporation of monoliths with sharp edges within microchannels. The monolith length was easily tuned from 160 to 400μm through simple change in the magnification of the objective and was foundto be repeatable (relative standard deviation <7.5%). Further application for on-chip monolith-assisted solid - phase extraction is demonstrated for fluorescently labeled peptide. Both binding and subsequent elution behaviors were found to fully agree with a cation-exchange mechanism in concordance with the presence of phosphate groups at the monolith surface. Graphical abstract In-chip microscope-UV-synthesis of monolithic plugs with sharp edges.