Photodegradation of free base and zinc porphyrins in the presence and absence of oxygen.

Comparison of photostability in degassed and aerated toluene solutions is reported for 5,10,15,20-tetraphenylporphyrin, 5,10,15-tri(p-tolyl)porphyrin, and their zinc analogues. After degassing, quantum yields of photodegradation are higher, but the photodecomposition rates decrease. Lower stability in deoxygenated solutions is due to much longer triplet lifetimes: 200-300 microseconds, compared to 200-360 ns in non-degassed toluene. For the zinc porphyrins, the LC-MS results show that the initial photoproduct contains two oxygen atoms. Based on electronic absorption and calculations, it is assigned to dehydrated zinc biladienone structure, relatively stable in toluene, but readily demetallated in dichloromethane. A similar species is formed also in the case of free bases, but it then undergoes hydration due to traces of water present in the solvent. Zinc derivatives were found to form biladienones even in degassed solutions. To explain this observation, we postulate formation of a complex with remaining oxygen or oxygen-containing species which is not removed by freeze-thaw procedure. This hypothesis is confirmed by MS results and by the analysis of photodegradation products obtained when zinc porphyrin is complexed with dimethylsulfoxide (DMSO). Under these circumstances, changes in absorption are the same as in the absence of DMSO when non-degassed toluene is used, but irradiation of deoxygenated solutions leads to a different photoproduct. For both degassed and non-degassed solvents, complexation with DMSO results in the enhancement of photostability.

Tunable-wavelength nanosecond laser tailoring of plasmon resonance spectra of gold nanoparticle colloids.

Metal nanoparticles have applications across a range of fields of science and industry. While there are numerous existing methods to facilitate their large-scale production, most face limitations, particularly in achieving reproducible processes and minimizing undesirable impurities. Common issues are varying particle sizes and aggregates with unfavorable spectral properties. Researchers are currently developing methods to separate or modify nanoparticle sizes and shapes post-synthesis and to eliminate impurities. One promising approach involves laser light irradiation and enables the changing of nanoparticle sizes and shapes while controlling crucial spectral parameters. In this work, we present a novel extension of this method by irradiating nanoparticle colloids with variable-wavelength nanosecond laser pulses on both sides of the extinction band. Our results demonstrate the use of gradual laser wavelength tuning to optimize the photothermal reshaping of gold nanorods and achieve precise control over the plasmon resonance band. By irradiating both sides of the plasmon resonance band, we execute a multistep tuning process, controlling the band's width and spectral position. A statistical analysis of SEM images reveals differences in the nanorod morphology when irradiated on the long- or short-wavelength side of the plasmon resonance band. The fine-tuning of plasmonic spectral properties is desirable for various applications, including the development of sensors and filters and the exploitation of the photothermal effect. The findings of this study can be extended to other plasmonic nanostructures.

Replacement of the phosphodiester backbone between canonical nucleosides with a dirhenium carbonyl "click" linker-a new class of luminescent organometallic dinucleoside phosphate mimics.

The first-in-class luminescent dinucleoside phosphate analogs with a [Re2(µ-Cl)2(CO)6(µ-pyridazine)] "click" linker as a replacement for the natural phosphate group are reported together with the synthesis of luminescent adenosine and thymidine derivatives having the [Re2(µ-Cl)2(CO)6(µ-pyridazine)] entity attached to positions 5' and 3', respectively. These compounds were synthesized by applying inverse-electron-demand Diels-Alder and copper(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition reactions in three or four steps. The obtained compounds exhibited orange emission (λPL ≈ 600 nm, ΦPL ≈ 0.10, and τ = 0.33-0.61 µs) and no toxicity (except for one nucleoside) to human HeLa cervical epithelioid and Ishikawa endometrial adenocarcinoma cancer cells in vitro. Furthermore, the compounds' ability to inhibit the growth of Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacterial strains was moderate and only observed at a high concentration of 100 µM. Confocal microscopy imaging revealed that the "dirhenium carbonyl" dinucleosides and nucleosides localized mainly in the membranous structures of HeLa cells and uniformly inside S. aureus and E. coli bacterial cells. An interesting finding was that some of the tested compounds were also found in the nuclei of HeLa cells.

Solvent effects on the photooxidation of indolepyrazines.

Photodestruction of 2-(pyrazin-2'-yl)-1H-indole and 2,5-di(1H-indol-2'-yl)pyrazine involves singlet oxygen generation and its rapid insertion into the indole ring with the formation of benzoxazinone derivatives: 2-(pyrazin-2-yl)-4H-3,1-benzoxazin-4-one and 2-[5-(1H-indol-2-yl)pyrazin-2-yl]-4H-3,1-benzoxazin-4-one. The quantum yield of this reaction strongly depends on the environment. It is definitely smaller in protic methanol than in aprotic acetonitrile or n-hexane. The observed effect of photostabilization is explained by formation of hydrogen bonded complexes between the chromophore and alcohol, which results in lower triplet formation efficiency and, in consequence, decrease of singlet oxygen formation quantum yield.

Isotope effects observed in diluted D2O/H2O mixtures identify HOD-induced low-density structures in D2O but not H2O.

Normal and heavy water are solvents most commonly used to study the isotope effect. The isotope effect of a solvent significantly influences the behavior of a single molecule in a solution, especially when there are interactions between the solvent and the solute. The influence of the isotope effect becomes more significant in D2O/H2O since the hydrogen bond in H2O is slightly weaker than its counterpart (deuterium bond) in D2O. Herein, we characterize the isotope effect in a mixture of normal and heavy water on the solvation of a HOD molecule. We show that the HOD molecule affects the proximal solvent molecules, and these disturbances are much more significant in heavy water than in normal water. Moreover, in D2O, we observe the formation of low-density structures indicative of an ordering of the solvent around the HOD molecule. The qualitative differences between HOD interaction with D2O and H2O were consistently confirmed with Raman spectroscopy and NMR diffusometry.

Influence of local microenvironment on the double hydrogen transfer in porphycene.

We performed time-resolved transient absorption and fluorescence anisotropy measurements in order to study tautomerization of porphycene in rigid polymer matrices at cryogenic temperatures. Studies were carried out in poly(methyl methacrylate) (PMMA), poly(vinyl butyral) (PVB), and poly(vinyl alcohol) (PVA). The results prove that in all studied media hydrogen tunnelling plays a significant role in the double hydrogen transfer which becomes very sensitive to properties of the environment below approx. 150 K. We also demonstrate that there exist two populations of porphycene molecules in rigid media: "hydrogen-transferring" molecules, in which tautomerization occurs on time scales below 1 ns and "frozen" molecules in which double hydrogen transfer is too slow to be monitored with nanosecond techniques. The number of "frozen" molecules increases when the sample is cooled. We explain this effect by interactions of guest molecules with a rigid host matrix which disturbs symmetry of porphycene and hinders tunnelling. Temperature dependence of the number of hydrogen-transferring molecules suggests that the factor which restores the symmetry of the double-minimum potential well in porphycene are intermolecular vibrations localized in separated regions of the amorphous polymer.

Photoeradication of bacteria with porphycenes: Substituent effects on the efficiency.

Considering the world-wide problem of growing antibiotic resistance of bacteria, photodynamic inactivation (PDI) has a potential to become the treatment approach against some infectious diseases. In our study, four differently substituted porphycenes were compared in terms of their bactericidal activity against E. faecalis. All tested compounds had a similar photophysical characteristics, i.e., there were no significant differences in the location of absorption bands or molar absorption coefficients. Also, singlet oxygen generation quantum yields were very similar. Surprisingly, differently substituted porphycenes caused very diverse PDI effects. Special attention was drawn to the tert-butyl moieties. Our studies demonstrated that the presence of these substituents lowers the bactericidal potential significantly and can completely block the activity when more than one moiety is introduced to the molecule. The porphycenes lacking tert-butyl groups exhibited much higher PDI potential and we assign this effect to different interactions of the differently substituted porphycenes with the bacterial cells. Most likely, the presence of tert-butyls impairs cell penetration by the photosensitizer. These results remind that the favorable photophysical characteristics do not ensure that the compound considered as a potential PDI agent can reach the microbial cells.

Towards More Photostable, Brighter, and Less Phototoxic Chromophores: Synthesis and Properties of Porphyrins Functionalized with Cyclooctatetraene.

Free base and zinc porphyrins functionalized with cyclooctatetraene (COT), a molecule known as a good triplet-state quencher, have been obtained and characterized in detail by structural, spectral, and photophysical techniques. Substitution with COT leads to a dramatic decrease of the intrinsic lifetime of the porphyrin triplet. As a result, photostability in oxygen-free solution increases by two to three orders of magnitude. In non-degassed solutions, improvement of photostability is about tenfold for zinc porphyrins, but the free bases become less photostable. Similar quantum yields of photodegradation in free base and zinc porphyrins containing the COT moiety indicate a common mechanism of photochemical decomposition. The new porphyrins are expected to be much less phototoxic, since the quantum yield of singlet oxygen formation strongly decreases because of the shorter triplet lifetime. The reduction of triplet lifetime should also enhance the brightness and reduce blinking in porphyrin chromophores emitting in single-molecule regime, since the duration of dark OFF states will be shorter.