Highly Efficient Photoinitiation Systems Based on Dibenzo[a,c]phenazine Sensitivity to Visible Light for Dentistry.

In this work, photoinitiation systems based on dibenzo[a,c]phenazine sensitivity to visible light were designed for their potential application in dentistry. Modification of the structure of dibenzo[a,c]phenazine consisted of introducing electron-donating and electron-withdrawing substituents and heavy atoms into position 11. The synthesized compounds are able to absorb radiation emitted by dental lamps during photoinitiation of the polymerization process. In the presence of acrylates, dibenzo[a,c]phenazines show excellent photoinitiating abilities in systems containing an electron donor or a hydrogen-atom donor as a second component. The developed systems initiate the polymerization process comparable to a commercial photoinitiator, i.e., camphorquinone. Moreover, the performed studies showed a significant shortening of the polymerization time and a reduction in the amount of light absorber. This indicates that polymeric materials are obtained at a similar rate despite a significant reduction in the concentration of the newly developed two-component photoinitiating systems.

The Influence of the Alkylamino Group on the Solvatochromic Behavior of 5-(4-substituted-arylidene)-1,3-dimethylpyrimidine-2,4,6-triones: Synthesis, Spectroscopic and Computational Studies.

Advances in electronics and medical diagnostics have made organic dyes extremely popular as key functional materials. From a practical viewpoint, it is necessary to assess the spectroscopic and physicochemical properties of newly designed dyes. In this context, the condensation of 1,3-dimethylbarbituric acid with electron-rich alkylaminobenzaldehyde derivatives has been described, resulting in a series of merocyanine-type dyes. These dyes exhibit intense blue-light absorption but weak fluorescence. An electron-donating alkylamino group at position C4 is responsible for the solvatochromic behavior of the dyes since the lone electron pair of the nitrogen atom is variably delocalized toward the barbituric ring, which exhibits electron-withdrawing properties. This was elucidated, taking into account the different geometry of the amino group. The intramolecular charge transfer in the molecules is responsible for the relatively high redshift in absorption and fluorescence spectra. Additionally, an increase in solvent polarity moves the absorption and fluorescence to lower energy regions. The observed solvatochromism is discussed in terms of the four-parameter Catalán solvent polarity scale. The differences in the behavior of the dyes were quantified with the aid of time-dependent density functional theory calculations. The obtained results made it possible to find regularities linking the basic spectroscopic properties of the compounds with their chemical structure. This is important in the targeted search for new, practically important dyes.

Design of Dyes Based on the Quinoline or Quinoxaline Skeleton towards Visible Light Photoinitiators.

Dyes based on quinoline and quinoxaline skeletons were designed for application as visible light photoinitiators. The obtained compounds absorb electromagnetic radiation on the border between ultraviolet and visible light, which allows the use of dental lamps as light sources during the initiation of the photopolymerization reaction. Their another desirable feature is the ability to create a long-lived excited state, which enables the chain reaction to proceed through the mechanism of intermolecular electron transfer. In two-component photoinitiating systems, in the presence of an electron donor or a hydrogen atom donor, the synthesized compounds show excellent abilities to photoinitiate the polymerization of acrylates. In control tests, the efficiency of photopolymerization using modified quinoline and quinoxaline derivatives is comparable to that obtained using a typical, commercial photoinitiator for dentistry, camphorquinone. Moreover, the use of the tested compounds requires a small amount of photoinitiator (only 0.04% by weight) to initiate the reaction. The research also showed a significant acceleration of the photopolymerization process and shortening of the reaction time. In practice, this means that the new two-component initiating systems can be used in much lower concentrations without slowing down the speed of obtaining polymer materials. It is worth emphasizing that these two features of the new initiating system allow for cost reduction by reducing financial outlays on both materials (photoinitiators) and electricity.

The Use of Polymer Membranes for the Recovery of Copper, Zinc and Nickel from Model Solutions and Jewellery Waste.

A polymeric inclusion membrane (PIM) consisting of matrix CTA (cellulose triacetate), ONPPE (o-nitrophenyl pentyl ether) and phosphonium salts (Cyphos 101, Cyphos 104) was used for separation of Cu(II), Zn(II) and Ni(II) ions. Optimum conditions for metal separation were determined, i.e., the optimal concentration of phosphonium salts in the membrane, as well as the optimal concentration of chloride ions in the feeding phase. On the basis of analytical determinations, the values of parameters characterizing transport were calculated. The tested membranes most effectively transported Cu(II) and Zn(II) ions. The highest recovery coefficients (RF) were found for PIMs with Cyphos IL 101. For Cu(II) and Zn(II), they are 92% and 51%, respectively. Ni(II) ions practically remain in the feed phase because they do not form anionic complexes with chloride ions. The obtained results suggest that there is a possibility of using these membranes for separation of Cu(II) over Zn(II) and Ni(II) from acidic chloride solutions. The PIM with Cyphos IL 101 can be used to recover copper and zinc from jewellery waste. The PIMs were characterized by AFM and SEM microscopy. The calculated values of the diffusion coefficient indicate that the boundary stage of the process is the diffusion of the complex salt of the metal ion with the carrier through the membrane.

Study on New Dental Materials Containing Quinoxaline-Based Photoinitiators in Terms of Exothermicity of the Photopolymerization Process.

Modern dentistry places great demands on the dental composites used for filling tooth cavities or treating cavitated tooth decay. The aim of the work was to modify the properties of composites by changing the initiators and co-initiators. This was achieved by using initiators based on a quinoxaline skeleton and co-initiators that are derivatives of acetic acid, which is an advantage of these photoinitiating systems due to the elimination of aromatic amines from the photocurable composition. The composites also differed in dental fillers. The effect of the compounds on the exothermicity of the photopolymerization process, the surface morphology of the obtained materials and the maximum compressive strength were determined. The photoinitiating capacity of the two-component systems was tested by the microcalorimetric method using the multifunctional monomer TMPTA, typical for dental filler compositions. The new photoinitiating systems show particularly good efficiency of free radical polymerization initiation, which occurs by the photoinduced intermolecular electron transfer (PET) mechanism. The comparison of the tested systems with camphorquinone, a photoinitiator traditionally used in dentistry, made it possible to observe a decrease in temperature during photopolymerization without a significant decrease in the polymerization rate or increase in photocuring time, as well as a better homogeneity of the surface of the obtained polymeric materials. This indicates that dye-acetic acid derivative systems may be useful in dental applications.

Acenaphthoquinoxaline Derivatives as Dental Photoinitiators of Acrylates Polymerization.

A series of dyes based on the acenaphthoquinoxaline skeleton was synthesized. Their structure was modified by introducing electron-withdrawing and electron-donating groups, increasing the number of conjugated double bonds and the number and position of nitrogen atoms, as well as the arrangement of aromatic rings (linear or angular). The dyes were investigated as a component in the photoinitiating systems of radical polymerization for a potential application in dentistry. They acted as the primary absorber of visible light and the acceptor of an electron, which was generated from a second component being an electron donor. Thus, the radicals were generated by the photoinduced intermolecular electron transfer (PET) process. Electron donors used differed in the type of heteroatom, i.e., O, S and N and the number and position of methoxy substituents. To test the ability to initiate the polymerization reaction by photoinduced hydrogen atom transfer, we used 2-mercaptobenzoxazole as a co-initiator. The effectiveness of the photoinitiating systems clearly depends on both the modified acenaphthoquinocaline structure and the type of co-initiator. The lower amount of heat released during the chain reaction and the polymerization rate comparable to this achieved for the photoinitiator traditionally used in dentistry (camphorquinone) indicates that the studied dyes may be valuable in this field.

Separation and Recovery of Gold(III), Palladium(II) and Platinum(IV) by Solvent Extraction Using a New ß-Diketone Derivative from Acidic Solutions.

This study indicates that a new amine derivative of ß-diketone (EDAB-acac) can be successfully used in an acidic medium (HCl) to separate a mixture containing Au(III), Pd(II), and Pt(IV) ions using solvent extraction. The study was conducted in single and ternary model solutions. The impact of acid concentration and the type of solvent (toluene, chloroform, methylene chloride, 2-ethylhexanol) on separation efficiency was discussed. It has been shown that increasing the HCl concentration in the aqueous phase does not favor extraction. In contrast, solvents with high donor numbers (methylene chloride, 2-ethylhexanol) increase both the extraction percentage of Pd and Au as well as the separation coefficients of Pd in relation to Au and Pt. The palladium(II) and gold(III) (which form 4-coordinated planar [MCl4]2- complexes) are extracted most efficiently, Pd(II) (87-93%) and Au(III) (56-62%). The stripping of Au(III), Pd(II), and Pt(IV) ions from the EDAB-acac-methylene chloride phase was also investigated using 0.5 M ammonia aq., mineral acid (5 M HCl, 5 M HNO3), 0.1 M thiourea in HCl and 0.5 M ammonium thiocyanate. A 3-step stripping process was proposed for the recovery of Pd(II), Au(III), and Pt(IV) from the Pd-Au-Pt mixture in the EDAB-acac-methylene chloride system. In the first stage, the aqueous phase is treated with 5 M HNO3 (Pt separation), followed by the application of 0.5 M ammonia (Pd separation) and, finally, 0.1 M thiourea in HCl (Au separation). The solvent extraction with EDAB-acac in acidic medium (HCl) can be used for separation of Pd(II) and Au(III) ions from e-waste leach solutions.

Effective Singlet Oxygen Sensitizers Based on the Phenazine Skeleton as Efficient Light Absorbers in Dye Photoinitiating Systems for Radical Polymerization of Acrylates.

A series of dyes based on the phenazine skeleton were synthesized. They differed in the number of conjugated double bonds, the arrangement of aromatic rings (linear and/or angular system), as well as the number and position of nitrogen atoms in the molecule. These compounds were investigated as potential singlet oxygen sensitizers and visible light absorbers in dye photoinitiating systems for radical polymerization. The quantum yield of the singlet oxygen formation was determined by the comparative method based on the 1H NMR spectra recorded for the tested dyes in the presence of 2,3-diphenyl-p-dioxene before and after irradiation. The quantum yield of the triplet state formation was estimated based on the transient absorption spectra recorded using the nanosecond flash photolysis technique. The effectiveness of the dye photoinitiating system was characterized by the initial rate of trimethylolpropane triacrylate (TMPTA) polymerization. In the investigated photoinitiating systems, the sensitizer was an electron acceptor, whereas the co-initiator was an electron donor. The effectiveness of TMPTA photoinitiated polymerization clearly depended on the arrangement of aromatic rings and the number of nitrogen atoms in the modified phenazine structure as well as the quantum yield of the triplet state formation of the photosensitizer in the visible light region.

New Polymer Inclusion Membranes in the Separation of Palladium, Zinc and Nickel Ions from Aqueous Solutions.

The new polymer inclusion membrane (PIM) with a 1-alkyltriazole matrix was used to separate palladium(II) ions from aqueous chloride solutions containing a mixture of Zn-Pd-Ni ions. The effective conditions for transport studies by PIMs were determined based on solvent extraction (SX) studies. Furthermore, the values of the stability constants and partition coefficients of M(II)-alkyltriazole complexes were determined. The values of both constants increase with the growing hydrophobicity of the 1-alkyltriazole molecule and have the highest values for the Pd(II) complexes. The initial fluxes, selectivity coefficients, and recovery factors values of for Pd, Zn and Ni were determined on the basis of membrane transport studies. The transport selectivity of PIMs were: Pd(II) > Zn(II) > Ni(II). The initial metal ion fluxes for all the cations increased with the elongation of the alkyl chain in the 1-alkyltriazole, but the selectivity coefficients decreased. The highest values of the initial fluxes at pH = 4.0 were found for Pd(II) ions. The best selectivity coefficients Pd(II)/Zn(II) and Pd(II)/Ni(II) equal to 4.0 and 13.4, respectively, were found for 1-pentyl-triazole. It was shown that the microstructure of the polymer membrane surface influences the kinetics of metal ion transport. Based on the conducted research, it was shown that the new PIMs with 1-alkyltriazole can be successfully used in an acidic medium to separate a mixture containing Pd(II), Zn(II) and Ni(II) ions.

New Polymer Inclusion Membrane in the Separation of Nonferrous Metal Ion from Aqueous Solutions.

The new polymer inclusion membrane (PIM) with ethylenediamine-bis-acetylacetone (EDAB-acac) matrix was used for the separation of Zn(II) solutions containing non-ferrous metal ions (Co(II), Ni(II) Cu(II), Cd(II)). The effective conditions for carrying out transport studies by PIMs were determined on the basis of solvent extraction studies. The values of the stability constants and partition coefficients of M(II)-EDAB-acac complexes were determined from the extraction studies. The stability constants increase in series Ni(II) < Cu(II) < Co(II) < Cd(II) < Zn(II), and their logarithms are 8.85, 10.61, 12.73, 14.50, and 16.84, respectively. The transport selectivity of the PIMs were: Zn(II) > Cd(II) > Co(II) > Cu(II) > Ni(II). The established stability constants of the complexes also decrease in this order. The values of three parameters: initial flux, selectivity coefficient, and recovery factor of a given metal after 12 h were selected for the comparative analysis of the transport process. The highest values of the initial fluxes were received for Zn(II), Cd(II), and Co(II). They are, depending on the composition of the mixture, in the range 9.87-10.53 µmol/m2, 5.26-5.61 µmol/m2, and 7.43-7.84 µmol/m2 for Zn(II), Co(II), and Cd(II), respectively. The highest recovery factors were observed for Zn(II) ions (90-98.0%). For Cd, Co and Cu, the recovery factors are high and are within the range 76-83%, 64-79%, and 51-66%, respectively.

Application of Polymer Inclusion Membranes Doped with Alkylimidazole to Separation of Silver and Zinc Ions from Model Solutions and after Battery Leaching.

New materials, such as polymer inclusion membranes, can be used for water and wastewater treatment. In this paper, the selective transport of silver(I) and zinc(II) ions from nitrate solutions through the polymer inclusion membranes (PIMs), which consist of cellulose triacetate as a polymeric support, o-nitrophenyl pentyl ether as a plasticizer, and either 1-hexylimidazole (1) or 1-hexyl-2-methylimidazole (2) as an ion carrier, is studied. Both Zn(II) and Ag(I) model solutions (CM = 0.001 M, pH = 6.5), as well as the solutions after the leaching of a spent battery with a silver-zinc cell (silver-oxide battery), are tested. The results show that Zn(II) ions are effectively transported through PIMs containing either carrier, whereas Ag(I) is more easily transported through PIMs doped with (1). In the case of the leaching solution after 24 h transport, the recovery coefficients of Ag(I) and Zn(II) for PIMs doped with (1) are 86% and 90%, respectively, and for PIMs doped with (2), 47% and 94%, respectively. The influence of basicity and structure of carrier molecules on transport kinetics is discussed as well. PIMs are characterized by using an atomic force microscopy (AFM) technique.

Separation of Zn(II), Cr(III), and Ni(II) Ions Using the Polymer Inclusion Membranes Containing Acetylacetone Derivative as the Carrier.

Polymer inclusion membranes (PIMs) doped with ethylenodiamino-bis-acetylacetone as fixed carrier was applied for the investigation of the facilitated transport of Zn(II), Cr(III), and Ni(II) ions from an aqueous nitrate feed phase (cM = 0.001 mol/dm3). The optimal membrane composition (amount of carrier and o-NPPE-plasticizer) was determined. For the optimal polymer inclusion membranes doped with ethylenodiamino-bis-acetylacetone, the following patterns of transport selectivity were found: Zn(II) > Cr(III) > Ni(II). The initial flux of Zn(II), Cr(III), and Ni(II) ions was 6.37 µmol/m2∙s, 5.53 µmol/m2∙s, and 0.40 µmol/m2∙s, respectively. The selectivity coefficients equal to 1.2 and 15.9 were found for Zn(II)/Cr(III) and Zn(II)/Ni(II), respectively. After 24-h transport, the recovery factor of Zn(II), Cr(III), and Ni(II) were 90%, 65%, and 6%, respectively. The polymer inclusion membranes doped with ethylenodiamino-bis-acetylacetone were characterized by scanning electron microscopy and non-contact atomic force microscopy. The influence of membrane morphology on transport process was discussed.

Relationship between structure and photoinitiating abilities of selected bromide salts of 2-oxo-2,3-dihydro-1H-imidazo[1,2-a]pyridine (IMP): influence of the solvent and the substitution in benzaldehyde on the course of its reaction with IMP.

2-Oxo-2,3-dihydro-1H-imidazo[1,2-a]pyridinium bromide and its C3-substituted derivatives have been synthesized and structurally characterized by X-ray crystallography and quantum chemical calculations. Their potential as photoinitiators for free-radical polymerization has been investigated experimentally and compared with theoretical results. It has been established that the course of the reaction that introduces the substituted benzylidene group to the imidazole ring is different in the protic and dipolar aprotic solvents, and also depends on the character of the substituent, as the energy change in the reaction favours either R1R2C=CHR3 or R1R2CH-CH(OCH3)R3 formation.

New type of bonding formed from an overlap between pi aromatic and pi C=O molecular orbitals stabilizes the coexistence in one molecule of the ionic and neutral meso-ionic forms of imidazopyridine.

New bis(imidazo)pyridine dye has been synthesized and tested as a potential photoinitaitor for free-radical polymerization induced with the visible emission of an argon ion laser. The X-ray analysis based on data collected at 170 and 130 K, as well as density functional theory (DFT) calculations, revealed the presence of two different forms of imidazopyridine rings within the same molecule. These two forms of the same moiety had not only different geometries but different electronic structures as well. One of the imidazopyridine rings was in the ionic form, while the other was in the meso-ionic form. DFT calculations provided an explanation for such an observed phenomena. The averaging of ionic and meso-ionic forms of imidazopyridine rings within the same molecule is hindered because of an attractive interaction between them. Analysis of electronic density revealed that, indeed, a new type of bonding is formed as the result of an overlap between pi aromatic and pi C=O molecular orbitals. This bonding, like the hydrogen bond, is primarily of electrostatic character, and its energy was estimated at 3.5 kcal/mol.