Methacrylic Acid Derivatives Research Articles

Myrcene-itaconate Diels-Alder cycloadducts in the synthesis of photocurable polyesters for the 3D printing of fully biobased resins

Photopolymerization-based 3D printing techniques, such as vat photopolymerization (VP), unfortunately still strongly rely on the use of fossil-based (meth)acrylate monomers for the formulation of photo hardening resins. Because of that many researchers have recently directed their efforts towards the replacement of methacrylic and acrylic acid derivatives with biobased counterparts. Indeed, in this work, we introduce a novel approach for producing sixteen fully biobased resins for VP, based on photocurable polyesters synthesized starting from bio-sourced reagents. Itaconic acid, widely recognized as an effective biobased photocurable monomer, and myrcene, a terpene consisting of two isoprene units, are employed in a Diels-Alder cycloaddition to achieve a co-monomer (My-DMI) for the new photocurable polyesters. By exploring various molecular weights, diols and ratios between itaconate and My-DMI, we synthesized eight different polyesters. By combining these with appropriately designed reactive diluents, we successfully tuned the mechanical properties of the 3D printed materials, ranging from very flexible to extremely rigid, depending on the diol chain length and itaconate contents. Additionally, we provide a detailed evaluation of the biobased content of each formulation according to the OK BIOBASED labelling for plastics, finding biobased content as high as 97 % in most cases.

LuMA-Functionalized Thermosensitive Hydrogel: A Versatile and Robust Dopamine-Triggered Platform for Diverse Biomolecules Sensing.

It is of great significance for the analysis of multiple biomarkers because a single biomarker is difficult to accurately achieve early diagnosis, disease course monitoring, and prognosis evaluation. Herein, a luminescence thermosensitive hydrogel was synthesized by radical polymerization using a methacrylic acid derivative monomer of luminol (LuMA) as luminescent, N-isopropylacrylamide (NIPAM) as thermosensitive monomer, and acrydite-oligonucleotides [dopamine (DA) aptamer, DNA C1, and DNA C2] as recognition elements. The combined DA based on the affinity interaction between the DA and the aptamer on the hydrogel polymer chain was electrochemically oxidized to dopamine quinone during the electrochemiluminescence (ECL) scanning, which effectively quenched the ECL signal of LuMA due to the resonance energy transfer (RET). In addition, the thermosensitive hydrogel showed swelling-collapse characteristics when the temperature was below and above the volume phase transition temperature. Undergoing the collapse process initiated by the temperature, the RET efficiency was further enhanced due to the shortened distance between the energy donor and acceptor, showing a 1.4 times signal amplification and achieving sensitive detection of DA with a limit of detection (LOD) of 1.7 × 10-10 M. For a proof of concept application, coupled with the target-induced release of DA from the DNA-magnetic beads bioconjugations based on duplex-specific nuclease (DSN)-assisted target recycling amplification strategy and DNAzyme cleavage reaction, this ECL-RET approach was successfully used to evaluate multiple targets including miRNA-141 and MUC1 with the LOD of 2.5 aM and 1.6 fg/mL, respectively. The excellent performances of the versatile and robust ECL-RET hydrogel in multiple target sensing showed potential applications in clinical diagnosis and disease therapeutic assay.

Acrylate and Methacrylate Polymers' Applications: Second Life with Inexpensive and Sustainable Recycling Approaches.

Polymers are widely employed in several fields thanks to their wide versatility and the easy derivatization routes. However, a wide range of commercial polymers suffer from limited use on a large scale due to their inert nature. Nowadays, acrylate and methacrylate polymers, which are respectively derivatives of acrylic or methacrylic acid, are among the most proposed materials for their useful characteristics like good biocompatibility, capping ability toward metal clusters, low price, potentially recyclability and reusability. Here, we discuss the advantages and challenges of this class of smart polymers focusing our attention on their current technological applications in medical, electronic, food packaging and environmental remediation fields. Furthermore, we deal with the main issue of their recyclability, considering that the current commercial bioplastics are not yet able to meet the global needs as much as to totally replace fossil-fuel-based products. Finally, the most accredited strategies to reach recyclable composites based on acrylic polymers are described.

Study of the synthesis of a copolymer of isodecyl- and benzylmethacrylates after radiation initiation

Polymerization was carried out using the method of radiation initiation. Experiments were carried out on methacrylic acid derivatives with bulky substituents (isodecyl and benzyl). The regularities of its formation are investigated. The conditions for obtaining a homogeneous copolymer are determined. A polymer with a molecular weight of more than 106 g/mol was obtained. An increase in the viscosity of the copolymer with an increase in the temperature of the solution was shown.

Platinum-Catalyzed Deuteration of Acrylic and Methacrylic Acid Derivatives

Key words deuteration - platinum on carbon - acrylic acid derivatives - methacrylic acid derivatives

Direct Deuteration of Acrylic and Methacrylic Acid Derivatives Catalyzed by Platinum on Carbon in Deuterium Oxide

AbstractThe platinum on carbon (Pt/C)‐catalyzed deuteration of acrylic and methacrylic acid derivatives in deuterium oxide (D2O) efficiently proceeded to give the corresponding acrylic acid‐d3 and methacrylic acid‐d5 derivatives. The olefinic functionality, as well as the methyl group on the unsaturated functionality of the substrate, were satisfactorily deuterated via the hydrogen (H)‐deuterium (D) exchange reaction. The obtained deuterated compounds are useful building blocks and efficiently converted to the corresponding desired products including a polymer without the degradation of the original deuterium contents.magnified image

Potentiometric Langmuir Isotherm Analysis of Histamine-Selective Molecularly Imprinted Polymer-Based Field-Effect Transistor

In this study, we report label-free and selective histamine detection using a molecularly imprinted polymer (MIP)-coated gate field-effect transistor (FET). First, we designed the histamine-selective MIP; methacrylic acid derivatives were chosen as a functional monomer to induce the change in molecular charges based on the histamine/monomer complex in the prepolymer solution, because histamine contains several hydrogen bond acceptors such as amino groups; moreover, the crosslinker/monomer ratio in the polymer was controlled to strengthen the structure of the polymer matrix and to enhance the selectivity of the MIP to histamine. As a result, the histamine-templated MIP (HMIP)-coated FET showed a good electrical response to histamine at a concentration of 100 μM and above, enabling the detection of histamine secreted from mast cells based on allergic responses. Moreover, more selective detection to histamine was realized by using an HMIP with higher crosslink density, as shown by comparing the electrical response upon adding L-histidine to an HMIP-FET, which has a similar chemical structure to histamine. The enhancement of selectivity to histamine was clarified on the basis of the binding constant estimated by potentiometric Langmuir isotherm analysis.

Ethylene glycol dimethacrylate and diethylene glycol dimethacrylate exhibits cytotoxic and genotoxic effect on human gingival fibroblasts via induction of reactive oxygen species

Although methacrylic acid derivatives in their polymeric form are considered to be safe, insufficient polymerization and the release of monomers due to either mechanical or enzymatical factors can lead to their reaching millimolar concentrations in local tissue. The present study evaluates the effect of two methacrylate monomers – ethylene glycol dimethacrylate (EGDMA) and diethylene glycol dimethacrylate (DEGDMA) – on human gingival fibroblasts (HGFs). Both monomers were found to reduce cells viability in MTT assay, increase apoptosis and cause cell cycle arrest in G1/G0 phase. They also increased intracellular reactive oxygen species (ROS) production as measured by DCFH-DA and DHE probes and increased expression of GPx4 and SOD2. Both monomers increased DNA damage in comet assay. Moreover, HGFs were not able to repair those lesions within 120min of repair incubation. However, the monomers were not found to have any effect on the integrity of isolated plasmids. We postulate that EGDMA and DEGDMA exhibit their cytotoxic and genotoxic properties via increased production of ROS, which cause DNA damage, affect apoptosis, viability and cell cycle. Further studies are needed to better understand the properties of methacrylic acid monomers and to evaluate the risk that they cause for patients, dentists and dental technicians.

A methacrylic hyaluronic acid derivative for potential application in oral treatment of celiac disease

Objective: Aim of this work was the synthesis of a methacrylic hyaluronic acid (HA) derivative and the production, via photocrosslinking, of related hydrogels loaded with an endopeptidase intended for a potential oral treatment of celiac disease.Methods: The methacrylic derivative of HA was prepared through a one-pot procedure involving the reaction with ethylenediamine (EDA) and methacrylic anhydride (MA). The obtained derivative, named HA-EDA-MA, was used to prepare photocrosslinked hydrogels loaded with a prolyl endopeptidase derived from Flavobacterium meningosepticum (PEP FM) able to detoxify gliadin. Obtained hydrogels were recovered as gels or freeze-dried powders.Results: Hydrogels obtained as freeze-dried powders, are able to protect loaded enzyme from degradation due to freeze-drying process and from alteration during storage, overall in the presence of a cryoprotectant. All photocrosslinked HA-EDA-MA hydrogels (gels and powders) release PEP FM in simulated intestinal fluid in sustained manner and in active form. HA-EDA-MA hydrogels are nontoxic as demonstrated through in vitro studies on BALB 3T3 cells.Conclusions: Prepared hydrogels show a potential application for oral treatment of celiac disease thanks to the possibility to release enzymes able to detoxify the gliadin peptide that induces the immunogenic response.

Highly efficient antifouling property based on self‐generating hydrogel layer of polyacrylamide coatings

ABSTRACTPursuit of robust antifouling coatings is a persistent objective for marine materials. We present here the experimental realization of a series of polyacrylamide‐based resins with a self‐generating hydrogel layer, arising from the polymerization of acrylamide (AM), butyl acrylate, methacrylic acid, and AM derivatives. The mechanical strength and thermal stability are markedly enhanced due to the change of the structure of modified resins. The preliminary results indicate that resultant resins with crosslinking structure show satisfactory abrasion resistance and swelling properties. The results of antifouling panel testing in shallow submergence for three months reveal that the addition of AM derivatives leads to generation of a thin soft and dynamic layer of hydrogel, which enhances antifouling properties. The formation of hydrogel and self‐generating property make it promising in various antifouling applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44111.

Thermodynamics of interfacial interactions in composites based on nanodispersed NiO and methacrylic acid derivatives

Interfacial interactions in composites based on nanodispersed nickel oxide and methacrylate polymer matrices are studied via isothermal microcalorimetry. The thermochemical cycle is used to estimate the concentration dependences of the enthalpies of mixing of nickel oxide with, respectively, poly(methyl methacrylate), poly(butyl methacrylate), poly(acrylic acid), poly(methacrylic acid), and the butyl methacrylate copolymers containing 1 and 5 mol % methacrylic acid units. On the basis of these data, the maximum enthalpies of adhesion and the parameters of the glassy structure of the polymers are calculated. It is shown that the increase in the absolute values of the maximum enthalpy of adhesion is related to a gain in the fraction of carboxyl groups in the macromolecular chain. Strengthening of interfacial interactions for glassy polymers correlates with an increase in the fraction of metastable vacancies and in the thickness of the adhesion glassy layer.

Polymers for nanolitography: New strategy of the design and synthesis of copolymers based on methacrylic acid derivatives with cyclobutyldicyclopropylmethyloxymethyl, 3-sulfolanyl, and 1-perfluoroethylcyclohexyl pendant groups

Polymers for nanolitography: New strategy of the design and synthesis of copolymers based on methacrylic acid derivatives with cyclobutyldicyclopropylmethyloxymethyl, 3-sulfolanyl, and 1-perfluoroethylcyclohexyl pendant groups

Well‐defined N‐Isopropylacrylamide Dual‐Sensitive Copolymers with LCST ≈38 °C in Different Architectures: Linear, Block and Star Polymers

AbstractReversible addition‐fragmentation chain transfer (RAFT) polymerization is used to prepare temperature‐ and pH‐sensitive statistical copolymers with lower critical solution temperature (LCST) close to 38 °C at pH 7.4 based on N‐isopropylacrylamide and methacrylic acid derivative comonomers with a pKa close to 6. Statistical copolymers are re‐activated to prepare amphiphilic block copolymers and star polymers with cross‐linked core. The LCST is maintained by varying the architecture; however, the LCST originated behaviour changes due to self‐aggregation. Statistical copolymers and short block copolymers show complex aggregation, whereas mid‐size block copolymers and star polymers show shrinkage of aggregate dimensions. The pH of the medium has a profound impact on the self‐assembling behaviour of the different polymer architectures.

Evaluation of Cell‐Material Interactions on Newly Designed, Printable Polymers for Tissue Engineering Applications

AbstractThe generation of advanced scaffolds for tissue engineering is increasingly implemented by rapid prototyping techniques and therefore designed materials. Two novel polymeric networks based on newly synthesized carboxyfunctionalized polyacrylates were created to fit the requirements of 3D printing processes regarding viscosity and their surface tension. The polyacrylates presented carboxylic groups either without any spacer, or, in the case of mono‐(2‐acryloxyethyl)‐succinate, with a substantial spacing from the polymer backbone. The material properties were characterized with rheometry, FTIR, XPS, and contact angle measurements. Polymer surfaces were prepared and seeded with primary human dermal microvascular endothelial cells (HDMEC). Cell–material interaction with the different polymer surfaces were investigated by light microscopy, water soluble tetrazolium‐1 (WST‐1) viability assay, fluorescein diacetate/propidium iodide (FDA/PI) staining, and acetylated low‐density lipoprotein (acLDL) assay. Thus, the cell confluence, viability, and functionality of the HDMEC were evaluated. The non‐spaced methacrylic acid derivative was proved in cell culture regarding its biocompatibility. Along with its appropriate physical properties, the novel network‐generating polymeric blends constitute promising candidates for future scaffold design in tissue engineering.

Grafting CVD of Poly(vinyl pyrrolidone) for Durable Scleral Lens Coatings

AbstractGrafting (g)CVD from the monomer 1‐vinyl‐2‐pyrrolidone (VP) and the Type II initiator benzophenone (BP) under 254 nm UV irradiation yields durable hydrophilic coatings on substrates of poly(methacrylic acid) (PMA) derivatives, desirable for scleral lens applications. The gCVD polymerization of the VP monomer is essentially complete, and little excess BP remains in the film. Process optimization, through single variable and two fractional factorial experiments, result in retention of >90% of the as‐deposited film thickness after rinsing. Increasing the initiator dosing time beyond 10 min, or the UV exposure time beyond 5 min, has little effect on the as‐deposited thickness, or percentage of film retained after rinsing. This suggests that UV irradiation rapidly transforms most of the BP absorbed on the surface to initiating radicals. Once sufficient initiator dosage and UV exposure have been achieved, the initial deposition thickness is controlled primarily by the total flux of monomer to the surface, which is consistent with previous studies. For all samples, thickness loss occurs primarily during the first 30 days of saline soak‐testing with no statistically significant loss (p > 0.25) during the next 90 days of soak testing. While the additional UV exposure time has a limited effect on initial film thickness, it does increase long term thickness retention, most likely by forming crosslinked and branched structures within the film. All samples tested retain sufficient gCVD coating thickness to impart improved hydrophilicity at the surface throughout the entire 120 day saline soak‐testing period. The fractional factorial experiments correlate improved hydrophilicity with an interaction between initiator dosage time and UV exposure time. Indeed, decreasing these two process variables in tandem provides the greatest reduction in contact angle. While the uncoated PMA displayed 92.3° ± 2.1° advancing and 86.7° ± 3.0° receding contact angles with water, the most hydrophilic gCVD coating lowers the advancing and receding contact angles to 39.5° ± 2.6° and 36.2° ± 1.6°, respectively.

Incorporation of acid polymethacrylates into temperature sensitive hydrogels using electron beam irradiation

In this work, electron beam irradiation was used to prepare hydrogels from aqueous solutions of monomers and/or linear polymers. Poly(N-isopropylacrylamide) (PNIPAAm) and polymers of methacrylic acid derivatives were used to generate the different temperature sensitive hydrogels. The effects of irradiation dose and N,N’-methylenebisacrylamide (BIS) crosslinking agent were also studied. The polymethacrylate content in co-polymeric hydrogels was varied (5, 10, 15 and 20 mol%). The temperature dependence of the swelling behavior of the hydrogels was characterized. The influence of polymethacrylate content on the swelling characteristics of the hydrogels was investigated. The incorporation of polymers from methacrylic acid derivatives into hydrogels was effectively achieved under optimum conditions.

Radical copolymerization of maleic anhydride with organotin acrylates

Copolymerization of maleic anhydride (MA) with trialkylstannylmethacrylates has been studied. Copolymerization constants (r1r2) have been determined for maleic anhydride and trialkylstannylmethacrylates, the parameters Q2 and e2 have been calculated for (CH3)3Sn- (C2H7)3 Sn- and (n-C4H9)3Sn- and (n-C4H9)3Sn- methacrylic acid derivatives: Q2 = 0.31, 0.27, 0.23 and 0.18; e2 = − 0.64, − 0.75, − 0.81 and − 0.88. Kinetic regularities of the reaction have been studied. It has been shown that organotin copolymers composition, as well as their model compound structures, are characterized by the occurrence of coordinate bonds of type. There has been revealed the effect of internal complexation in radical copolymerization responsible for both monomer links laternation along macromolecular chain and possible stereodirection of the reaction. The reactivity of complexomers MA-TBSM and MA- Styrene (St) has been studied by means of terpolymerization.

Investigation into the influence of organic modifiers and ultradispersed hybrid fillers on the structure and properties of glass-ceramic coatings prepared by the sol-gel method

Glass-ceramic coatings on nickel and its alloys are produced from organic-inorganic hybrids by the sol-gel method. The coatings are applied using sol-gel systems composed of tetraethoxysilane (inorganic dopant), as well as of finely dispersed oxide and ultradispersed hybrid fillers. Acrylic and methacrylic acid derivatives are taken as organic modifiers. Oligocarbonate dimethacrylate-substituted tetranuclear titanium oxide clusters are used as the ultradispersed hybrid filler. The influence of the organic modifiers and ultradispersed hybrid fillers on the physicochemical processes occurring in the sol-gel systems and on the electrical parameters of the coatings are experimentally studied, and the data obtained are analyzed.

Photodimerization of Anthryl Moieties in a Poly(methacrylic acid) Derivative as Reversible Cross-linking Step in Molecular Imprinting

Abstract A methodology for reversible molecular imprinting is presented. A molecularly imprinted polymer (MIP) is prepared by photo-cross-linking poly(methacrylic acid) (PMAA) with anthryl moieties as photo-cross-linking sites in the presence of an antimalarial drug cinchonidine as a template molecule, resulting in enhanced binding capacity to cinchonidine, compared with non-imprinted polymers. MIP is then “initialized” by exposure to shortwave UV that cleaves the anthracene-dimer-based cross-links, resulting in the reduced binding capacity comparable to the non-imprinted polymers.

Effects of the chemical structure on the heat resistance of thermoplastic expandable microspheres

AbstractThe effects of various additional non‐nitrile‐containing monomers on the heat resistance of thermoplastic expandable microspheres containing acrylonitrile and methacrylonitrile were investigated to determine the correlation between the chemical structure and expandable properties. Thermoplastic expandable microspheres were synthesized by suspension polymerization, with acrylonitrile and methacrylonitrile as the main ingredients and seven kinds of methacrylic acid derivatives, methacrylic acid, and acrylic acid as non‐nitrile‐containing monomers. The expandable properties, that is, the maximum expansion temperature, the expansion start temperature, and the maximum dimension change, were measured with thermomechanical analysis. For the development of heat‐resistant microspheres, polymer structures with smaller functional free volumes, higher glass‐transition temperatures, and higher cohesive energy densities, such as methyl acrylic acid, were applied as non‐nitrile‐containing monomers. Molecular structures such as COOH groups with strong electrostatic interactions and hydrogen‐bonding forces were found to be suitable for high heat resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1306–1312, 2005