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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.

The presented paper concerns current knowledge of commercial and alternative photoinitiator systems used in dentistry. It discusses alternative and commercial photoinitiators and focuses on mechanisms of polymerization process, in vitro measurement methods and factors influencing the degree of conversion and hardness of dental resins. PubMed, Academia.edu, Google Scholar, Elsevier, ResearchGate and Mendeley, analysis from 1985 to 2020 were searched electronically with appropriate keywords. Over 60 articles were chosen based on relevance to this review. Dental light-cured composites are the most common filling used in dentistry, but every photoinitiator system requires proper light-curing system with suitable spectrum of light. Alternation of photoinitiator might cause changing the values of biomechanical properties such as: degree of conversion, hardness, biocompatibility. This review contains comparison of biomechanical properties of dental composites including different photosensitizers among other: camphorquinone, phenanthrenequinone, benzophenone and 1-phenyl-1,2 propanedione, trimethylbenzoyl-diphenylphosphine oxide, benzoyl peroxide. The major aim of this article was to point out alternative photoinitiators which would compensate the disadvantages of camphorquinone such as: yellow staining or poor biocompatibility and also would have mechanical properties as satisfactory as camphorquinone. Research showed there is not an adequate photoinitiator which can be as sufficient as camphorquinone (CQ), but alternative photosensitizers like: benzoyl germanium or novel acylphosphine oxide photoinitiators used synergistically with CQ are able to improve aesthetic properties and degree of conversion of dental resin.

Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications such as pharmaceuticals, photoinitiators and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends on indirect and inefficient, multi-step procedures. Here, we report a simple, effective ‘one-pot’ synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-n-butyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and it requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately catalytic use of the tributyltin reagent, thereby avoiding the formation of substantial Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride.State-of-the-art industrial methods for transforming P4 into useful phosphorus compounds currently rely on indirect, multi-step strategies. It has now been shown that straightforward one-pot reactions can convert P4 directly into industrially relevant products while requiring only mild conditions and simple, inexpensive reagents—and can also functionalize P4 catalytically.

Photopolymerization is a polymerization reaction where a light source provides energy for the formation of active species and further follows the conventional polymerization process. This polymerization technique has recently gained interest because of its high curing rate, lower energy consumption, low volatile organic component and relatively low cost. In such a system, the photoinitiator is a vital component as it governs the curing rate. It is a chemical substance that absorbs the radiation and forms reactive species that further attacks the monomer and leads to the photopolymerization reaction. The photoinitiators employed are expensive, oxygen-sensitive, possess pungent odour and migrate to the film surface, resulting in yellowing and degradation of the polymeric system. Thus, it is a requisite to decrease the concentration of a photoinitiator in a particular system. The paper briefly discusses alternate methods for conventionally photoinitiator-based photopolymerization, such as short-wavelength sources, unique monomers such as electron acceptor/donor system, thiol-ene system and specific particles.

Even though numerous organic dyes which are used as photoinitiators/photocatalysts during photopolymerization have been systematically investigated and collected in previous reviews, further designs of these chromophores and the developments in high-performance photoinitiating systems have emerged in recent years, which play the crucial role in 3D printing/Vat polymerization. Here, in this mini-review, various families of organic dyes that are used as newly synthesized photoinitiators/photocatalysts which were reported in literature during 2021–2022 are specified by their photoinitiation mechanisms, which dominate their performance during photopolymerization, especially in 3D printing. Markedly, visible light-induced polymerization could be employed in circumstances not only upon the irradiation of artificial light sources, e.g., in LEDs, but also in sunlight irradiation. Furthermore, a short overview of the achievements of newly developed mechanisms, e.g., RAFT, photoinitiator-RAFT, and aqueous RAFT using organic chromophores as light-harvesting compounds to induce photopolymerization upon visible light irradiation are also thoroughly discussed. Finally, the reports on the semiconducting nanomaterials that have been used as photoinitiators/photocatalysts during photopolymerization are also introduced as perspectives that are able to expand the scope of 3D printing and materials science due to their various advantages such as high extinction coefficients, broad absorption spectra, and having multiple molecular binding points.

The first phase of the development of a white pigmented paint formulation suitable for LED UV curing in the R&D department of a large paint factory is presented, focussing on the search for the most suitable photoinitiator. The importance of co-operation between industry and academia is also demonstrated. Various LED UV photoinitiators were added to a base coat formulation in concentrations of 1-7% and 0.1-1.5% for those known to be very efficient but at the same time causing significant yellowing. Formulations with higher proportions of photoinitiators tend to cure better, but only to a certain extent. The type I phosphine oxide photoinitiators showed promising curing efficiency, while a type II thioxantone photoinitiator proved to be the most efficient of those tested, but caused a yellow colour after curing. It is therefore not the best choice for white paints. Further investigations should focus on a wider range of test conditions, such as different feed rates or combinations of multiple photoinitiators at different concentrations, to determine the optimal curing conditions.

Biocompatibility is important for the 3D printing of resins used in medical devices and can be affected by photoinitiators, one of the key additives used in the 3D printing process. The choice of ingredients must be considered, as the toxicity varies depending on the photoinitiator, and unreacted photoinitiator may leach out of the polymerized resin. In this study, the use of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate (TPO-L) as a photoinitiator for the 3D printing of resin was considered for application in medical device production, where the cytotoxicity, colour stability, dimensional accuracy, degree of conversion, and mechanical/physical properties were evaluated. Along with TPO-L, two conventional photoinitiators, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BAPO) and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), were considered. A total of 0.1 mol% of each photoinitiator was mixed with the resin matrix to prepare a resin mixture for 3D printing. The specimens were printed using a direct light processing (DLP) type 3D printer. The 3D-printed specimens were postprocessed and evaluated for cytotoxicity, colour stability, dimensional accuracy, degree of conversion, and mechanical properties in accordance with international standards and the methods described in previous studies. The TPO-L photoinitiator showed excellent biocompatibility and colour stability and possessed with an acceptable dimensional accuracy for use in the 3D printing of resins. Therefore, the TPO-L photoinitiator can be sufficiently used as a photoinitiator for dental 3D-printed resin.

The quadratic optical nonlinearity arising from two-photon absorption provides the crucial spatial concentration of optical excitation in three-dimensional (3D) laser nanoprinting, with widespread applications in technical and life sciences. Femtosecond lasers allow for obtaining efficient two-photon absorption but are accompanied by a number of issues, including higher-order processes, cost, reliability and size. Here we introduce two-step absorption replacing two-photon absorption as the primary optical excitation process. Under suitable conditions, two-step absorption shows the same quadratic optical nonlinearity as two-photon absorption. We present a photoresist system based on a photoinitiator supporting two-step absorption, a scavenger and a well-established triacrylate. We show that this system allows for printing state-of-the-art 3D nanostructures and beyond. In these experiments, we use ~100 μW optical power from an inexpensive, compact continuous-wave semiconductor laser diode emitting at 405 nm wavelength. Our work opens the door to drastic miniaturization and cost reduction of 3D laser nanoprinters.As an alternative to high-resolution fabrication by two-photon absorption, researchers demonstrate a two-step absorption process that employs inexpensive light sources.

The range of applications for additive manufacturing is expanding quickly, including mass production of athletic footwear parts 1 , dental ceramics 2 and aerospace components 3 as well as fabrication of microfluidics 4 , medical devices 5 , and artificial organs 6 . The light-induced additive manufacturing techniques 7 used are particularly successful owing to their high spatial and temporal control, but such techniques still share the common motifs of pointwise or layered generation, as do stereolithography 8 , laser powder bed fusion 9 , and continuous liquid interface production 10 and its successors 11 , 12 . Volumetric 3D printing 13 – 20 is the next step onward from sequential additive manufacturing methods. Here we introduce xolography, a dual colour technique using photoswitchable photoinitiators to induce local polymerization inside a confined monomer volume upon linear excitation by intersecting light beams of different wavelengths. We demonstrate this concept with a volumetric printer designed to generate three-dimensional objects with complex structural features as well as mechanical and optical functions. Compared to state-of-the-art volumetric printing methods, our technique has a resolution about ten times higher than computed axial lithography without feedback optimization, and a volume generation rate four to five orders of magnitude higher than two-photon photopolymerization. We expect this technology to transform rapid volumetric production for objects at the nanoscopic to macroscopic length scales. By combining the use of photoswitchable photoinitators and intersecting light beams, objects and complex systems can be produced rapidly with higher definition than is possible using state-of-the art macroscopic volumetric methods.

High-speed high-resolution 3D printing of polymers is highly desirable for many applications, yet still technologically challenging. Today, optics-based printing is in the lead. Projection-based linear optical approaches have achieved high printing rates of around 106 voxels s–1, although at voxel volumes of >100 μm3. Scanning-based nonlinear optical approaches have achieved voxel volumes of <1 μm3, but suffer from low printing speed or high cost because of the required femtosecond lasers. Here we present an approach that we refer to as light-sheet 3D laser microprinting. It combines image projection with an AND-type optical nonlinearity based on two-colour two-step absorption. The underlying photoresin is composed of 2,3-butanedione as the photoinitiator, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl as the scavenger and dipentaerythritol hexaacrylate as the multifunctional monomer. Using continuous-wave laser diodes at 440 nm wavelength for projection and a continuous-wave laser at 660 nm for the light-sheet, we achieve a peak printing rate of 7 × 106 voxels s–1 at a voxel volume of 0.55 μm3.High-speed, high-resolution optics-based printing typically requires femtosecond pulsed lasers. We demonstrate optical printing using indigo-blue laser diodes and a red continuous-wave laser, achieving a peak printing rate of 7 × 106 voxels s–1 at a voxel volume of 0.55 µm3.