Photodynamic Effect of 5,10,15,20-Tetrakis[4-(3-N,N-dimethylaminopropoxy)phenyl]chlorin towards the Human Pathogen Candida albicans under Different Culture Conditions

Photocytotoxic activity sensitized by 5,10,15,20-tetrakis[4-(3-N,N-dimethylaminopropoxy)phenyl]chlorin (TAPC) was investigated in Candida albicans under different culture conditions. Planktonic cells incubated with 2.5 μM TAPC were eradicated after 5 min irradiation with white light. Studies in the presence of reactive oxygen species scavengers indicated the involvement of mainly a type II mechanism. Furthermore, cell growth of C. albicans was suppressed in the presence of 5 μM TAPC. A decrease in pseudohyphae survival of 5 log was found after 30 min irradiation. However, the photokilling of this virulence factor reached a 1.5 log reduction in human serum. The uptake of TAPC by pseudohyphae decreased in serum due to the interaction of TAPC with albumin. The binding constant of the TAPC-albumin complex was ~104 M−1, while the bimolecular quenching rate constant was ~1012 s−1 M−1, indicating that this process occurred through a static process. Thus, the photoinactivation of C. albicans was considerably decreased in the presence of albumin. A reduction of 2 log in cell survival was observed using 4.5% albumin and 30 min irradiation. The results allow optimizing the best conditions to inactivate C. albicans under different culture conditions.

Spectroscopic Study on the Reaction of Singlet-Excited Nile Blue with Certain Antioxidants

The photoinduced interaction of nile blue (NB) with various antioxidant molecules was investigated by fluorescence quenching technique and lifetime measurements. The various substituted catecholic compounds are employed as quenchers to evaluate their antioxidant activity. The formations of ground state complex between NB and quencher molecules observed from the UV-Visible absorption spectroscopy. The bimolecular quenching rate constants (kq) values depend on presence of substituent and its electronic properties of quencher molecules. Fluorescence quenching experiments have been performed at three different temperatures to assess the thermodynamic parameters. Time resolved fluorescence measurements suggest that the fluorescence quenching of NB with antioxidant molecules undergoes static quenching mechanism. The bond dissociation enthalpy (BDE) values reveal the discharge of HTfrom the antioxidant molecules. The electronic properties play an important role in the antioxidant activity of quencher molecules. The mechanism of fluorescence quenching between NB and quencher molecules are analysed based on the fluorescence quenching experiments, cyclic voltammetry experiments and BDE calculations.

Elucidating the Photoluminescence Quenching in Ensulizole: An Artificial Water Soluble Sunscreen

Employing natural or artificial sunscreens is essential to protect the skin from ultraviolet radiations that cause premature aging and develop melanoma and other forms of skin cancer. The 2-Phenylbenzimidazole-5-sulfonic acid, commonly known as ensulizole is a water-soluble artificial sunscreen that absorbs mostly UV-B (280 nm − 315 nm) radiations and protects the skin against the harmful effects of these radiations. Steady-state absorption indicates a strong absorption feature at 303 nm and a weak at 316 nm that have been identified as π → π* and n → π* transitions, respectively. The photoluminescence (PL) spectra indicate that the PL of ensulizole is less Stokes-shifted in polar solvents and more Stokes-shifted in non-polar solvents. The average PL lifetime of ensulizole is longer in non-polar solvents as compared to polar solvents and it exhibits the shortest PL lifetime in aqueous medium that signifies its efficiency in water. This suggests in non-polar solvents intersystem crossing is the dominant mode of relaxation of the excited ππ* state. Furthermore, an increase of pH of ensulizole solution decreases the PL intensity and the lifetime. Stern-Volmer equation is employed to evaluate bimolecular quenching rate constant kq that suggests the diffusional dynamic mode of PL quenching is operative.

Fluorescence Quenching Studies on the Interactions between Chosen Fluoroquinolones and Selected Stable TEMPO and PROXYL Nitroxides

The influence of the stable 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) nitroxide and its six C4-substituted derivatives, as well as two C3-substituted analogues of 2,2,5,5-tetramethylpyrrolidynyl-N-oxyl (PROXYL) nitroxide on the chosen fluoroquinolone antibiotics (marbofloxacin, ciprofloxacin, danofloxacin, norfloxacin, enrofloxacin, levofloxacin and ofloxacin), has been examined in aqueous solutions by UV absorption as well as steady-state and time-resolved fluorescence spectroscopies. The mechanism of fluorescence quenching has been specified and proved to be purely dynamic (collisional) for all the studied systems, which was additionally confirmed by temperature dependence experiments. Moreover, the selected quenching parameters—that is, Stern–Volmer quenching constants and bimolecular quenching rate constants—have been determined and explained. The possibility of electron transfer was ruled out, and the quenching was found to be diffusion-limited, being a result of the increase in non-radiative processes. Furthermore, as the chosen nitroxides affected the fluorescence of fluoroquinolone antibiotics in different ways, an influence of the structure and the type of substituents in the molecules of both fluoroquinolones and stable radicals on the quenching efficiency has been determined and discussed. Finally, the impact of the solvent’s polarity on the values of bimolecular quenching rate constants has been explained. The significance of the project comes from many applications of nitroxides in chemistry, biology and industry.

Porphyrin based metal-organic frameworks with record sensitivity in optical oxygen sensing

The optical oxygen sensing capabilities of the porphyrin-based metal-organic frameworks, PCN-224, Pt(II)PCN-224 and Pd(II)PCN-224 were investigated. The bimolecular quenching constants (kq) of 37000 (PCN-224), 6700 (Pd(II)PCN-224) and 3900 Pa-1s-1 (Pt(II)PCN-224)...

BOVINE SERUM ALBUMIN FLUORESCENCE QUENCHING BY TANNIC ACID IN DIMETHYLSULFOXIDE CONTAINING SOLUTIONS

Bovine serum albumin (BSA) interaction with tannic acid (TA) has been studied in dimethylsulfoxide (DMSO) aqueous solutions at different temperatures (293 and 303 K). To find out the fluorescence quenching mechanism of BSA in the presence of TA, the fluorescence data were analyzed according to the modified Stern-Volmer equation based on the approach of the existence of a “sphere of action” (a type of apparent static quenching). The values of apparent static and bimolecular quenching constants were calculated. The effect of DMSO and temperature on BSA–TA interactions is explained on the basis of structural changes in the “sphere of action” of the fluorophore due to the possible inclusion of DMSO molecules in this sphere.

Interaction of Nitroglycerin with Bovine Serum Albumin and the Influence of Metal Ions on the Binding

The effect of Cu2+, Ca2+, Mg2+and Zn2+ on the interaction between nitroglycerin and bovine serum albumin was investigated. The bimolecular quenching rate constant, the Stern-Volmer quenching constant, the binding constants and the number of binding sites were calculated in the absence and presence of Cu2+, Ca2+, Mg2+and Zn2+. The quenching constants of nitroglycerin to bovine serum albumin were increased in the presence of metal ions. Static quenching mechanism was also confirmed. The binding constants of nitroglycerin to bovine serum albumin were influenced by different metal ions. The enthalpy change, free energy chang, entropy change and the distance between the donor and the acceptor at different temperatures were calculated. The results indicated that energy transfer from bovine serum albumin to nitroglycerin occurs with high probability.