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.

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.

Controlling the fluorescence quantum yields of benzothiazole-difluoroborates by optimal substitution.

Precise tuning of the fluorescence quantum yield, vital for countless applications of fluorophores, remains exceptionally challenging due to numerous factors affecting energy dissipation phenomena often leading to its counterintuitive behavior. In contrast to the absorption and emission wavelength which can be precisely shifted to the desired range by simple structural changes, no general strategy exists for controllable modification of the fluorescence quantum yield. The rigidification of the molecular skeleton is known to usually enhance the emission and can be practically realized via the limiting molecular vibrations by aggregation. However, the subtle balance between the abundant possible radiative and non-radiative decay pathways makes the final picture exceptionally sophisticated. In the present study, a series of nine fluorophores obtained by peripheral substitution with two relatively mild electron donating and electron withdrawing groups are reported. The obtained fluorescence quantum yields range from dark to ultra-bright and the extreme values are obtained for the isomeric molecules. These severe changes in emission efficiency have been shown to arise from the complex relationship between the Franck-Condon excited state and conical intersection position. The experimental findings are rationalized by the advanced quantum chemical calculations delivering good correlation between the measured emission parameters and theoretical radiative and internal conversion rate constants. Therefore, the described substituent exchange provides a method to rigorously adjust the properties of molecular probes structurally similar to thioflavin T.

A Modified Oxazolone Dye Dedicated to Spectroscopy and Optoelectronics.

Here we present a newly synthesized bifunctional organic chromophore with appealing spectroscopic and nonlinear optical features. The positions of absorption and emission maxima of the dye vary with increasing solvent polarity and exhibit positive solvatochromism. The determined change in the dipole moment upon excitation based on the Bilot and Kawski theory is 5.94 D, which corresponds to the intermolecular displacement of a charge equal to 1.24 Å. An investigated organic-based system represents a significant, repeatable, and stable over time optical signal modulation in the manner of the refractive index value. Its magnitude is varied both by optical pumping intensity as well as by external frequency modulation, which indicates that such system is an alluring and alternative core unit for optoelectronic devices and complex networks. Then, the same active system, due to the nonresonant mechanism of higher harmonics of light inducement, can provide second and third harmonic signals. According to the introduced laser line spatial modifications (parallel or perpendicular polarization directions), it is resulted in output SHG signal with magnitude varied about 100%. Its magnitude is noticeably small; however, to construct sensitive optical sensors or infrared indicators, such feature may guarantee satisfying circumstances.

Multifunctional Oxazolone Derivative as an Optical Amplifier, Generator, and Modulator.

An optical control of many working optoelectronic systems (real-time sensors, optical modulators, light amplifiers, or phase retarders) giving efficient optical gain or remote signal modulation is currently included as scientifically and industrially interesting. In here, an oxazolone derivative as the multifunctional organic system is given in this contribution. The molecule possesses a stilbene group and an oxazolone heteroatomic ring, which implies effective refractive index manipulation and multimode lasing action, respectively. The light modulation is repeatable and stable, also in the hundreds of Hz regime. On the other hand, the amplified optical signal can be easily generated by an external optical pumping source. Thus, signal control is fully available, as is read-in and read-out of the information in real time. Furthermore, this third-order, nonlinear, optical phenomenon using a third harmonic generation technique was also observed. We discovered that only by changing the energy and time regime of the supplied optical signal is the optical or nonlinear optical response observed. Two heteroenergetic molecular states (trans (E) and cis (Z)) can efficiently operate in modern multifunctional optoelectronic systems, which can provide and generate an optical signal. Such functionalities are commonly used in all-optical photonic switchers and logic gates and can be utilized in optical-core networks and computers.

Fluorescent Chitosan Modified with Heterocyclic Aromatic Dyes.

Chitosan is a valuable, functional, and biodegradable polysaccharide that can be modified to expand its applications. This work aimed to obtain chitosan derivatives with fluorescent properties. Three heterocyclic aromatic dyes (based on benzimidazole, benzoxazole, and benzothiazole) were synthesized and used for the chemical modification of chitosan. Emission spectroscopy revealed the strong fluorescent properties of the obtained chitosan derivatives even at a low N-substitution degree of the dye. The effect of high-energy ultraviolet radiation (UV-C) on modified chitosan samples was studied in solution with UV-Vis spectroscopy and in the solid state with FTIR spectroscopy. Moreover, cytotoxicity towards three different cell types was evaluated to estimate the possibilities of biomedical applications of such fluorescent chitosan-based materials. It was found that the three new derivatives of chitosan were characterized by good resistance to UV-C, which suggests the possibility of using these materials in medicine and various industrial sectors.

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.

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.

Effect of the Chloro-Substitution on Electrochemical and Optical Properties of New Carbazole Dyes.

Carbazole derivatives are the structural key of many biologically active substances, including naturally occurring and synthetic ones. Three novel (E)-2-(2-(4-9H-carbazol-9-yl)benzylidene)hydrazinyl)triazole dyes were synthesized with different numbers of chlorine substituents attached at different locations. The presented research has shown the influence of the number and position of attachment of chlorine substituents on electrochemical, optical, nonlinear, and biological properties. The study also included the analysis of the use of the presented derivatives as potential fluorescent probes for in vivo and in vitro tests. Quantum-chemical calculations complement the conducted experiments.

Aromatic Amines in Organic Synthesis. Part II. p-Aminocinnamaldehydes.

Ten derivatives of p-aminocinnamic aldehydes were prepared from the reaction of either aromatic amines with dimethylaminoacrolein or benzaldehydes with acetaldehyde. Their chemical structure and purity were verified by 1H NMR, 13C NMR and IR spectroscopic methods. We found that the synthesis applying dimethylaminoacrolein as the reagent gets better yields than the one based on the reaction with acetaldehyde. The yields of the cinnamic aldehydes varied according to the type of the amino group and the number and position of the substituents. The basic spectroscopic properties of the p-aminocinnamic aldehydes are also described since the compounds may be a precursor for the synthesis of dyes for diverse applications, e.g., in medicine and optoelectronics.

Controlling Two-Photon Action Cross Section by Changing a Single Heteroatom Position in Fluorescent Dyes.

The optimization of nonlinear optical properties for "real-life" applications remains a key challenge for both experimental and theoretical approaches. In particular, for two-photon processes, maximizing the two-photon action cross section (TPACS), the figure of merit for two-photon bioimaging spectroscopy, requires simultaneously controlling all its components. In the present Letter, a series of difluoroborates presenting various heterocyclic rings as an electron acceptor have been synthesized and their absorption, fluorescence, photoisomerization, and two-photon absorption features have been analyzed using both experimental and theoretical approaches. Our results demonstrate that the TPACS values can be fine-tuned by changing the position of a single heteroatom, which alters the fluorescence quantum yields without changing the intrinsic two-photon absorption cross section. This approach offers a new strategy for optimizing TPACS.

Highly Effective Sensitizers Based on Merocyanine Dyes for Visible Light Initiated Radical Polymerization.

The 5-(4-substituted-arylidene)-1,3-dimethylpyrimidine-2,4,6-triones were tested as visible light sensitizers for phenyltrialkylborate salts applied to initiate polymerization processes. The initiation occurs as a result of photoinduced electron transfer from the borate salt to the merocyanine dye. The main factor that facilitates the step of the reaction is the free energy change for electron transfer. Its value is favorable according to the reduction properties of the dyes influenced by the type of amino groups and the oxidation potentials of the borate salts. The observed bleaching of the dyes during photopolymerization affects the yield of both the alkyl radical and sensitizer-based radical formation and thus the efficiency of the photopolymerization.

2'-(1H-phenanthro[9,10-d]imidazol-2-yl)-phenyl-4-carboxylic acid N-hydroxysuccinimide ester: A new phenanthroimidazole derivative as a fluorescent probe for medical imaging applications.

In this study a new probe (2'-(1H-phenanthro[9,10-d]imidazol-2-yl)-phenyl-4-carboxylic acid N-hydroxysuccinimide ester, PB1-1) was synthesized and presented, containing the ester group as reactive group for medical imaging applications. The tests included a comparison to the PB1 probe with the aldehyde group described earlier. Also, the photophysics of PB1 and PB1-1 when conjugated to albumin (HSA) and concanavalin A (Con A) was studied. The fluorescence anisotropy measurements and the method of fluorescence quenching of protein were used to examine these interactions. The results showed that both dyes are highly bound to the studied proteins, especially PB1-1. In the present study we also compared the stability of prepared conjugates. The in vitro study have shown that all tested compounds presented to be usable in the case of fixated cell staining. PB1-1-ConA and PB1-1-HSA were characterized with the lowest cytotoxicity during the MTT assay, and thus should be more suitable for live imaging applications than PB1-ConA and PB1-HSA. The results obtained in this work confirmed the theses presented in in silico studies as to the correctness of the choice of ester group as actively binding to the protein. At the same time, we have experimentally demonstrated the significant influence of a probe-protein linker on the spectral properties of conjugates used in medical imaging. We have clearly indicated that a detailed analysis of derivatives with different reactive group allows for proper probe selection. We also pointed out that based on the geometric skeleton of one dye, a whole range of fluorescent probes with different absorption and fluorescence spectra can be obtained for in vitro tests in medical imaging.

Electrospray ionization collision induced dissociation of thiocarbocyanine and selenocarbocyanine dyes.

The effect of the properties of sulphur and selenium atoms, the composition and location of substituents (-CH3 , -OCH3 , -C2 H5 , and -C3 H6 -((N+ Br- )C5 H5 )), and the charge state on the collision induced dissociation (CID) behaviour of ions generated by electrospray ionization (ESI) of thiocarbocyanine and selenocarbocyanine dyes have been investigated. The results show that, for of all the examined singly charged ions, the main dissociation channel was related to the formation of distonic ions, generated as a result of cleavages within the dimethine bridge. In the case of doubly charged ions (with propyl-pyridinium substituents), competition between fragmentation processes related to charges located at different nitrogen atoms has been observed. The S/Se replacement also has an impact on the CID behaviour of the examined carbocyanine dyes. On the basis of the performed CID MS/MS experiments, general rules for the CID of thiocarbocyanine and selenocarbocyanine dyes have been proposed.

Influence of the Nature of the Amino Group in Highly Fluorescent Difluoroborates Exhibiting Intramolecular Charge Transfer.

A series of difluoroborates were synthesized from CH acids. All compounds were substituted with dialkylamino groups (NR2). The lone electron pair of the nitrogen atom of this donor moiety is variably delocalized toward the difluoroborate core that acts as the electron acceptor. This was rationalized in light of the various geometries of the amino group. The degree of charge transfer was quantified on the basis of the results of time-dependent density functional theory calculations.

Spectral and physicochemical properties of difluoroboranyls containing N,N-dimethylamino group studied by solvatochromic methods.

The solvatochromism of the dyes was analyzed based on the four-parameter scale including: polarizability (SP), dipolarity (SdP), acidity (SA) and basicity (SB) parameters by method proposed by Catalán. The change of solvent to more polar caused the red shift of absorption and fluorescence band position. The frequency shifts manifest the change in the dipole moment upon excitation. The ground-state dipole moment of the difluoroboranyls was estimated based on changes in molecular polarization with temperature. Moreover, the Stokes shifts were used to calculate the excited state dipole moments of the dyes. For the calculation, the ground-state dipole moments and Onsager cavity radius were also determined theoretically using density functional theory (DFT). The experimentally determined excited-state dipole moments for the compounds are higher than the corresponding ground-state values. The increase in the dipole moment is described in terms of the nature of the excited state.

The trans/cis photoisomerization in hydrogen bonded complexes with stability controlled by substituent effects: 3-(6-aminopyridin-3-yl)acrylate case study.

The association of aminopyridine-based acrylic acid and its salt was studied by NMR titration experiments. The AA (acceptor, acceptor) hydrogen-bonding pattern present in the salt forms a complex readily with a DD (donor, donor) hydrogen-bonding pattern of the substituted ureas even in polar and competitive environment. The double carbon-carbon bond in the acrylic acid derivative is subjected to photoisomerization. This is dependent on the association with substituted urea derivatives. The substituent in ureas influences the trans/cis isomerization kinetics and position of the photostationary state. Two mechanisms that influence the photoisomerization were proposed. To the best of our knowledge, the trans/cis photoisomerization influenced by the substituent in such a hydrogen-bonding pattern has not observed previously. It was shown that interaction with urea derivatives causes lowering of the trans-to-cis photoreaction rates.

Synthesis, photophysical and biological properties of a new oxazolone fluorescent probe for bioimaging: an experimental and theoretical study.

In this study, a new oxazolone derivative 4-{N,N-bis[2-phenyl-4-benzylidene-1,3-oxazol-5(4H)-one]amino}benzaldehyde (PB3) was synthesized and investigated as a fluorescent dye. The spectroscopic properties in different solvents were thoroughly studied. The experimental data were supported by quantum-chemical calculations using density functional theory. Measurements and theoretical calculations showed that the PB3 dye is characterized by non-monotonic solvatochromism, a strongly polar charge transfer excited state, a large Stokes' shift, a high fluorescence quantum yield and a high fluorescence lifetime. Bioconjugate complexes (PB3-concanavalin A) were studied by circular dichroism (CD) spectroscopy. The results showed that the secondary structure of concanavalin A was not significantly influenced by the PB3-fluorophore. Conventional fluorescence microscopy imaging of Candida albicans cells, incubated with the PB3-concanavalin A, was demonstrated. The results from cytochemistry experiments demonstrate that the PB3 dye has valuable advantages compared to the other long-wavelength dyes in typical fluorescence-based cell labeling applications. In vitro tolerance was evaluated by the MTT method in the human colon adenocarcinoma cell line HT29. The PB3 and bioconjugate complexes (PB3-concanavalin A), in the range of concentrations tested, were not considerably toxic. The AutoDock simulations showed LYS46 as the most likely active site for covalent bond formation during PB3-concanavalin A conjugation. In addition, theoretical studies have shown that PB3 is characterized by good bioavailability and absorption/transmission across the cell membrane. This molecule will not bioaccumulate in living organisms and should be excreted in urine without interacting with other drugs. This work provided promising results for the red fluorescent probe (PB3) as a valuable alternative to commercial probes designed for cellular labeling in biological and biomedical research.

Two-photon absorption of BF2-carrying compounds: insights from theory and experiment.

This communication presents a structure-property study of a few novel pyridine-based difluoroborate compounds with a N-BF2-O core, which exhibit outstanding fluorescence properties. To exploit their potential for two-photon bioimaging, relationships between the two-photon action cross section and systematic structural modifications have been investigated and unravelled.

Photophysical Properties of Phenacylphenantridine Difluoroboranyls: Effect of Substituent and Double Benzannulation.

In this study we present a new series of phenantridine-based substituted difluoroboranyls. The effects of substitution and double benzannulation on their photophysical properties were examined with experimental techniques and compared with the results obtained for previously reported quinoline and isoquinoline derivatives. The experimental characterizations are supported by state-of-the-art quantum-chemical calculations. In particular, the theoretical calculations were performed to gain insights into the complex nature of the relevant excited-states. These calculations reveal that both the nature of the substituent and its position on the phenyl ring significantly impact the magnitude of the electronic charge transferred upon excitation. Additionally, vibrationally resolved spectra were determined allowing for the analysis of the key vibrations playing a role in the band shapes.