Exploiting Visible-Light Induced Radical to Cation Transformation Pathway for Reactivity Enhanced Electrophilic Aromatic Substitution Polymerization of Heteroaromatics.

A straightforward approach is employed to synthesize methylene-bridged poly(hetero aromatic)s based on furan, pyrrole, thiophene, and thiophene derivatives. The process involves an electrophilic aromatic substitution reaction facilitated by a visible light-initiated system consisting of manganese decacarbonyl and an iodonium salt. The approach mainly relies on the formation of halomethylium cation, the attack of this cation to heteroaromatic, regeneration of methylium cation on the heteroaromatic, and reactivity differences between halomethylium and heteroaromatic methylium cations for successful polymerizations. This innovative synthetic strategy lead to the formation of polymers with relatively high molecular weights as the stoichiometric imbalance between the comonomers increased. Accordingly, these newly obtained polymers exhibit remarkable fluorescence properties, even at excitation wavelengths as low as 330 nm. Moreover, by harnessing the halogens at chain ends of homopolymers, block copolymers are successfully synthesized, offering opportunities for tailored applications in diverse fields.

High-performance photoinitiating systems for new generation dental fillings.

OBJECTIVES: To obtain new generation dental composites with improved performance properties compared to currently available dental fillings on the market and to determine the influence of new initiating systems on final product parameters such as degree of cure, hardness, color, and shrinkage. METHODS: In order to verify the effectiveness of the developed initiating systems, typical spectroscopic, electrochemical, and kinetic studies using the real-time FT-IR method were shown. Moreover, paste dental fillings were prepared, the compositions were irradiated with the dental lamp, and the degrees of cross-linking were measured by Raman spectroscopy. The polymerization shrinkage was also determined using the rheometer. In addition, their hardness was examined on the Shore scale. Finally, the color analysis of the composites in the L*a*b* color space was compared with the VITA CLASSIC colorant. RESULTS: It was shown that, due to their excellent spectroscopic and electrochemical properties, new quinazolin-2-one can act as co-initiators in cationic and radical photopolymerization. It was demonstrated that the most effective composite containing the initiator system in the form of 3-SCH3Ph-Q, IOD, MDEA, and an inorganic filler as nanometric silica and a bonding agent is cured more than 90% after just 1 cycle of dental lamp exposure (30 s), the hardness of the composite after curing on the Shor Scale is 82 ± 4, and the polymerization shrinkage is less than 2.8%. SIGNIFICANCE: The article demonstrates effective new initiator systems as an alternative to CQ/amine for obtaining new-generation dental composites. The developed dental composites are a big competition to the currently used dental fillings on the market.

Influence of the Type of Nanofillers on the Properties of Composites Used in Dentistry and 3D Printing.

Photopolymerization is a growing field with an extensive range of applications and is environmentally friendly owing to its energy-efficient nature. Such light-assisted curing methods were initially used to cure the coatings. However, it has become common to use photopolymerization to produce 3D objects, such as bridges or dental crowns, as well as to cure dental fillings. In this study, polymer nanocomposites containing inorganic nanofillers (such as zinc nano-oxide and zinc nano-oxide doped with two wt.% aluminum, titanium nano-oxide, kaolin nanoclay, zirconium nano-oxide, aluminum nano-oxide, and silicon nano-oxide) were fabricated and studied using Real Time FT-IR to investigate the effects of these nanoadditives on the final conversion rates of the obtained nanocomposites. The effects of the fillers on the viscosity of the produced nanocomposites were also investigated, and 3D prints of the selected nanocomposites were presented.

Visible Light Induced High Resolution and Swift 3D Printing System by Halogen Atom Transfer.

3D printing technology offers solutions for numerous needs in industry and the daily life of individuals. In recent years, most research efforts have focused on this technology as the market share has grown and requirements have become specified in their related fields. In this work, a novel visible light induced 3D printing system with high resolution and short printing time using dimanganese decacarbonyl (Mn2 (CO)10 ) in combination with organic halides is reported. The radicals formed through halogen abstraction by photochemically generated manganese pentacarbonyl from organic halides with high quantum efficiency initiate the polymerization of acrylic resins. The kinetics of the process using various halide-containing molecules in the photoinitiaiting system are investigated with real-time fourrier transform infrared spectroscopy and photo-differential scanning calorimetry analyses, and the characteristics of 3D printouts are presented and compared with that of the commercial photoinitiator, 2,4,6-trimethylbenzoyl)phosphine oxide without Mn2 (CO)10 . The results obtained confirm that the combination of Mn2 (CO)10 and structurally diverse organic halides is a class of promising 3D system for various applications.

Novel Formulations Containing Fluorescent Sensors to Improve the Resolution of 3D Prints.

Three-dimensional printing in SLA (stereolithography) and DLP (digital light processing) technologies has recently been experiencing a period of extremely rapid development. This is due to the fact that researchers recognise the many advantages of 3D printing, such as the high resolution and speed of the modelling and printing processes. However, there is still a search for new resin formulations dedicated to specific 3D printers allowing for high-resolution prints. Therefore, in the following paper, the effects of dyes such as BODIPY, europium complex, and Coumarin 1 added to light-cured compositions polymerised according to the radical mechanism on the photopolymerisation process speed, polymerisation shrinkage, and the final properties of the printouts were investigated. The kinetics of the photopolymerisation of light-cured materials using real-time FT-IR methods, as well as printouts that tangibly demonstrate the potential application of 3D printing technology in Industry 4.0, were examined. These studies showed that the addition of dyes has an effect on obtaining fluorescent prints with good resolution.

Selective Cytotoxicity of Complexes with N,N,N-Donor Dipodal Ligand in Tumor Cells.

The present article demonstrates selective cytotoxicity against cancer cells of the complexes [Co(LD)2]I2∙CH3OH (1), [CoLD(NCS)2] (2) and [VOLD(NCS)2]∙C6H5CH3 (3) containing the dipodal tridentate ligand LD = N,N-bis(3,5-dimethylpyrazol-1-ylmethyl)amine), formed in situ. All tested complexes expressed greater anticancer activities and were less toxic towards noncancerous cells than cisplatin. Cobalt complexes (1 and 2) combined high cytotoxicity with selectivity towards cancer cells and caused massive tumour cell death. The vanadium complex (3) induced apoptosis specifically in cancer cells and targeted proteins, controlling their invasive and metastatic properties. The presented experimental data and computational prediction of drug ability of coordination compounds may be helpful for designing novel and less toxic metal-based anticancer species with high specificities towards tumour cells.

Fluorescence assay for the determination of glutathione based on a ring-fused 2-pyridone derivative in dietary supplements.

Herein, a novel fluorescent method for the determination of GSH levels in aqueous solutions involving the utilization of citric acid as a derivatization reagent was developed. Therefore, the crucial parameters of the derivatization process were established from what has resulted in the development of a sensitive, reproducible, and accurate GSH assay. The method was validated, and its applicability in the characterization of the GSH concentration in dietary supplements concerning the selectivity in the determination of GSH over GSSG was both confirmed. The chemical structure of the new fluorophore 3-[(carboxymethyl)carbamoyl]-5-oxo-2,3-dihydro-5H-[1,3]thiazolo[3,2-a]pyridine-7-carboxylic acid - CTPC was elucidated using detailed NMR: one-dimensional (1H, 13C), as well as two-dimensional NMR spectra (1H-1H COSY, 1H-13C HSQC, 1H-13C HMBC, 1H-15N HSQC, 1H-15N HMBC) experiments. Besides, the essential optical, biological and antioxidative properties of CTPC were investigated.

Phytochemical Molecules from the Decarboxylation of Gomphrenins in Violet Gomphrena globosa L.-Floral Infusions from Functional Food.

Herein, the generation of decarboxylated derivatives of gomphrenin pigments exhibiting potential health-promoting properties and the kinetics of their extraction during tea brewing from the purple flowers of Gomphrena globosa L. in aqueous and aqueous citric acid solutions were investigated. Time-dependent concentration monitoring of natural gomphrenins and their tentative identification was carried out by LC-DAD-ESI-MS/MS. The high content of acylated gomphrenins and their principal decarboxylation products, 2-, 15-, 17-decarboxy-gomphrenins, along with minor levels of their bidecarboxylated derivatives, were reported in the infusions. The identification was supported by the determination of molecular formulas of the extracted pigments by liquid chromatography coupled with high-resolution mass spectrometry (LCMS-IT-TOF). The influence of plant matrix on gomphrenins' stability and generation of their derivatives, including the extraction kinetics, was determined by studying the concentration profiles in the primary and diluted infusions. Isolated and purified acylated gomphrenins from the same plant material were used for the preliminary determination of their decarboxylated derivatives. The acylated gomphrenins were found to be more stable than nonacylated ones. Citric acid addition had a degradative influence on natural gomphrenins mainly during the longer tea brewing process (above 15 min); however, the presence of plant matrix significantly increased the stability for betacyanins' identification.

Moving Towards a Finer Way of Light-Cured Resin-Based Restorative Dental Materials: Recent Advances in Photoinitiating Systems Based on Iodonium Salts.

The photoinduced polymerization of monomers is currently an essential tool in various industries. The photopolymerization process plays an increasingly important role in biomedical applications. It is especially used in the production of dental composites. It also exhibits unique properties, such as a short time of polymerization of composites (up to a few seconds), low energy consumption, and spatial resolution (polymerization only in irradiated areas). This paper describes a short overview of the history and classification of different typical monomers and photoinitiating systems such as bimolecular photoinitiator system containing camphorquinone and aromatic amine, 1-phenyl-1,2-propanedione, phosphine derivatives, germanium derivatives, hexaarylbiimidazole derivatives, silane-based derivatives and thioxanthone derivatives used in the production of dental composites with their limitations and disadvantages. Moreover, this article represents the challenges faced when using the latest inventions in the field of dental materials, with a particular focus on photoinitiating systems based on iodonium salts. The beneficial properties of dental composites cured using initiation systems based on iodonium salts have been demonstrated.

A New Approach to Micromachining: High-Precision and Innovative Additive Manufacturing Solutions Based on Photopolymerization Technology.

The following article introduces technologies that build three dimensional (3D) objects by adding layer-upon-layer of material, also called additive manufacturing technologies. Furthermore, most important features supporting the conscious choice of 3D printing methods for applications in micro and nanomanufacturing are covered. The micromanufacturing method covers photopolymerization-based methods such as stereolithography (SLA), digital light processing (DLP), the liquid crystal display-DLP coupled method, two-photon polymerization (TPP), and inkjet-based methods. Functional photocurable materials, with magnetic, conductive, or specific optical applications in the 3D printing processes are also reviewed.

Double Role of Diphenylpyridine Derivatives as Fluorescent Sensors for Monitoring Photopolymerization and the Determination of the Efficiencies of the Generation of Superacids by Cationic Photoinitiators.

Novel fluorescent sensors with electron-donating or electron-withdrawing substituents incorporated into a chromophore group based on 2,6-diphenylpyridine were designed and synthesised. The spectroscopic properties of these compounds were studied. Moreover, the positive solvatochromism of 2,6-bis-(4-methylsulphanylphenyl)pyridine (PT-SCH3) in selected solvents was studied by measurement of the absorption and emission spectra and analysed using the Dimroth-Reichardt solvent parameter set. After that, the performance of a series of 2,6-diphenylpyridine derivatives as fluorescent molecular sensors for monitoring free-radical and cationic photopolymerization processes by the Fluorescence Probe Technique (FPT) was studied. As a consequence of this stage of research, the effect of substituents on the sensitivity of the 2,6-diphenylpyridine derivatives as sensors during photopolymerization has been evaluated and discussed. It has been found that compounds containing strong electron-donating substituent (PT-SCH3) slightly shift their fluorescence spectrum during the free-radical polymerization of monomer, which enables the monitoring of the polymerization progress using the fluorescence intensity ratio measured at two different wavelengths as the progress indicator. The position of the fluorescence spectrum of 2,6-diphenylpyridine derivatives with electron-withdrawing substituents is practically insensitive to changes occurring in their environment. Hence, it is recommended to use these compounds with different indicators of the progress of the photopolymerization process based on normalised intensity of fluorescence (Imax/I0). Among the compounds studied, 2,6-bis(4-methylsulphanylphenyl)pyridine (PT-SCH3) turned out to be the best fluorescent sensor for the purpose of monitoring free-radical polymerization by FPT. Consequently, the dual application of the selected 2,6-diphenylpyridine derivatives is proposed: (a) as fluorescent sensors for monitoring the free-radical photopolymerization progress, and (b) as spectroscopic sensors for the determination of efficiencies of the generation of superacids by cationic photoinitiators during the cationic photopolymerization process. Finally, a new method for determining the relative efficiency of the photogeneration of superacids during the photo cleavage of onium salt has been devised and applied for the evaluation of the performance of 2,6-diphenylpyridine derivatives.

Water-Soluble Photoinitiators in Biomedical Applications.

Light-initiated polymerization processes are currently an important tool in various industrial fields. The advancement of technology has resulted in the use of photopolymerization in various biomedical applications, such as the production of 3D hydrogel structures, the encapsulation of cells, and in drug delivery systems. The use of photopolymerization processes requires an appropriate initiating system that, in biomedical applications, must meet additional criteria such as high water solubility, non-toxicity to cells, and compatibility with visible low-power light sources. This article is a literature review on those compounds that act as photoinitiators of photopolymerization processes in biomedical applications. The division of initiators according to the method of photoinitiation was described and the related mechanisms were discussed. Examples from each group of photoinitiators are presented, and their benefits, limitations, and applications are outlined.

New, highly versatile bimolecular photoinitiating systems for free-radical, cationic and thiol-ene photopolymerization processes under low light intensity UV and visible LEDs for 3D printing application.

1-Amino-4-methyl-naphthalene-2-carbonitrile derivatives are proposed for the role of photosensitizers of iodonium salt during the photopolymerization processes upon near UV-A and visible ranges. Remarkably, 1-amino-4-methyl-naphthalene-2-carbonitrile derivatives are highly versatile allowing access to photoinitiating systems for (i) the cationic photopolymerization of epoxide monomers with a ring opening mechanism and vinyl ether monomers with chain growth mechanisms (ii) the free-radical photopolymerization of acrylate monomers, (iii) the photopolymerization of interpenetrated polymer networks (IPNs) based on epoxide and acrylate monomers under air and under laminate in an oxygen-free atmosphere (iv) the thiol-ene photopolymerization processes. Excellent polymerization profiles are obtained during all types of photopolymerization processes. The initiation mechanisms are analyzed through steady state photolysis, cyclic voltammetry and fluorescence experiments. Moreover, the newly developed bimolecular photoinitiating systems were investigated by applying an additive manufacturing process under visible light sources. Furthermore, vat photopolymerization processes using IPN compositions, which are polymerizable by using new photoinitiating systems, provide high resolution and speeds. For these reasons, new bimolecular photoinitiating systems are promising initiators for photopolymerization-based 3D printing process to fabricate 3D structures.

Multifunctional biphenyl derivatives as photosensitisers in various types of photopolymerization processes, including IPN formation, 3D printing of photocurable multiwalled carbon nanotubes (MWCNTs) fluorescent composites.

A series of 2-(diethylamino)-4-(1-ethylpropyl)-6-phenyl-benzene-1,3-dicarbonitrile derivatives were investigated in terms of photosensitisation in various photopolymerization processes in UV-A and vis light conditions. A full spectroscopic analysis of the tested compounds was performed. In addition to excellent spectroscopic properties, these compounds enable highly efficient photopolymerization processes, including free-radical, cationic and hybrid photopolymerization. As proven by a real-time FTIR study, these photosensitisers allow the formation of both thin and thick layers from different monomers. Finally, the investigated 2-(diethylamino)-4-(1-ethylpropyl)-6-phenyl-benzene-1,3-dicarbonitrile derivatives were used to obtain multiwalled carbon nanotubes (MWCNTs) composites for which the degree of conversion was determined using real-time FT-IR and Photo-Differential Scanning Calorimetry (Photo-DSC). Selected derivatives were applied as photosensitisers in two-component photoinitiating systems, operating according to the mechanism of photo-oxidation and photo-reduction, for the preparation of photo-cured MWCNTs composites. The importance of the quantity of multiwalled carbon nanotubes (MWCNTs) added to the polymeric matrix on the curing degree is also discussed in this study. The structures of the MWCNTs composites were analysed using an optical and fluorescence microscope. Moreover, this study also examines the applicability of new photoinitiator systems for printing nanocomposites by vat photopolymerization, which has gained increasing attention in recent years. Therefore, photocurable nanocomposite resin based on methacrylates was used for 3D printing in room temperature and atmospheric conditions, under a visible LED with emission at 405 nm, in order to obtain fluorescent photocurable patterns.

Applicability of 1,6-Diphenylquinolin-2-one Derivatives as Fluorescent Sensors for Monitoring the Progress of Photopolymerisation Processes and as Photosensitisers for Bimolecular Photoinitiating Systems.

The applicability of new 1,6-diphenylquinolin-2-oneas derivatives as fluorescent molecular sensors for monitoring the progress of photopolymerisation processes by Fluorescence Probe Technique (FPT) has been tested. The progress of cationic, free-radical and thiol-ene photopolymerisation for commercially available monomers: triethylene glycol divinyl ether (TEGDVE), trimethylolpropane triacrylate (TMPTA) and trimethylpropane tris(3-mercaptopropropionate) (MERCAPTO) was monitored. It was found that new derivatives of 1,6-diphenylquinolin-2-one shifted their fluorescence spectra towards shorter wavelengths with the progress of polymerisation, which enabled monitoring the progress in terms of fluorescence intensity ratios as the progress indicator. Derivatives of 1,6-diphenylquinolin-2-one show sensitivity to changes in both polarity and viscosity in the surrounding microenvironment during photopolymerisation processes. Therefore, it was shown that they are good candidates to act as fluorescent sensors for monitoring the kinetics of very quick processes, such as photopolymerisation processes. Furthermore, the effect of the nature of substituents attached to the 1,6-diphenylquinolin-2-one ring on the characteristics of emission spectra was identified. Moreover, the sensitivity of fluorescent sensors was compared with commercially available model sensors, such as 7-diethylamino-4-methylcoumarin (Coumarin 1) and trans-2-(2',5'-dimethoxyphenyl)ethenyl-2,3,4,5,6-pentafluorobenzene (25ST). Moreover, it was also proven that selected derivatives of 1,6-diphenylquinolin-2-one exhibit an accelerating effect on the progress of cationic photopolymerisation of vinyl monomers (TEGDVE). Thus, the new 1,6-diphenylquinolin-2-one derivatives can be successfully used both as molecular fluorescence sensors to monitor the progress of photopolymerisation processes and as diaryliodonium salt photosensitisers to initiate cationic photopolymerisation processes in a UV-A range of 365 nm.

The Applicability of 2-amino-4,6-diphenyl-pyridine-3-carbonitrile Sensors for Monitoring Different Types of Photopolymerization Processes and Acceleration of Cationic and Free-Radical Photopolymerization Under Near UV Light.

The performance of a series of 2-amino-4,6-diphenyl-pyridine-3-carbonitrile derivatives as fluorescent molecular sensors for monitoring photopolymerization processes of different monomers by the Fluorescence Probe Technique (FPT) was studied. It has been shown that the new derivatives are characterized by much higher sensitivity than the commercially available 7-diethylamino-4-methylcoumarin (Coumarin 1) and trans-2-(2',5'-dimethoxyphenyl)ethenyl-2,3,4, 5,6-pentafluorobenzene (25ST) probes. It has been discovered that the 2-amino-4,6-diphenyl-pyridine-3-carbonitrile derivatives accelerate the cationic photopolymerization process initiated with diphenyliodonium photoinitiators at the wavelength where the photoinitiator alone does not work. They are particularly efficient for the photoinitiation of cationic photopolymerization of an epoxide and vinyl monomers. Consequently, the application of the 2-amino-4,6-diphenyl-pyridine-3-carbonitrile derivatives in a dual role: (a) as fluorescent sensors for monitoring the free-radical, thiol-ene and cationic polymerization progress, and (b) as long-wavelength co-initiators for diphenyliodonium salts initiators, is proposed.

Applicability of samarium(III) complexes for the role of luminescent molecular sensors for monitoring progress of photopolymerization processes and control of the thickness of polymer coatings.

Applicability of 15 trivalent samarium complexes as novel luminescent probes for monitoring progress of photopolymerization processes or thickness of polymer coatings by the Fluorescence Probe Technique (FPT) was studied. Three groups of samarium(III) complexes were evaluated in cationic photopolymerization of triethylene glycol divinyl ether monomer (TEGDVE) and free-radical photopolymerization of trimethylolpropane triacrylate (TMPTA). The complexes were the derivatives of tris(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate)samarium(III), tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionate)samarium(III) and tris(4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate)samarium(III), which were further coordinated with auxiliary ligands, such as 1,10-phenanthroline, triphenylphosphine oxide, tributylphosphine oxide and trioctylphosphine oxide. It has been found that most of the complexes studied are sensitive enough to be used as luminescent probes for monitoring progress of cationic photopolymerization of vinyl ether monomers over entire range of monomer conversions. In the case of free-radical polymerization processes, the samarium(III) complexes are not sensitive enough to changes of microviscosity and/or micropolarity of the medium, so they cannot be used to monitor progress of the polymerization. However, high stability of luminescence intensity of some of these complexes under free-radical polymerization conditions makes them good candidates for application as thickness sensors for polymer coatings prepared by free-radical photopolymerization. A quantitative relationship between a coating thickness and the luminescence intensity of the samarium(III) probes has been derived and verified experimentally within a broad range of the thicknesses.