Microwave assisted synthesis, photophysical and redox properties of (phenothiazinyl)vinyl-pyridinium dyes

Găină, Luiza; Torje, Ioana; Gál, Emese; Lupan, Alexandru; Bischin, Cristina; Silaghi‐Dumitrescu, Radu; Damian, Grigore; Lönnecke, Peter; Cristea, Castelia; Silaghi‐Dumitrescu, Luminiţa

doi:10.1016/j.dyepig.2013.10.044

Cited by 18 publications

(7 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Going further, we investigated the steady-state and time-resolved fluorescence emission properties of dyes 3b and 3a in solid state, under one-photon excitation at 485 nm. Upon excitation at 485 nm the novel 3b and 3a dyes displayed distinct fluorescence emissions in the solid state (λ em = 650 nm for 3b and λ em = 720 nm for 3a ), likewise previously reported PVP dyes 3a and 3c (λ em = 749 nm for 3a and λ em = 668 nm for 3c [11]).…”

Section: Optical Propertiessupporting

confidence: 84%

“…Continuing our previous investigations dedicated to the synthesis and characterization of (phenothiazinyl)vinyl-pyridinium (PVP) dyes [11], in this work the series of cationic methine dyes was extended with three new representatives (i.e., 3b, 3a and 3d), exhibiting structural adjustments designed to modulate their optical properties by introducing an auxochromic bromo-substituent at the electron-donor phenothiazine unit 3b and to modify the aggregation properties of the dye by attaching different alkyl chains and varying the counter ion at the pyridinium electron withdrawing unit 3a , 3d. In our pursuit for finding greener synthetic alternatives to the traditional methods to carry out organic synthesis, in our previous experiments the PVP dyes were conveniently synthesized by microwaves assisted condensation of phenothiazine carbaldehyde with methylpyridinium salts in dry media, while in this work we examine the benefits of ultrasound assisted and mechanochemical synthetic procedures, as candidates for environmentally friendly protocols proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements.…”

Section: Introductionmentioning

confidence: 83%

See 1 more Smart Citation

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

Stoean

Rugină

Focșan

et al. 2021

IJMS

Self Cite

View full text Add to dashboard Cite

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a’ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a’ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.

show abstract

Section: Optical Propertiessupporting

confidence: 84%

Section: Introductionmentioning

confidence: 83%

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

Stoean

Rugină

Focșan

et al. 2021

IJMS

Self Cite

View full text Add to dashboard Cite

show abstract

“…In this context, it was suggested that the autocatalytic behavior might be relevant for acute in vivo poisoning, while at physiological nitrite concentrations there are antioxidant systems (small antioxidant molecules, proteins and enzymes) that might scavenge the propagator species [ 20 ]. Furthermore, hemoglobin’s free radical reactivity, in reactions related to these and where high-valent iron and free radicals are generated, is of more general analytical importance [ 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 ]. In this context, experiments where small quantities of different antioxidant molecules were added to the nitrite + oxy reaction were also performed as detailed in the Supporting Information (Figure S25) .…”

Section: Resultsmentioning

confidence: 99%

The Reaction of Oxy Hemoglobin with Nitrite: Mechanism, Antioxidant-Modulated Effect, and Implications for Blood Substitute Evaluation

et al. 2018

Self Cite

View full text Add to dashboard Cite

The autocatalytic reaction between nitrite and the oxy form of globins involves free radicals. For myoglobin (Mb), an initial binding of nitrite to the iron-coordinated oxygen molecule was proposed; the resulting ferrous-peroxynitrate species was not detected, but its decay product, the high-valent ferryl form, was demonstrated in stopped-flow experiments. Reported here are the stopped flow spectra recorded upon mixing oxy Hb (native, as well as chemically-derivatized in the form of several candidates of blood substitutes) with a supraphysiological concentration of nitrite. The data may be fitted to a simple kinetic model involving a transient met-aqua form, in contrast to the ferryl detected in the case of Mb in a similar reaction sequence. These data are in line with a previous observation of a transient accumulation of ferryl Hb under auto-catalytic conditions at much lower concentrations of nitrite (Grubina, R. et al. J. Biol. Chem. 2007, 282, 12916). The simple model for fitting the stopped-flow data leaves a small part of the absorbance changes unaccounted for, unless a fourth species is invoked displaying features similar to the oxy and tentatively assigned as ferrous-peroxynitrate. Density functional theory (DFT) calculations support this latter assignment. The reaction allows for differentiating between the reactivities of various chemically modified hemoglobins, including candidates for blood substitutes. Polymerization of hemoglobin slows the nitrite-induced oxidation, in sharp contrast to oxidative-stress type reactions which are generally accelerated, not inhibited. Sheep hemoglobin is found to be distinctly more resistant to reaction with nitrite compared to bovine Hb, at large nitrite concentrations (stopped-flow experiments directly observing the oxy + nitrite reaction) as well as under auto-catalytic conditions. Copolymerization of Hb with bovine serum albumin (BSA) using glutaraldehyde leads to a distinct increase of the lag time compared to native Hb as well as to any other form of derivatization examined in the present study. The Hb-BSA copolymer also displays a slower initial reaction with nitrite under stopped-flow conditions, compared to native Hb.

show abstract

“…Pursuing our interest in developing environmentally friendly procedures for the synthesis of new phenothiazine and ferrocene derivatives [23][24][25][26][27] and perceiving the importance of α-aminoacetonitrile derivatives as pharmaceutical and agrochemical intermediates with a great number of α-aminonitrile derivatives which were proved to have remarkable biological properties exhibiting enzymatic activity as potent and selective protease inhibitors, fungicidal and herbicidal activity [17], we designed an efficient, simple, and ecofriendly synthetic procedure for the preparation of new synthetic compounds containing joint phenothiazine/ferrocene and α-amino-nitrile pharmacophoric units. In this work we report the experimental procedure for the ultrasound-assisted addition of the TMSCN nucleophile to heterocyclic aldimines.…”

Section: Introductionmentioning

confidence: 99%

Ultrasound-assisted Strecker synthesis of novel 2-(hetero)aryl-2-(arylamino)acetonitrile derivatives

Gál

Gaina

Petkes

et al. 2020

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

This work describes an efficient, simple, and ecofriendly sonochemical procedure for the preparation of new α-(arylamino)acetonitrile derivatives C-substituted with phenothiazine or ferrocene units. The synthetic protocol is based on the Strecker reaction of a (hetero)aryl aldimine substrate with trimethylsilyl cyanide (TMSCN) in poly(ethylene glycol) (PEG) solution. The advantages of the sonochemical versus the conventional α-(arylamino)acetonitrile synthesis are the significantly shorter reaction time (30 min instead of 72 hours), the higher purity and the easier separation of the product that precipitated from the reaction mixture in crystalline form as depicted by scanning electron microscopy (SEM) analysis. The single crystal X-ray diffraction analysis disclosed the arrangement of the α-(arylamino)acetonitrile molecules in the aggregated crystalline state as a racemic mixture. The mutagenic/antimutagenic potential for three representative derivatives containing phenothiazinyl, ferrocenyl, and phenyl units, respectively, was evaluated by the Ames Salmonella/microsome test using S. typhimurium TA98 and TA100 strains with and without metabolic activation. The preliminary screening results pointed out that the C-(hetero)aryl-α-(arylamino)acetonitrile derivatives can be considered genotoxically safe and possibly antimutagenic.

show abstract

Microwave assisted synthesis, photophysical and redox properties of (phenothiazinyl)vinyl-pyridinium dyes

Cited by 18 publications

References 29 publications

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

The Reaction of Oxy Hemoglobin with Nitrite: Mechanism, Antioxidant-Modulated Effect, and Implications for Blood Substitute Evaluation

Ultrasound-assisted Strecker synthesis of novel 2-(hetero)aryl-2-(arylamino)acetonitrile derivatives

Contact Info

Product

Resources

About