Methacrylate Groups Research Articles

Photo-Cross-Linkable Human Albumin Colloidal Gels Facilitate In Vivo Vascular Integration for Regenerative Medicine.

Biodegradable cellular and acellular scaffolds have great potential to regenerate damaged tissues or organs by creating a proper extracellular matrix (ECM) capable of recruiting endogenous cells to support cellular ingrowth. However, since hydrogel-based scaffolds normally degrade through surface erosion, cell migration and ingrowth into scaffolds might be inhibited early in the implantation. This could result in insufficient de novo tissue formation in the injured area. To address these challenges, continuous and microsized strand-like networks could be incorporated into scaffolds to guide and recruit endogenous cells in rapid manner. Fabrication of such microarchitectures in scaffolds is often a laborious and time-consuming process and could compromise the structural integrity of the scaffold or impact cell viability. Here, we have developed a fast single-step approach to fabricate colloidal hydrogels, which are made up of randomly packed human serum albumin-based photo-cross-linkable microparticles with continuous internal networks of microscale voids. The human serum albumin conjugated with methacrylic groups were assembled to microsized aggregates for achieving unique porous structures inside the colloidal gels. The albumin hydrogels showed tunable mechanical properties such as elastic modulus, porosity, and biodegradability, providing a suitable ECM for various cells such as cardiomyoblasts and endothelial cells. In addition, the encapsulated cells within the hydrogel showed improved cell retention and increased survivability in vitro. Microporous structures of the colloidal gels can serve as a guide for the infiltration of host cells upon implantation, achieving rapid recruitment of hematopoietic cells and, ultimately, enhancing the tissue regeneration capacity of implanted scaffolds.

Composition-controlled degradation behavior of macroporous scaffolds from three-armed biodegradable macromers

Acidification of implant microenvironment and inflammation due to degradation products of high molecular weight poly(α‑hydroxy acids) like PLA and PLGA is a risk that can limit their use in regenerative medicine, tissue engineering and drug delivery. We developed macromers that consist of a three-armed core with varying degrees of ethoxylation, hydrolytically degradable oligolactide blocks and terminal methacrylate groups (TriLA macromers) for cross-polymerization into monolithic or macroporous structures. Within the macromer platform, biophysical and biochemical properties can be adjusted by macromer chemistry. In this work, eight new macromer types with a reduced degree of methacrylation or substitution of a fraction of the lactic acid units with glycolic acid were successfully synthesized starting from a fully methacrylated, oligolactide-based TriLA macromer. Chemical characterization confirmed feed-dependent glycolic acid integration and controlled reduction in degree of methacrylation. The degradation behavior of macroporous scaffolds made by solid lipid templating from both the previously established and the new macromers was systematically investigated. In general, the scaffolds displayed continuous mass loss over time when the onset time of degradation was passed. Depending on arm length as well as hydrophilicity of the oligomeric building blocks, degradation half-life ranged from 3 to 4 weeks to over 81 weeks. Glycolic acid integration accelerated network degradation more effectively than an increase in core molecule hydrophilicity. The observed, adjustable degradation profiles with only moderate medium acidification and a dominant phase of almost linear mass loss make this material platform promising for regenerative and drug delivery applications.

Novel Ionic Conducting Composite Membrane Based on Polymerizable Ionic Liquids.

In this work, the design and characterization of new supported ionic liquid membranes, as medium-temperature polymer electrolyte membranes for fuel-cell application, are described. These membranes were elaborated by the impregnation of porous polyimide Matrimid® with different synthesized protic ionic liquids containing polymerizable vinyl, allyl, or methacrylate groups. The ionic liquid polymerization was optimized in terms of the nature of the used (photo)initiator, its quantity, and reaction duration. The mechanical and thermal properties, as well as the proton conductivities of the supported ionic liquid membranes were analyzed in dynamic and static modes, as a function of the chemical structure of the protic ionic liquid. The obtained membranes were found to be flexible with Young’s modulus and elongation at break values were equal to 1371 MPa and 271%, respectively. Besides, these membranes exhibited high thermal stability with initial decomposition temperatures > 300 °C. In addition, the resulting supported membranes possessed good proton conductivity over a wide temperature range (from 30 to 150 °C). For example, the three-component Matrimid®/vinylimidazolium/polyvinylimidazolium trifluoromethane sulfonate membrane showed the highest proton conductivity—~5 × 10−2 mS/cm and ~0.1 mS/cm at 100 °C and 150 °C, respectively. This result makes the obtained membranes attractive for medium-temperature fuel-cell application.

Injectable thiol-ene hydrogel of galactoglucomannan and cellulose nanocrystals in delivery of therapeutic inorganic ions with embedded bioactive glass nanoparticles

We propose an injectable nanocomposite hydrogel that is photo-curable via light-induced thiol-ene addition between methacrylate modified O-acetyl-galactoglucomannan (GGMMA) and thiolated cellulose nanocrystal (CNC-SH). Compared to free-radical chain polymerization, the orthogonal step-growth of thiol-ene addition allows a less heterogeneous hydrogel network and more rapid crosslinking kinetics. CNC-SH reinforced the GGMMA hydrogel as both a nanofiller and a crosslinker to GGMMA resulting in an interpenetrating network via thiol-ene addition. Importantly, the mechanical stiffness of the GGMMA/CNC-SH hydrogel is mainly determined by the stoichiometric ratio between the thiol groups on CNC-SH and the methacrylate groups in GGMMA. Meanwhile, the bioactive glass nanoparticle (BaGNP)-laden hydrogels of GGMMA/CNC-SH showed a sustained release of therapeutic ions in simulated body fluid in vitro, which extended the bioactive function of hydrogel matrix. Furthermore, the suitability of the GGMMA/CNC-SH formulation as biomaterial resin to fabricate digitally designed hydrogel constructs via digital light processing (DLP) lithography printing was evaluated.

Light-promoted synthesis of surface-grafted polymers bearing pyridine groups by metal-free ATRP in microliter volumes

Polymers with pendant pyridine groups (PPPGs) are pH responsive weak polyelectrolytes potentially attractive for many applications such as sensors, antibacterial coatings, and ion gating systems. Synthesis of PPPGs by classical atom transfer radical polymerization (ATRP) is very challenging due to highly probable formation of monomer/metal complexes. In response to that, we report here a facile synthetic strategy to obtain surface-grafted PPPGs that utilizes light-mediated ATRP. Metal-free surface-initiated ATRP catalyzed by 10-phenylphenothiazine is used to polymerize three isomeric monomers with methacrylate groups attached at various positions of a pyridine ring. The reactivity of the isomers is compared for selection of optimal monomer structure leading to thick brushes. The polymerizations are conducted under visible light, at ambient conditions, and using only microliter volumes of the reaction mixture that is important for reducing the complexity and costs of the process as well as limiting chemical waste. The observed linear dependency of the brush thickness vs polymerization time for poly(pyridin-3-yl methacrylate) (PP3M) grafted from indium tin oxide or silicon wafers indicated the controlled characteristics of the developed method. The obtained PP3M brush demonstrated pH responsive behavior associated with protonation of pyridine groups in acidic solution and adoption of highly stretched conformation below pKa.

Cationic Polymer-Coated Magnetic Nanoparticles with Antibacterial Properties: Synthesis and In Vitro Characterization.

Uniformly sized magnetite nanoparticles (Dn = 16 nm) were prepared by a thermal decomposition of Fe(III) oleate in octadec-1-ene and stabilized by oleic acid. The particles were coated with Sipomer PAM-200 containing both phosphate and methacrylic groups available for the attachment to the iron oxide and at the same time enabling (co)polymerization of 2-(dimethylamino)ethyl methacrylate and/or 2-tert-butylaminoethyl methacrylate at two molar ratios. The poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[2-(dimethylamino)ethyl methacrylate-co-2-tert-butylaminoethyl methacrylate] [P(DMAEMA-TBAEMA)] polymers and the particles were characterized by 1H NMR spectroscopy, size-exclusion chromatography, transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, magnetometry, and ATR FTIR and atomic absorption spectroscopy. The antimicrobial effect of cationic polymer-coated magnetite nanoparticles tested on both Escherichia coli and Staphylococcus aureus bacteria was found to be time- and dose-responsive. The P(DMAEMA-TBAEMA)-coated magnetite particles possessed superior biocidal properties compared to those of P(DMAEMA)-coated one.

β-Cyclodextrin-Polyacrylamide Hydrogel for Removal of Organic Micropollutants from Water

Water pollution by various toxic substances remains a serious environmental problem, especially the occurrence of organic micropollutants including endocrine disruptors, pharmaceutical pollutants and naphthol pollutants. Adsorption process has been an effective method for pollutant removal in wastewater treatment. However, the thermal regeneration process for the most widely used activated carbon is costly and energy-consuming. Therefore, there has been an increasing need to develop alternative low-cost and effective adsorption materials for pollutant removal. Herein, β-cyclodextrin (β-CD), a cheap and versatile material, was modified with methacrylate groups by reacting with methacryloyl chloride, giving an average degree of substitution of 3 per β-CD molecule. β-CD-methacrylate, which could function as a crosslinker, was then copolymerized with acrylamide monomer via free-radical copolymerization to form β-CD-polyacrylamide (β-CD-PAAm) hydrogel. Interestingly, in the structure of the β-CD-PAAm hydrogel, β-CD is not only a functional unit binding pollutant molecules through inclusion complexation, but also a structural unit crosslinking PAAm leading to the formation of the hydrogel 3D networks. Morphological studies showed that β-CD-PAAm gel had larger pore size than the control PAAm gel, which was synthesized using conventional crosslinker instead of β-CD-methacrylate. This was consistent with the higher swelling ratio of β-CD-PAAm gel than that of PAAm gel (29.4 vs. 12.7). In the kinetic adsorption studies, phenolphthalein, a model dye, and bisphenol A, propranolol hydrochloride, and 2-naphthol were used as model pollutants from different classes. The adsorption data for β-CD-PAAm gel fitted well into the pseudo-second-order model. In addition, the thermodynamic studies revealed that β-CD-PAAm gel was able to effectively adsorb the different dye and pollutants at various concentrations, while the control PAAm gel had very low adsorption, confirming that the pollutant removal was due to the inclusion complexation between β-CD units and pollutant molecules. The adsorption isotherms of the different dye and pollutants by the β-CD-PAAm gel fitted well into the Langmuir model. Furthermore, the β-CD-PAAm gel could be easily recycled by soaking in methanol and reused without compromising its performance for five consecutive adsorption/desorption cycles. Therefore, the β-CD-PAAm gel, which combines the advantage of an easy-to-handle hydrogel platform and the effectiveness of adsorption by β-CD units, could be a promising pollutant removal system for wastewater treatment applications.

Monomer Conversion, Dimensional Stability, Biaxial Flexural Strength, Ion Release, and Cytotoxicity of Resin-Modified Glass Ionomer Cements Containing Methacrylate-Functionalized Polyacids and Spherical Pre-Reacted Glass Fillers.

The aim of this study was to prepare RMGICs for pulp protection that contain polyacids functionalized with methacrylate groups (CMs) to enable light-activated polymerization without the need for toxic 2-hydroxyethyl methacrylate (HEMA) monomers. The effects of using CM liquids with 0 or 5 wt% HEMA on the physical/mechanical properties and cytotoxicity of the experimental RMGICs were assessed. Spherical pre-reacted glass fillers (SPG) were used as the powder phase. The experimental RMGICs were prepared by mixing SPG with CM liquid (0 wt% HEMA, F1) or CMH liquid (5 wt% HEMA, F2). Commercial materials (Vitrebond, VB; TheraCal LC, TC) were used for the comparisons. The degree of monomer conversion and fluoride release of both F1 and F2 were significantly lower than those of VB. F1 showed comparable biaxial flexural strength with VB but higher strength than TC. The dimensional stability (mass/volume changes) of the experimental materials was comparable with that of the commercial materials. F1 and F2 exhibited higher Sr/Ca ion release and relative cell viability than VB. The use of CMH liquid reduced the strength but enhanced the fluoride release of the experimental RMGICs. In conclusion, the experimental RMGICs showed comparable strength but lower cytotoxicity compared to the commercial RMGICs. These novel materials could be used as alternative materials for pulp protection.

Enhanced mechanical performance of aDGEBAepoxyresin‐basedshape memory polymer by introducing graphene oxide via covalent linking

AbstractShape memory polymers (SMP) are prepared, via dual thiol‐epoxy/thiol‐ene reactions, from diglycidyl ether of bisphenol A (DGEBA), a trithiol (TMP), a tetraallyl amine (TAA), and small amounts (0.1–0.5 wt.%) of graphene oxide either pristine (GO) or functionalized with methacrylate groups (GOM). The incorporation of GOMto the epoxy resin network permits a good load transfer, which is reflected in improved properties such as Young modulus (from 220 to 519 MPa), tensile strength (from 46.3 to 69.2 MPa), Izod impact strength (from 0.051 to 0.42 J/mm), torque (from 0.008 to 0.031 Nm), and glass transition temperature (from 75 to 105°C). Such improvement in properties is attributed to the incorporation of GOMvia covalent linking, which is a good strategy for improving polymer‐particle interaction and particle dispersion. The epoxy‐based SMP also show high storage modulus (up to 2.36 GPa) and high deformation capacity, which are reflected in good shape fixity (between 97% and 100%) and thermo‐induced shape recovery (between 97% to 99.7%) behaviors in flexion mode tests.

Rheological Properties, Surface Microhardness, and Dentin Shear Bond Strength of Resin-Modified Glass Ionomer Cements Containing Methacrylate-Functionalized Polyacids and Spherical Pre-Reacted Glass Fillers.

The aim of this study was to prepare experimental resin-modified glass ionomer cements (RMGICs) containing low levels of hydroxyethyl methacrylate (HEMA) for pulp protection. Liquid and powder phases of the experimental RMGICs were polyacid functionalized with methacrylate groups and spherical pre-reacted glass fillers (SPG). Two types of liquid phase containing 0 wt. % HEMA (CM liquid) or 5 wt. % HEMA (CMH liquid) were formulated. The experimental RMGICs were prepared by mixing SPG fillers with CM liquid (F1) or CMH liquid (F2). Rheological properties were examined using a strain-controlled rheometer (n = 5). The Vickers microhardness (n = 5) and dentin shear bond strength (SBS) (n = 10) of the materials were tested. Commercial pulp protection materials (Vitrebond and TheraCal LC) were used as comparisons. The viscosity and surface microhardness of F1 (22 m Pa·s, 18 VHN) and F2 (18 m Pa·s, 16 VHN) were significantly higher than those of Vitrebond (6 mPa·s, 6 VHN) and TheraCal (0.1 mPa·s, 7 VHN). The SBS of F1 (10.7 MPa) and F2 (11.9 MPa) was comparable to that of Vitrebond (15.4 MPa) but higher than that of TheraCal LC (5.6 MPa). The addition of 5 wt. % HEMA showed no significant effect on viscosity, surface microhardness, or SBS of the experimental RMGICs. The experimental materials showed higher viscosity and microhardness but similar SBS when compared with the commercial RMGIC.

Adhesive Resins with High Shelf-Life Stability Based on Tetra Unsaturated Monomers with Tertiary Amines Moieties

This work reports the use of two monomers with two tertiary amines and four methacrylic (TTME) or acrylic (TTAC) terminal groups as co-initiators in the formulation of experimental resin adhesive systems. Both monomers were characterized by FT-IR and 1H NMR spectroscopies. The control adhesive was formulated with BisGMA, TEGDMA, HEMA, and the binary system CQ-EDAB as a photo-initiator system. For the experimental adhesives, the EDAB was completely replaced for the TTME or the TTAC monomers. The adhesives formulated with TTME or TTAC monomers achieved double bond conversion values close to 75%. Regarding the polymerization rate, materials formulated with TTME or TTAC achieved lower values than the material formulated with EDAB, giving them high shelf-life stability. The degree of conversion after shelf simulation was only reduced for the EDAB material. Ultimate tensile strength, translucency parameter, and micro-tensile bond strength to dentin were similar for control and experimental adhesive resins. Due to their characteristics, TTME and TTAC monomers are potentially useful in the formulation of photopolymerizable resins for dental use with high shelf-life stability.

Sunitinib-Loaded Chondroitin Sulfate Hydrogels as a Novel Drug-Delivery Mechanism for the Treatment of Pancreatic Neuroendocrine Tumors.

Pancreatic neuroendocrine tumors (PanNETs) are increasingly common. Experts debate whether small tumors should be resected. Tumor destruction via injection of cytotoxic agents could offer a minimal invasive approach to this controversy. We hypothesize that a new drug delivery system comprising chondroitin sulfate (CS) hydrogels loaded with sunitinib (SUN) suppresses tumor growth in PanNET cells. Injectable hydrogels composed of CS modified with methacrylate groups (MA) were fabricated and loaded with SUN. Loading target was either 200 µg (SUN200-G) or 500 µg (SUN500-G) as well as sham hydrogel with no drug loading (SUN0-G). SUN release from hydrogels was monitored in vitro over time and cytotoxicity induced by the released SUN was evaluated using QGP-1 and BON1 PanNET cell lines. QGP-1 xenografts were developed in 35 mice and directly injected with 25 µL of either SUN200-G, SUN500-G, SUN0-G, 100 µL of Sunitinib Malate (SUN-inj), or given 40 mg/kg/day oral sunitinib (SUN-oral). SUN-loaded CSMA hydrogel retained complete in vitro cytotoxicity toward the QGP-1 PanNET and BON-1 PanNET cell lines for 21 days. Mouse xenograft models with QGP-1 PanNETs showed a significant delay in tumor growth in the SUN200/500-G, SUN-inj and SUN-oral groups compared with SUN0-G (p = 0.0014). SUN500-G hydrogels induced significantly more tumor necrosis than SUN0-G (p = 0.04). There was no difference in tumor growth delay between SUN200/500G, SUN-inj, and SUN-oral. This study demonstrates that CSMA hydrogels loaded with SUN suppress PanNETs growth. This drug delivery could approach represents a novel way to treat PanNETs and other neoplasms via intratumoral injection.

Effect of the methacrylic group on the degradation of polar achiral composites after successive poling cycles and appearance of antiferroelectric behaviour

We are studying a polar system composed of a polymer and its monomer in a 2:1 ratio. Although both components are non-chiral, their mixture shows a high spontaneous polarization due to hydrogen bond structuration. The original system shows a decrease in the spontaneous polarization through successive poling cycles. We replace the methacrylic moiety on two monomers with different aliphatic tail length (octyloxy/dodecyloxy) for a non-polymerizable isobutyric group. We study their mesomorphism as pure molecules and forming part of the composites by differential scanning calorimetry, polarizing optical microscopy and powder X-ray diffraction. We compare how the successive poling cycles affects the polar response as pyroelectric signal (γ) and loop hysteresis of these new polymer-isobutyric monomer composites vs their conventional counterpart polymer-methacrylic monomer composites. We found a decrease in the pyroelectric response with successive poling cycling in all composites. Regarding the structure of the composites obtained with the new saturated monomers, they exhibited polar behaviour. Surprisingly, for the isobutyric monomer with a dodecyloxy tail, the composite shown antiferroelectric behaviour unlike the ferroelectric methacrylic counterpart. The new phenomena must be due to steric hindrance caused by the bulky isobutyric group, forcing the monomers to lie between the sidechain of the polymer with the bulkier isobutyric group at the alkyl chain layer interface rather than near the polymeric main chain.

Metal adsorption properties of multi‐functional PAMAM dendrimer based gels

AbstractMetal adsorption studies are getting important and there are many functional adsorbents developed recently. Here, we report the synthesis of multifunctional PAMAM G2 (polyamidoamine) possessing methacryl, amine, hydroxyl and phosphonate groups used in free radical curing gel formulations. UV curable gel is conducted in the presence of acrylamide, bisacrylamide, and polyethylene glycol diacrylate. Adsorption study of the resulting novel sorbents (gels) are carried out with a series of metals. Through a comprehensive study, structure–property relationship of the series gels is conducted by using different amount of amine, hydroxyl, and/or phosphonate ester groups on the PAMAM G2. Selected metals are Cr3+, Fe3+, Ni2+, Cu2+, Ag+, and Cd2+ within a series of hard, intermediate, and soft ionic species. Adsorption study is carried out in pure water environment at neutral pH. Metal ions removal percentages and adsorption capacities of gel adsorbents are calculated by using atomic absorption spectroscopy. There is relationship between the overall functional groups presence in gel formulation and swelling densities for removing the metal ions. Introducing dendrimer into the gel formulation enhanced the metal ions adsorption against to Bare GEL formulation which do not possess dendrimer units. Consequently, the maximum removal efficiency has been obtained for Cr3+ and Fe3+.

Novel Multifunctional Epoxy (Meth)Acrylate Resins and Coatings Preparation via Cationic and Free-Radical Photopolymerization.

In this work, a series of novel multifunctional epoxy (meth)acrylate resins based on a low-viscosity aliphatic triepoxide triglycidyl ether of trimethylolethane (TMETGE) and acrylic acid (AA) or methacrylic acid (MMA) have been synthesized. Thanks to the performed modification, the obtained prepolymers have both epoxides as well as carbon–carbon double bonds and differ in their amount. The obtained results indicate that the carboxyl-epoxide addition esterification occurs in the presence of a catalyst (triphenylphosphine) at a temperature of 90 °C, whilst the required degree of conversion can be achieved simply by varying both the reagents ratio and reaction time. The structure of synthesized copolymers was confirmed by spectroscopic analyses (FT-IR, 1H NMR, 13C NMR) and studied regarding its nonvolatile matter content (NV), acid value (PAVs), as well as its epoxy equivalent value (EE). Due to the presence of both epoxy and double carbon–carbon pendant groups, one can apply two distinct mechanisms: (i) cationic ring-opening polymerization or (ii) free-radical polymerization to crosslink polymer chains. Synthesized epoxy (meth)acrylate prepolymers were further employed to formulate photocurable coating compositions. Hence, when cationic photoinitiators were applied, polyether-type polymer chains with pending acrylate or methacrylate groups were formed. In the case of free-radical polymerization, epoxy (meth)acrylates certainly formed a poly(meth)acrylate backbone with pending epoxy groups. Further, photopolymerization behavior and properties of cured coatings were investigated regarding some structural factors and parameters. Moreover, reaction rate coefficients of photo-cross-linking by both cationic ring-opening and free-radical photopolymerization of the received epoxy (meth)acrylate resins were determined via real-time infrared spectroscopy (RT-IR). Lastly, basic physicomechanical properties, such as tack-free time, hardness, adhesion, gloss, and yellowness index of cured coatings, were evaluated.

Bio-Based Hydrogels With Ion Exchange Properties Applied to Remove Cu(II), Cr(VI), and As(V) Ions From Water.

Hydrogels with ion exchange properties were synthesized from compounds derived from wood biopolymer hemicellulose and from commercial vinyl monomers to be tested as active materials for the removal of Cu(II), Cr(VI), and As(V) ions. The hemicellulose O-acetyl galactoglucomannan (GGM) was used as the precursor material, and through a transesterification reaction, GGM was converted into a macromonomer GGM–glycidyl methacrylate (GGM-GMA). Subsequently, the GGM-GMA macromonomer, containing more than one methacrylate group, was used as a crosslinking agent in the synthesis of hydrogels through free-radical polymerization reactions in combination with a 2-acrylamido-2-methyl-1-propanesulfonic acid monomer to produce a cation exchange hydrogel. Also, (3-acrylamidopropyl)trimethylammonium chloride monomer was applied together with the GGM-GMA to form hydrogels that can be used as anion exchange hydrogel. The hydrogels were characterized by Fourier transform-infrared (FT-IR), 1H-NMR spectroscopy, and thermogravimetric analysis (TGA), as well as derivative thermogravimetry (DTG). The microstructure of the hydrogels was characterized by scanning electron microscopy (SEM) analysis with X-ray microanalysis energy-dispersive spectroscopy (EDS). The results obtained regarding the absorption capacity of the Cu(II), Cr(VI), and As(V) ions were studied as a function of the pH value and the initial concentration of the metal ions in the solutions. Absorption was carried out in consecutive batches, and it was found that the poly(GGM-GMA/AMPSH) hydrogel reached an absorption capacity of 90 mg g–1 for Cu(II). The poly(GGM-GMA/APTACl) hydrogel reached values of 69 and 60 mg g–1 for Cr(VI) and As(V) oxyanions, respectively. Tests with polymer blends (mixtures of anionic and cationic hydrogels) were also carried out to remove Cu(II), Cr(VI), and As(V) ions from multi-ionic solutions, obtaining satisfactory results.

Efficient and selective extraction of azamethiphos and chlorpyrifos residues from mineral water and grape samples using magnetic mesoporous molecularly imprinted polymer

A magnetic mesoporous molecularly imprinted polymers was synthesized on the surface of magnetic nanoparticles silanized with 3-(trimethoxysilyl) propyl methacrylate to introduce reactive methacrylate groups. Subsequently, methacrylic acid monomers were grafted onto the surface of this adsorbent functionalized via polymerization by precipitation. Magnetic mesoporous molecularly imprinted polymer was properly characterized by different techniques and applied as adsorbent in magnetic solid phase extraction for selective determination of two organophosphorus pesticides, azamethiphos and chlorpyrifos, in mineral water and grape samples. After sample preparation optimization, recoveries of 99.56% and 98.86% were obtained for azamethiphos and chlorpyrifos, respectively. The magnetic solid phase extraction coupled to HPLC-UV presented limit of quantification of 5 ng mL−1, linearity ranged of 5 to 1000 ng mL−1, in addition to adequate accuracy, precision and robustness. The pesticides showed stability in the matrix and were satisfactorily quantified in real mineral water and grape samples.

Cross-linking of antimicrobial polymers with hexamethylene diamine to prevent biofouling in marine applications

The design of antimicrobial polymers is a growing field, as they may replace conventional antimicrobial agents leading to plenty of advantages in marine applications. Polymers with active functional groups may act as carriers for antimicrobial agents. The antimicrobial polymers P(SSAmC16-co-GMAx) and P(VBCHAM-co-AAx) bearing quaternary ammonium compounds, either electrostatically bound (cetyltrimethylammonium 4-styrene sulfonate, SSAmC16) or covalently attached (vinyl benzyl dimethylhexadecylammonium chloride, VBCHAM), were prepared in the present work. The cross-linking agent hexamethylene diamine (HMDA) was used for the reaction between copolymers’ reactive groups, epoxide groups of glycidyl methacrylate (GMA) or carboxylic groups of acrylic acid (AA), with the amine groups. Various blends of each reactive copolymer with hexamethylene diamine in different compositions were prepared and the cross-linking reaction was explored through solution casting after curing at room temperature (RT), 80 °C and 120 °C for 24 h in order to find the best conditions for the designing of a firm and strong coating. In a further step, specific blend combinations of the reactive antimicrobial copolymers combined with hexamethylene diamine were used to coat pre-weighed aquaculture nets which were cross-linked at 120 °C and used in laboratory accelerated conditions as well as in real conditions by immersion of the nets at an aquaculture unit in the Saronic Bay of Greece. The modified nets along with blank nets were tested in terms of antifouling efficacy for 35 days in accelerated conditions and 30 days in real conditions. The novel cross-linked antimicrobial coatings indicated high antifouling activity and high cleaning efficacy as the fouling microorganisms at the end of the test were easily removed from the coated net in contrast to the uncoated net after high pressure cleaning.

Preparation of photo-crosslinkable acrylic copolymer and its debonding property on silicon wafer

As silicon wafers become thinner and easier to warp, it is important to improve production efficiency of dies. In the wafer grinding and dicing process, photo-crosslinkable pressure sensitive adhesive (PSA) tapes are applied to fix the silicon wafer and greatly increase die yield. The PSA tapes must be peeled easily without any residues after UV light irradiation. Herein, a hydroxyl group containing copolymer was first synthesized from 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid and hydroxyethyl acrylate monomers via free radical polymerization, followed by the introduction of methacrylate groups through the addition reaction of 2-isocyanatoethyl methacrylate with hydroxyl groups on side chain of copolymers. The photo-crosslinkable adhesive was then prepared by the mixing the copolymers with photoinitiator and aziridine crosslinker. Glass transition temperature (Tg) and storage modulus of the photo-crosslinked adhesives increased with UV irradiation time, which benefited the picking-up process. A digital microscope was used to observe the surface morphology of the debonded silicon wafers and excellent debonding effect occurred after 40 s UV irradiation.

Evaluation of flexural properties and dynamic mechanical analysis of glass fiber-reinforced polyamide resin.

The aim of this study was to evaluate flexural strength, elastic modulus and dynamic mechanical analysis (DMA) of heat-polymerized polymethyl methacrylate resin, polyamide resin and glass fiber-reinforced polyamide resin. Three groups were determined according to denture base materials as polymethyl methacrylate resin (H), polyamide resin (P) and glass fiber reinforced polyamide resin (R). Sixteen specimens for each denture base material were prepared with dimensions of 64x10x3.3 mm for three-point bending test. Two specimens for each denture base material were prepared with dimensions of 30x10x3 mm for DMA. Polymethyl methacrylate and polyamide specimens were prepared according to the manufacturer's recommendations. The silane was applied to glass fibers (4.5 mm length) 2% by weight of the polyamide resin, they were placed in polyamide resin cartilages and injected to the mold. The thermal aging procedure was applied to half of specimens of each material (n=8). Flexural strength and elastic modulus of the specimens were determined by three-point bending test at a speed of 5 mm/ min. DMA was performed to 1 specimen from each group to evaluate viscoelastic properties. Data were analyzed with one-way ANOVA, Tukey and Paired t tests. A statistically significant difference was found in flexural strength and elastic modulus values of denture base materials (p=0.00). The highest flexural strength and elastic modulus values were observed in polymethyl methacrylate group. There was no significant difference between polyamide and glass-fiber reinforced polyamide groups (p=0.497). No significant difference was determined in all threedenture base materials before and after aging procedure. The reinforcement with glass-fibers did not affect the flexural strength and elastic modulus of polyamide resin.