Synthesis, singlet oxygen generation and DNA photocleavage of β,β′-conjugated polycationic porphyrins

2019 ◽  
Vol 23 (06) ◽  
pp. 655-663 ◽  
Author(s):  
Li Chen ◽  
Yimei Zhao ◽  
Xinyu Sun ◽  
Jun Jiang ◽  
Fengshou Wu ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Fluorescence Emission ◽  
Binding Constants ◽  
Binding Mode ◽  
Binding Modes ◽  
Cleavage Rate ◽  
Oxygen Generation ◽  
Vis Spectroscopy ◽  
Pbr322 Plasmid ◽  
Ct Dna

In this paper, three [Formula: see text],[Formula: see text]-conjugated cationic porphyrin compounds were designed and synthesized. The structure of the intermediates and desired porphyrins were confirmed by UV, IR, 1H NMR, MS and elemental analysis. The interaction modes between these porphyrins and ct-DNA were studied by UV-vis spectroscopy and fluorescence emission spectroscopy. The results showed that PCP 1 had an external binding mode with DNA at low DNA concentration and could intercalate DNA with the increase of concentration. PCP 2 interacted with DNA through an external binding mode, and PCP 3 could insert into DNA. The binding constants ([Formula: see text] between PCP1[Formula: see text]PCP3 and ct-DNA were calculated to be 8.41 × 104, 7.33 × 104 and 4.14 × 104 M[Formula: see text], respectively. The singlet oxygen (1O[Formula: see text] generation of PCP1[Formula: see text]PCP3 was determined by the 1,3-diphenylisobenzofuran (DPBF) method using tetrapyridylporphyrin (H2TMPyP) as a reference. The 1O2 generation rate of PCP1[Formula: see text]PCP3 followed the order of PCP2 >PCP1>H2TMPyP >PCP3. Subsequently, the photocleavage effect of porphyrins on pBR322 plasmid DNA was studied by gel electrophoresis. At 10.0 [Formula: see text]M, PCP1 and PCP2 could cleave DNA completely. At 2.0 [Formula: see text]M, the cleavage rate of DNA by PCP3 was 57.5%, which was significantly higher than that of H2TMPyP (38.8%). These results verified that the amount of cationic ions in the porphyrin structure could affect the binding modes of porphyrins with DNA and their cleavage ability of DNA.

Host-guest complexes of anionic porphyrin sensitizers with cyclodextrins

2002 ◽  
Vol 06 (08) ◽  
pp. 514-526 ◽  
Author(s):  
Jiří Mosinger ◽  
Viktor Kliment ◽  
Jan Sejbal ◽  
Pavel Kubát ◽  
Kamil Lang
Keyword(s):  
Singlet Oxygen ◽  
Specific Binding ◽  
Photophysical Properties ◽  
Bathochromic Shift ◽  
Fluorescence Emission ◽  
Binding Constants ◽  
Quantum Yields ◽  
Hydroxyl Groups ◽  
Triplet States ◽  
Binding Modes

The photodynamic sensitizers zinc(II)- and palladium(II)-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrins and 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin form 1:1 and/or 1:2 supramolecular complexes with native cyclodextrins (CD) and 2-hydroxypropyl cyclodextrins (hpCD) in aqueous neutral solutions. The formation of these assemblies causes a bathochromic shift of the porphyrin Soret band in the UV-vis spectra and a red shift of the fluorescence emission bands. The binding constants span over three orders of magnitude, from 8.1 × 102 M −1 to 5.4 × 105 M −1 (or 1.1 × 106 M −2) depending on the size of the CD cavity and on the functionalization by adding 2-hydroxypropyl groups. The highest binding constants were obtained for hpβCD and hpγCD. The Nuclear Overhauser spectroscopy signals (ROESY) revealed three binding modes: i) inclusion of the porphyrin 4-sulfonatophenyl or 4-carboxyphenyl groups via the secondary face of βCD and hpβCD with sulfonic or carboxylic groups oriented towards the primary hydroxyl groups. ii) inclusion of the porphyrin groups via the primary face of γCD and hpγCD. iii) non-specific binding of the porphyrin monomers or aggregates on the cyclodextrin exterior. The inclusion host-guest complexation via i) or ii) does not influence the inherent photophysical properties of the monomeric porphyrins such as the quantum yields of fluorescence, the triplet states, and the singlet oxygen formation. Due to the deaggregation effect of cyclodextrins, the inclusion complexes remain efficient supramolecular sensitizers of singlet oxygen even under conditions of extensive aggregation in aqueous solutions.

N-Methylpyridylporphyrin tailed with folate conjugate as a potential lysosomal-targeted photosensitizer: Synthesis, DNA interaction, singlet oxygen and subcellular localization

2019 ◽  
Vol 23 (06) ◽  
pp. 679-684
Author(s):  
Yi-Mei Zhao ◽  
Qian-Qian Lu ◽  
Si Yao ◽  
Hui-Fang Su ◽  
Hong-Jian Liu ◽  
...  
Keyword(s):  
Photodynamic Therapy ◽  
Singlet Oxygen ◽  
Fluorescence Spectra ◽  
Binding Constants ◽  
Binding Mode ◽  
Dna Interaction ◽  
H Nmr ◽  
Calf Thymus ◽  
Folate Conjugate ◽  
Tumor Drugs

In recent years, great interest has been focused on the use of photosensitizers (PS) for photodynamic therapy (PDT) as safe and effective anti-tumor drugs. As a good lysosomal-targeted drug, folic acid (FA) is highly interesting as well. [Formula: see text]-methylpyridylporphyrin tailed with folate conjugate (Me-Por-FA) was newly designed and synthesized and the structure was confirmed by UV-vis, IR, 1H NMR, MS and elemental analysis. The interaction of this porphyrin with calf thymus DNA was the intercalative binding mode, which was confirmed by ultraviolet and fluorescence spectra, and the binding constants [Formula: see text] was 6.24 × 104 L/mol. The singlet oxygen (1O[Formula: see text] generated by Me-Por-FA was determined by 1, 3-diphenylisobenzofuran (DPBF) method using tetrapyridylporphyrin (H[Formula: see text]TMPyP) as a comparison with the following order: H2TMPyP > Me-Por-FA. Stained with LysoTracker[Formula: see text] Green DND-26, Me-Por-FA was mainly distributed over the lysosomes during 4 h, but H[Formula: see text]TMPyP was not. This suggests that Me-Por-FA could be developed as a targeted photosensitizer for precise photodynamic therapy.

DNA AND BSA INTERACTIONS OF COPPER(II) AND ZINC(II) COMPLEXES WITH ANTIFUNGAL AGENT FLUCONAZOLE

2021 ◽  
Author(s):  
Nevena Lj. Stevanović ◽  
Mia Stanković ◽  
Tina P. Andrejević ◽  
Darko P. Ašanin ◽  
Ivana M. Stanojević ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Bovine Serum Albumin ◽  
Emission Spectroscopy ◽  
Antitumor Agents ◽  
Fungal Infections ◽  
Fluorescence Emission ◽  
Binding Constants ◽  
Special Importance ◽  
Calf Thymus ◽  
Ct Dna

Aromatic nitrogen-containing heterocycles (N-heterocycles) have attracted a considerable attention as scaffolds for compounds, which have an application in different pharmacological areas, ranging from vitamins to different antimicrobial and antitumor agents. In this respect, azoles are of special importance as potent and broad-spectrum agents used for the treatment of many invasive fungal infections. In the present study, the interaction of the clinically used antifungal drug fluconazole (fcz) and its copper(II) and zinc(II) complexes, {[CuCl2(fcz)2].5H2O}n (1) and {[ZnCl2(fcz)2]·2C2H5OH}n (2), with calf thymus DNA (ct- DNA) and bovine serum albumin (BSA) has been investigated. Fluorescence emission spectroscopy was applied for the binding study of complexes 1 and 2 and fcz with ct-DNA and BSA, while cyclic voltammetry was additionally used for investigation of their interactions with ct-DNA. The values of calculated binding constants (KA) of the investigated compounds towards ct-DNA and BSA follow the order fcz < 1 < 2 and 2 < fcz < 1, respectively.

scholarly journals Study on Interaction of Cationic Porphyrazine with Synthetic Polynucleotides

2013 ◽  
Vol 36 (5-6) ◽  
pp. 125-132 ◽  
Author(s):  
Hamid Dezhampanah ◽  
Soghra Fyzolahjani
Keyword(s):  
Electrostatic Interactions ◽  
Fluorescence Emission ◽  
Binding Constants ◽  
Binding Mode ◽  
Calf Thymus ◽  
Quenching Process ◽  
Enthalpy And Entropy Changes ◽  
Enthalpy And Entropy ◽  
Hoff Equation ◽  
Groove Binding Mode

Interactions of cationic tetrakis (N, N′, N″, N‴- tetramethyltetra-3, 4-pyridinoporphyrazinatozinc (II) (Zn (tmtppa)) with synthetic polynucleotides, poly (G-C) and poly (A-T), and calf thymus DNA have been characterized in 7.5 mM phosphate buffer of pH 7.2 by UV-Vis absorption and fluorescence spectroscopy. The appearance of hypochromicity more than 30% in UV-Vis spectra of porphyrazine due to interaction of both poly (G-C) and poly (A-T) indicates interaction similar to that of porphyrazine with DNA.The binding constants were determined from the changes in the Q-band maximum of the porphyrazine spectra at various poly (G-C) and DNA concentrations. The values of K were 2.5 × 106M−1, 2.5 × 106M−1and 2.5 × 105M−1for poly (G-C), poly (A-T) and DNA, respectively, at 25°C. The thermodynamic parameters (ΔG°, ΔH°, ΔS°) were calculated using the van't Hoff equation at various temperatures. The enthalpy and entropy changes were determined to be 41.14 kJ mol−1and 260.50 J mol−1·K−1for poly (G-C) and 53.59 kJ mol−1and 285.46 J mol−1·K−1for DNA at 25°C. The positive and large values of the entropy and enthalpy suggest that both hydrophobic and electrostatic interactions may play an important role in the stabilization of the complex formation. The binding of polynucleotides to porphyrazine quenches fluorescence emission of ethidium bromide (EB), and the quenching process obeys linear Stern-Volmer relationship. The results reviled groove-binding mode of porphyrazine for both AT- and GC-rich polynucleotides of DNA.

scholarly journals A H2O2-Responsive Boron Dipyrromethene-Based Photosensitizer for Imaging-Guided Photodynamic Therapy

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 32 ◽  
Author(s):  
Zhi-Wei Wang ◽  
Dan Su ◽  
Xiao-Qiang Li ◽  
Jing-Jing Cao ◽  
De-Chao Yang ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Fluorescence Emission ◽  
Human Embryonic Lung ◽  
Buffer Solution ◽  
Promising Candidate ◽  
Oxygen Generation ◽  
Boron Dipyrromethene ◽  
Band Absorption ◽  
Phosphate Buffered Saline ◽  
Human Embryonic Lung Fibroblast

In this study, we demonstrate a novel H2O2 activatable photosensitizer (compound 7) which contains a diiodo distyryl boron dipyrromethene (BODIPY) core and an arylboronate group that quenches the excited state of the BODIPY dye by photoinduced electron transfer (PET). The BODIPY-based photosensitizer is highly soluble and remains nonaggregated in dimethyl sulfoxide (DMSO) as shown by the intense and sharp Q-band absorption (707 nm). As expected, compound 7 exhibits negligible fluorescence emission and singlet oxygen generation efficiency. However, upon interaction with H2O2, both the fluorescence emission and singlet oxygen production of the photosensitizer can be restored in phosphate buffered saline (PBS) solution and PBS buffer solution containing 20% DMSO as a result of the cleavage of the arylboronate group. Due to the higher concentration of H2O2 in cancer cells, compound 7 even with low concentration is particularly sensitive to human cervical carcinoma (HeLa) cells (IC50 = 0.95 μM) but hardly damage human embryonic lung fibroblast (HELF) cells. The results above suggest that this novel BODIPY derivative is a promising candidate for fluorescence imaging-guided photodynamic cancer therapy.

DNA Photocleavage and Binding Modes of Methylene Violet 3RAX and its Derivatives: Effect of Functional Groups

2017 ◽  
Vol 70 (7) ◽  
pp. 830 ◽  
Author(s):  
Ke Yang ◽  
Xiong Zhang ◽  
Fang Yang ◽  
Fengshou Wu ◽  
Xiulan Zhang ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Electrostatic Interactions ◽  
1H Nmr Spectroscopy ◽  
Binding Mode ◽  
Binding Modes ◽  
Oxygen Production ◽  
Groove Binding ◽  
Dna Photocleavage ◽  
Intercalative Mode ◽  
Methylene Violet

With 4′-amino-N,N-diethylaniline and aniline as starting materials, methylene violet 3RAX 1 and its derivatives 2–5 were synthesised. The five compounds were characterised by IR, UV-vis, and 1H NMR spectroscopy and mass spectrometry. The binding mode between the synthesised compounds and DNA were investigated. The results show that both compounds 1 and 5 bind to DNA by an intercalative mode, while compounds 2–4 interact with DNA through a mixed binding mode involving groove binding and electrostatic interactions. The photocleavage ability of the five compounds to DNA were calculated to be 38, 40, 30, 20, and 13 %, respectively, when their concentration was adjusted to 400 μM. The singlet oxygen production of compounds measured by the 1,3-diphenylisobenzofuran method was consistent with the trend of DNA photocleavage ability. The DNA studies suggest that the binding mode between methylene violet 3RAX and DNA, the ability of methylene violet 3RAX to generate singlet oxygen, and the DNA photocleavage activity could be adjusted through modification of the amino group on methylene violet 3RAX.

Germanium triazatetrabenzcorrole and germanium phthalocyanine: Synthesis, fluorescence and singlet oxygen generation

2018 ◽  
Vol 22 (09n10) ◽  
pp. 847-852 ◽  
Author(s):  
Xian-Fu Zhang ◽  
Xiaojie Sun
Keyword(s):  
Singlet Oxygen ◽  
Fluorescence Emission ◽  
Emission Spectra ◽  
Fluorescence Properties ◽  
Quantum Yields ◽  
Fluorescence Lifetimes ◽  
Fluorescence Emission Spectra ◽  
Oxygen Generation ◽  
Fluorescence Quantum Yields ◽  
Singlet Oxygen Generation

The synthesis, fluorescence properties and singlet oxygen generation capability of germanium tetrabenzotriazacorrole (LGeTBC), germanium phthalocyanine (Cl[Formula: see text]GePc) and their derivatives are described. Measurements include UV-vis absorption spectra, fluorescence emission spectra, fluorescence quantum yields fluorescence lifetimes, and singlet delta oxygen quantum yields. LGeTBC and its derivatives exhibit quite different spectral and fluorescence properties from their phthalocyanine precursor. Both LGeTBC and Cl[Formula: see text]GePc show high singlet delta oxygen quantum yields and suitable fluorescence quantum yields, indicating that they can act as good singlet oxygen photosensitizers for photodynamic therapy.

scholarly journals Study on the interaction between ketoprofen and bovine serum albumin by molecular simulation and spectroscopic methods

2011 ◽  
Vol 26 (6) ◽  
pp. 337-348 ◽  
Author(s):  
Jin Lian Zhu ◽  
Jia He ◽  
Hua He ◽  
Shu Hua Tan ◽  
Xiao Mei He ◽  
...  
Keyword(s):  
Bovine Serum Albumin ◽  
Serum Albumin ◽  
Molecular Simulation ◽  
Bovine Serum ◽  
Binding Constants ◽  
Simulation Method ◽  
Binding Mode ◽  
Tryptophan Residue ◽  
Vis Spectroscopy ◽  
Static And Dynamic Quenching

The interaction between ketoprofen and bovine serum albumin (BSA) was investigated by molecular simulation, fluorescence and UV-vis spectroscopy methods under the simulated physiological conditions. Molecular simulation method performed to reveal the possible binding mode or mechanism suggested the binding forces between ketoprofen and BSA were mainly hydrophobic interaction and hydrogen bond, which was in agreement with the thermodynamic study (ΔHΦand ΔSΦwere calculated to be 74.514 kJ/mol and 333.98 J/mol · K). The binding constants of ketoprofen and BSA at different temperatures (298, 310 and 318 K) were calculated according to the data obtained from fluorescence spectra and the results indicated that ketoprofen had strong ability to quench the intrinsic fluorescence of BSA via a combination of static and dynamic quenching. Meanwhile, the changes of the conformation of BSA caused by ketoprofen were qualitatively analyzed with the UV-vis and synchronous fluorescence spectroscopy. The distance between ketoprofen and tryptophan residue in BSA was calculated to be 1.58 nm.

Cationic Zn and Al phthalocyanines: synthesis, spectroscopy and photosensitizing properties

2007 ◽  
Vol 11 (08) ◽  
pp. 586-595 ◽  
Author(s):  
Dmitry A. Makarov ◽  
Olga A. Yuzhakova ◽  
Ludmila K. Slivka ◽  
Nina A. Kuznetsova ◽  
Vladimir M. Negrimovsky ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Structural Modification ◽  
Aqueous Media ◽  
Sewage Water ◽  
Oxygen Generation ◽  
Singlet Oxygen Generation ◽  
Vis Spectroscopy ◽  
Key Features ◽  
A Minor ◽  
Inactivation Of Bacteria

Several Zn (II) and Al (III) phthalocyanines bearing eight or sixteen positive charges on substituents of different structure have been prepared. Synthesized polycationic phthalocyanines have been studied in aqueous and alcoholic media by UV-vis spectroscopy and tested for their efficacy in singlet oxygen photosensitization. It has been found that a minor structural modification at the periphery of the photosensitizer allows control over its key features such as singlet oxygen generation due to specific intermolecular interactions in solution. The efficacy of polycationic phthalocyanines to sensitize tryptophan photobleaching in aqueous media and inactivation of bacteria in sewage water is also structure-dependent. Among the complexes studied, two dyes - zinc octakis(pyridiniomethyl)- and octakis[ N -(2-hydroxyethyl)- N , N -dimethylammoniomethyl]substituted phthalocyanines - are the best sensitizers and have high potential for photodynamic applications.

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