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OBJECTIVES: The aim of this study was to assess the cytotoxicity of novel polymerization co-initiators and their effect on cytokine release from human dental pulp stem cells (hDPSCs), comparing them with commonly used co-initiators. METHODS: Cells were isolated from the dental pulp of healthy human third molars. The new co-initiators, namely HDa1, HD4, HD1, and MHPTm, were evaluated and compared with the compounds dimethylaminoethyl amine benzoate (EDAB) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). These compounds were diluted in dimethylsulfoxide (DMSO) at concentrations ranging from 1 to 8 mM. hDPSCs were seeded onto 96-well plates and incubated for 48 h. Subsequently, the cells were exposed to different concentrations of the co-initiators mentioned for 24 h. After this period, the culture medium was removed, and mitochondrial metabolism was evaluated using the MTT assay, while cytokine release (IL-1ß, IL-6, IL-8, IL-10, TNF-α) was analyzed by the MAGPIX assay. Cells without exposure to the tested compounds served as controls. The data were analyzed using one-way ANOVA and Tukey's test. RESULTS: The compounds showed low toxicity, with 8 mM concentration causing the most significant reduction in mitochondrial metabolism. MHPTm was the most toxic co-initiator tested (compound bearing an amine functionality). All compounds up-regulated TNF-α, IL-10, IL-6, and IL-8, with HD4 exhibiting the most pronounced increase in IL-6 and IL-8. SIGNIFICANCE: The newly proposed co-initiators demonstrated reduced impact on mitochondrial metabolism, comparable to some traditional co-initiators. Despite their lower toxicity, HD4 increased IL-6 and IL-8 release, suggesting its potential involvement in triggering an inflammatory reaction, particularly in the short term.
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Various industrial activities release heavy metal ions into the environment, which represent one of the major toxic pollutants owing to their severe effects on the environment, humans, and all living species. Despite several technological advances and breakthroughs, wastewater treatment remains a critical global issue. Traditional techniques are dedicated to extracting heavy metal ions from diverse wastewater origins, encompassing coagulation/flocculation, precipitation, flotation, and ion exchange. Their cost, side toxicity, or ineffectiveness often limit their large-scale use. Due to their adaptable design, simple operation, and reasonable cost, membrane filtration and adsorption have proven their efficiency in removing metals from wastewater. Recently, adsorption-based filters have appeared promising in treating water. Within this range, filters incorporating natural, synthetic, or hybrid adsorbents present an appealing alternative to conventional approaches. This review aims to list and describe the conventional and advanced wastewater treatment methods by comparing their efficiency, cost, and environmental impact. Adsorption-based filters were highlighted due to the significant advantages they can provide.
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OBJECTIVES: Hydroperoxides are key constituents of two-component dental materials. The objective of this study was to evaluate the influence of the hydroperoxide structure on the reactivity and on the mechanical properties of self-cure composites. METHODS: Hydroperoxides HP1-3 were synthesized by selective catalytic oxidation of the corresponding para-substituted cumene precursors and isolated in high purity. They were characterized by 1H NMR and 13C NMR spectroscopy. 16 self-cure composites, based on the redox initiator system hydroperoxide (Cumene hydroperoxide (CHP), HP1-3 or tert.-Amyl hydroperoxide (TAH))/polymerizable thiourea ATU1/copper(II) acetylacetonate, were formulated in Sulzer Mixpac two-component syringes. An equimolar hydroperoxide/ATU1 ratio was selected for each self-cure composite. The reactivity and the final double-bond conversions obtained with these two-component materials was assessed using RT-FTIR spectroscopy. The flexural strength and modulus were measured using a three-point bending setup, after storage of the specimens for 45 min at 37 °C (dry) and for 24 h in water at 37 °C. The working time of each self-cure composite was measured using an oscillating rheometer. RESULTS: CHP derivatives bearing an electron withdrawing group (HP2: ester or HP3: nitrile) in the para position were found to be more reactive than CHP, whereas the compound bearing an electron donating group (tert-butyl, HP1) was less reactive; molecular modelling data were reported for a better understanding of this structure/reactivity/efficiency relationship. All CHP derivatives were more reactive than the aliphatic hydroperoxide TAH. Excellent mechanical properties were obtained with self-cure composites containing either CHP or a para-functionalized CHP derivative. By carefully selecting the amounts of oxidizing/reducing agents and metal catalyst, suitable working times can be obtained with all evaluated hydroperoxides. HP3, thanks to its high reactivity, is nonetheless the most promising compound. SIGNIFICANCE: The curing rate of self-cure composites can be adapted by modifying the structure of the hydroperoxide. In agreement with molecular modelling data, the incorporation of CHP derivatives bearing an electron withdrawing group in the para position is particularly attractive. Indeed, due to a significant reactivity enhancement, the desired properties (working time, flexural strength/modulus) can be obtained by incorporating moderate amounts of hydroperoxide/acylthiourea as well as particularly low contents of metal catalyst to the two-component dental materials.
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Resinas Compuestas , Peróxido de Hidrógeno , Ensayo de Materiales , Resinas Compuestas/química , Peróxido de Hidrógeno/química , Resistencia Flexional , Espectroscopía Infrarroja por Transformada de Fourier , Estructura Molecular , Derivados del Benceno/química , Módulo de Elasticidad , Materiales Dentales/química , Oxidación-Reducción , Espectroscopía de Resonancia Magnética , PolimerizacionRESUMEN
The utilization of two-component systems comprising camphorquinone (CQ) and aromatic amines has become prevalent in the photopolymerization. However, there are still concerns about the safety of this CQ/amine system, mainly because of the toxicity associated with the leaching of aromatic amines. In light of these concerns, this study aims to develop novel coinitiator combinations featuring CQ and amines which cannot be leached out of materials, enabling free radical polymerization of representative dentalmethacrylate resins under blue light irradiation. This approach involves the initial design and analysis of hydrogen donors with low CâH bond dissociation energy through molecular modeling. Subsequently, copolymerizable methacrylate functional groups are incorporated via chemical modification, allowing it to act as both coinitiator and copolymerization monomer to achieve low migrationand leachability properties. This work presents, for the first time, the synthesis of the innovative coinitiator and compares its performance with the benchmark CQ/ethyl-4-dimethylaminobenzoate (EDB)-based photoinitiation system (PIS). The results demonstrate the effectiveness of the newly proposed PIS. Finally, an in-depth investigation is conducted into the reaction mechanism associated with this PIS through molecular orbital calculations and electron spin resonance studies.
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Aminas , Polimerizacion , Aminas/química , Radicales Libres/química , Alcanfor/química , Alcanfor/análogos & derivados , Estructura MolecularRESUMEN
In this work, six benzothioxanthene-based oxime esters were employed as photoinitiators for photopolymerization under visible light (LED) and sunlight. Their abilities to behave as Typeâ I photoinitiators by mean of a photocleavage mechanism of oxime esters but also in multicomponent photoinitiating systems with an iodonium salt (through an electron transfer mechanism) were both explored with the different structures. Due to their broad absorption spectra tailing up 600â nm, photoinitiating properties of the benzothioxanthene-based oxime esters were systematically tested under excitation with low-intensity LED light at wavelengths of 405â nm and 450â nm. Additionally, parallel to the polymerization tests done under artificial light, the different benzothioxanthene-based oxime esters were also investigated as solar photoinitiators and displayed a high reactivity in France (Western Europe) even in winter conditions. For the best candidates i.e. the most reactive structures, direct laser write experiments were carried out, evidencing the interest of these structures.
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Investigations concerning the glyoxylate moiety as a photocleavable functional group for visible light photoinitiators, particularly in the initiation of free radical photopolymerization remain limited. This study introduces nine innovative carbazole-based ethyl glyoxylate derivatives (CEGs), which are synthesized and found to exhibit excellent photoinitiation abilities as monocomponent photoinitiating systems. Notably, these structures demonstrate robust absorption in the near-UV/visible range, surpassing the commercial photoinitiators. Moreover, the newly developed glyoxylate derivatives show higher acrylate function conversions compared to a benchmark photoinitiator (MBF) in free radical photopolymerization. Elucidation of the photoinitiation mechanism of CEGs is achieved through a comprehensive analysis involving the decarboxylation reaction and electron spin resonance spin trapping. Furthermore, their practical utility is confirmed during direct laser writing and 3D printing processes, enabling the successful fabrication of 3D printed objects. This study introduces pioneering concepts and effective strategies in the molecular design of novel photoinitiators, showcasing their potential for highly advantageous applications in 3D printing.
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A series of 15 dyes based on the 2-phenylnaphtho[2,3-d]thiazole-4,9-dione scaffold and 1 compound based on the 2,3-diphenyl-1,2,3,4-tetrahydrobenzo[g]quinoxaline-5,10-dione scaffold are studied as photoinitiators. These compounds are used in two- and three-component high-performance photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) and polyethylene glycol diacrylate (PEGDA) under sunlight. Remarkably, the conversion of TMPTA can reach ≈60% within 20 s, while PEGDA attains a 96% conversion within 90 s. To delve into the intricate chemical mechanisms governing the polymerization, an array of analytical techniques is employed. Specifically, UV-vis absorption and fluorescence spectroscopy, steady-state photolysis, stability experiments, fluorescence quenching experiments, cyclic voltammetry, and electron spin resonance spin trapping (ESR-ST) experiments, collectively contribute to a comprehensive understanding of the photochemical mechanisms. Photoinitiation capacities of these systems are determined using real-time Fourier transformed infrared spectroscopy (RT-FTIR). Of particular interest is the revelation that, owing to the superior initiation ability of these dyes, high-resolution 3D patterns can be manufactured by direct laser write (DLW) technology and 3D printing. This underscores the efficient initiation of free radical polymerization processes by the newly developed dyes under both artificial and natural light sources, presenting an avenue for energy-saving, and environmentally friendly polymerization conditions.
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The fabrication of structured zeolite adsorbents through photopolymerization-based 3D printing which offers a solution to the limitations of conventional shaping techniques has been demonstrated but many parameters still need to be optimized. In this study, we studied the influence of zeolite compensation cations on the photopolymerization and the composite's properties. Modified zeolites (LTA 4â A and FAU 13X exchanged with K+ , Li+ , Sr2+ , Ca2+ or Mg2+ ) were incorporated in PEGDA with BDMK as photoinitiator, and the formulation was cured under mild conditions (LED@405â nm, room temperature, under air). Our results indicate that the nature of zeolite compensation cations affects the colorimetric properties of polymer/zeolite composites: a better translucency parameter results in higher depth of cure. After calcination at 650 °C and complete removal of PEGDA, pure zeolitic monoliths were tested for adsorption of gas molecules of interest (carbon dioxide, dichlorobenzene and water). Structured 4â A and 13X monoliths obtained by 3D printing exhibit comparable adsorption capacity to commercial beads prepared from the same zeolites. This study enhances our understanding of the photopolymerization process involved in the production of polymer/zeolite composites. These composites are used in the fabrication of zeolitic objects through 3D printing, offering potential solutions to various environmental and dental challenges.
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Polystyrene (PS) particles were synthesized in ethanol/water mixture by dispersion polymerization using visible light irradiation, with either a N-heterocyclic carbene borane-based photoinitiating system (PIS) or a disulfide. With the full PIS and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as stabilizer, the size distributions were broad and the amount of PEGMA had a strong impact on the experiment reproducibility. The addition of a base solved the problem, leading to faster polymerizations, narrower size distributions and larger particles. With the disulfide as sole PIS, bigger and narrowly distributed PS particles were again formed. Quantitative conversion was achieved in each system, with particle size ranging between 100 and 350â nm. The use of poly(N-vinylpyrrolidone) as stabilizer led to significantly larger particles, up to 1.2â µm, with narrow size distributions. The production of such large latex particles by photoinitiated polymerizations is unprecedented.
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This paper explores the photochemical synthesis of noble metal nanoparticles, specifically gold (Au) and silver (Ag) nanoparticles, using a one-component photoinitiator system. The synthesis process involves visible light irradiation at a wavelength of 419 nm and an intensity of 250 mW/cm2. The radical-generating capabilities of the photoinitiators were evaluated using electron spin resonance (ESR) spectroscopy. The main objective of this study was to investigate how the concentration of metal salts influences the size and distribution of the nanoparticles. Proposed mechanisms for the photochemical formation of nanoparticles through photoinitiated radicals were validated using cyclic voltammetry. The results showed that the concentration of AgNO3 significantly impacted the size of silver nanoparticles, with diameters ranging from 1 to 5 nm at 1 wt% and 3 wt% concentrations, while increasing the concentration to 5 wt% led to an increase in the diameter of silver nanoparticles to 16 nm. When HAuCl4 was used instead of AgNO3, it was found that the average diameters of gold nanoparticles synthesized using both photoinitiators at different concentrations ranged between 1 and 4 nm. The findings suggest that variations in HAuCl4 concentration have minimal impact on the size of gold nanoparticles. The photoproduction of AuNPs was shown to be thermodynamically favorable, with the reduction of HAuCl4 to Au0 having ∆G values of approximately -3.51 and -2.96 eV for photoinitiators A and B, respectively. Furthermore, the photoreduction of Ag+1 to Ag0 was demonstrated to be thermodynamically feasible, with ∆G values of approximately -3.459 and -2.91 eV for photoinitiators A and B, respectively, confirming the effectiveness of the new photoinitiators on the production of nanoparticles. The synthesis of nanoparticles was monitored using UV-vis absorption spectroscopy, and their sizes were determined through particle size analysis of transmission electron microscopy (TEM) images.
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Nanopartículas del Metal , Nanopartículas del Metal/química , Oro/química , Plata/química , Procesos Fotoquímicos , Cloruro de Sodio , Cloruro de Sodio Dietético , Tamaño de la PartículaRESUMEN
In this study, we developed highly efficient nonwoven membranes by modifying the surface of polypropylene (PP) and poly(butylene terephthalate) (PBT) through photo-grafting polymerization. The nonwoven membrane surfaces of PP and PBT were grafted with poly(ethylene glycol) diacrylate (PEGDA) in the presence of benzophenone (BP) and metal salt. We immobilized tertiary amine groups as BP synergists on commercial nonwoven membranes to improve PP and PBT surfaces. In situ Ag, Au, and Au/Ag nanoparticle formation enhances the nonwoven membrane surface. SEM, FTIR, and EDX were used to analyze the surface. We evaluated modified nonwoven membranes for photocatalytic activity by degrading methylene blue (MB) under LED and sunlight. Additionally, we also tested modified membranes for antibacterial activity against E. coli. The results indicated that the modified membranes exhibited superior efficiency in removing MB from water. The PBT showed the highest efficiency in dye removal, and bimetallic nanoparticles were more effective than monometallic. Modified membranes exposed to sunlight had higher efficiency than those exposed to LED light, with the PBT/Au/Ag membrane showing the highest dye removal at 97% within 90 min. The modified membranes showed reuse potential, with dye removal efficiency decreasing from 97% in the first cycle to 85% in the fifth cycle.
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We report on a novel, to the best of our knowledge, active probe for scanning near-field optical microscopy (SNOM). A fluorescent nanosphere, acting as the secondary source, is grafted in an electrostatic manner at the apex of a polymer tip integrated into the extremity of an optical fiber. Thanks to the high photostability and sensitivity of the secondary source, the near-field interaction with a gold nanocube is investigated. It is shown that the spatial resolution is well defined by the size of the fluorescent nanosphere. The polarization-dependent near-field images, which are consistent with the simulation, are ascribed to the local excitation rate enhancement. Meanwhile, measurement of the distance-dependent fluorescence lifetime of the nanosphere provides strong evidence that the local density of states is modified so that extra information on nano-emitters can be extracted during near-field scanning. This advanced active probe can thus potentially broaden the range of applications to include nanoscale thermal imaging, biochemical sensors, and the manipulation of nanoparticles.
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Fomitiporia mediterranea (Fmed) is the primary Basidiomycota species causing white rot in European vineyards affected by the Esca complex of diseases (ECD). In the last few years, an increasing number of studies have highlighted the importance of reconsidering the role of Fmed in ECD etiology, justifying an increase in research interest related to Fmed's biomolecular pathogenetic mechanisms. In the context of the current re-evaluation of the binary distinction (brown vs. white rot) between biomolecular decay pathways induced by Basidiomycota species, our research aims to investigate the potential for non-enzymatic mechanisms adopted by Fmed, which is typically described as a white rot fungus. Our results demonstrate how, in liquid culture reproducing nutrient restriction conditions often found in wood, Fmed can produce low molecular weight compounds, the hallmark of the non-enzymatic "chelator-mediated Fenton" (CMF) reaction, originally described for brown rot fungi. CMF reactions can redox cycle with ferric iron, generating hydrogen peroxide and ferrous iron, necessary reactants leading to hydroxyl radical (â¢OH) production. These observations led to the conclusion that a non-enzymatic radical-generating CMF-like mechanism may be utilized by Fmed, potentially together with an enzymatic pool, to contribute to degrading wood constituents; moreover, indicating significant variability between strains.
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The copper II complex's novel benzimidazole Schiff base ligands were manufactured and gauged as a new photoredox catalyst/photoinitiator amalgamated with triethylamine (TEA) and iodonium salt (Iod) for the polymerization of ethylene glycol diacrylate while exposed to visible light by an LED Lamp at 405 nm with an intensity of 543 mW/cm2 at 28 °C. Gold and silver nanoparticles were obtained through the reactivity of the copper II complexes with amine/Iod salt. The size of NPs was around 1-30 nm. Lastly, the high performance of copper II complexes for photopolymerization containing nanoparticles is presented and examined. Ultimately, the photochemical mechanisms were observed using cyclic voltammetry. The preparation of the polymer nanocomposite nanoparticles in situ was photogenerated during the irradiation LED at 405 nm with an intensity of 543 mW/cm2 at 28 °C process. UV-Vis, FTIR, and TEM analyses were utilized for the determination of the generation of AuNPs and AgNPs which resided within the polymer matrix.
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Indolo[3,2-a]carbazole alkaloids have drawn a growing interest in recent years owing to their potential electrical and optical properties. With 5,12-dihydroindolo[3,2-a]carbazole serving as the scaffold, two novel carbazole derivatives are synthesized in this study. Both compounds are extremely soluble in water, with solubility surpassing 7% in weight. Intriguingly, the introduction of aromatic substituents contributed to drastically reduce the π-stacking ability of carbazole derivatives, while the presence of the sulfonic acid groups enables the resulting carbazoles remarkably soluble in water, allowing them to be used as especially efficient water-soluble PIs in conjunction with co-initiators, i.e., triethanolamine and the iodonium salt, respectively, employed as electron donor and acceptor. Surprisingly, multi-component photoinitiating systems based on these synthesized carbazole derivatives could be used for the in situ preparation of hydrogels containing silver nanoparticles via laser write procedure with a light emitting diode (LED)@405 nm as light source, and the produced hydrogels display antibacterial activity against Escherichia coli.
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Hidrogeles , Nanopartículas del Metal , Agua , Plata , CarbazolesRESUMEN
Currently, increasing attention has been focused on light-emitting diodes (LEDs)-induced photopolymerization. The common LEDs (e.g., LED at 365 nm and LED at 405 nm) possess narrow emission bands. Due to their light absorption properties, most commercial photoinitiators are sensitive to UV light and cannot be optimally activated under visible LED irradiation. Although many photoinitiators have been designed for LED-induced free radical polymerization and cationic polymerization, there is still the issue of the mating between photoinitiators and LEDs. Therefore, the development of novel photoinitiators, which could be applied under LED irradiation, is significant. Many photoinitiating systems have been reported in the past decade. In this review, some recently developed photoinitiators used in LED-induced photopolymerization, mainly in the past 5 years, are summarized and categorized as Type â photoinitiators, Type â ¡ photoinitiators, and dye-based photoinitiating systems. In addition, their light absorption properties and photoinitiation efficiencies are discussed.
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Benzophenone derivatives were evaluated as new photoinitiators in combination with triethylamine (TEA) and iodonium salt (Iod) for very rapid and efficient formation of metal nanoparticles in an organic solvent, by which silver and gold ions were reduced under light at 419 nm (photoreactor) with an irradiation intensity of 250 microwatts/cm2. The new benzophenone derivatives combined with TEA/Iod salt showed good production of metal nanoparticles (Au0 and Ag0) and a small size of nanoparticles of around 4-13 nm. The photochemical mechanisms for the production of initiating radicals were studied using cyclic voltammetry, where a negative ΔG of around -1.96 eV was obtained, which made the process favorable. The obtained results proved the formation of amine and phenyl radicals, which led to the reduction of gold III chloride or silver ions to the gold and silver NPs. The UV-vis spectroscopy technique was used as a very beneficial tool for the surface plasmon resonance band detection of metal nanoparticles. To sum up the results, we have observed that nanoparticles (NPs) were distributed differently in different photoinitiator systems and the particle size also changed by changing the system of initiation. In comparison to the system alone, not only were the nanoparticles smaller but they were also generated within a shorter period of irradiation time for the system BP\Iod\TEA. Finally, the quenching process of benzophenone fluorescence by the gold and silver nanoparticles was investigated.
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In mild conditions (under air, room temperature, no monomer purification and without any energy activation), redox free radical polymerization (RFRP) is considered as one of the most effective methods to polymerize (meth)acrylate monomers. In the past several years, there has been a growing interest in research on the development of new redox initiating systems (RISs), thanks mainly to the evolution of toxicity labeling and the stability issue of the current RIS based on peroxide and aromatic amine. In this study, a new, low-toxicity RIS based on thiophenium salt as the oxidant species is presented with various reductive species. The reactivity and the stability of the proposed RISs are investigated and the synthesis of new thiophenium salts reported.
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In order to discuss the polymerization effect from the substituted position and methoxy group of Type I photinitiators, a series of naphthalene-based oxime esters was designed and synthesized. Compared to the 2-naphthalene-substituted compound, the UV absorption region of the 1-naphthalene-based compound was greatly improved. In addition, the methoxy substitution exhibited longer absorption characteristics than did the methoxy-free one. The photochemical reaction behavior of these novel compounds was also studied by photolysis, cyclic voltammetry (CV), and electron spin resonance (ESR) experiments. Finally, the initiation abilities of naphthalene-based oxime esters toward trimethylolpropane triacrylate (TMPTA) monomer were conducted through the photo-DSC instrument under UV and a 405@nm LED lamp. Remarkedly, the naphthalene-based oxime ester (NA-3) that contains 1-naphthalene with o-methoxy substituent showed the rather red-shifted absorption region with the highest final conversion efficiency under UV (46%) and 405@nm LED (41%) lamp irradiation.
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The kinetics and the conversion features of two 3-component systems (A/B/N), based on the proposed new kinetic schemes of Mokbel and Mau et al, in which a visible LED is used to excite a copper complex to its excited triplet state (G*). The coupling of G* with iodonium salt and ethyl 4-(dimethylamino)benzoate (EDB) produces both free radical polymerization (FRP) of acrylates and the free radical promoted cationic polymerization (CP) of epoxides using various new copper complex as the initiator. Higher FRP and CP conversion can be achieved by co-additive of [B] and N, via the dual function of (i) regeneration [A], and (ii) generation of extra radicals. The interpenetrated polymer network (IPN) capable of initiating both FRP and CP in a blend of TMPTA and EPOX. The synergic effects due to CP include: (i) CP can increase viscosity limiting the diffusional oxygen replenishment; (ii) the cation also acts as a diluting agent for the IPN network, and (iii) the exothermic property of the CP. The catalytic cycle, synergic effects, and the oxygen inhibition are theoretically confirmed to support the experimental hypothesis. The measured results of Mokbel and Mau et al are well analyzed and matching the predicted features of our modeling.