G-quadruplexes (G4 s), as non-canonical DNA structures, attract a great deal of research interest in the molecular biology as well as in the material science fields. The use of small molecules as ligands for G-quadruplexes has emerged as a tool to regulate gene expression and telomeres maintenance. Meso-tetrakis-(N-methyl-4-pyridyl) porphyrin (TMPyP4) was shown as one of the first ligands for G-quadruplexes and it is still widely used. We report an investigation comprising molecular docking and dynamics, synthesis and multiple spectroscopic and spectrometric determinations on simple cationic porphyrins and their interaction with different DNA sequences. This study enabled the synthesis of tetracationic porphyrin derivatives that exhibited binding and stabilizing capacity against G-quadruplex structures; the detailed characterization has shown that the presence of amide groups at the periphery improves selectivity for parallel G4 s binding over other structures. Taking into account the ease of synthesis, 5,10,15,20-tetrakis-(1-acetamido-4-pyridyl) porphyrin bromide could be considered a better alternative to TMPyP4 in studies involving G4 binding.

• Klíčová slova
• DNA, G-quadruplexes, Molecular dynamics, Molecular recognition, NMR,
• MeSH
• cirkulární dichroismus MeSH
• DNA * chemie   MeSH
• G-kvadruplexy * MeSH
• ligandy MeSH
• porfyriny * chemie   MeSH
• simulace molekulární dynamiky MeSH
• simulace molekulového dockingu * MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• DNA * MeSH
• ligandy MeSH
• porfyriny * MeSH
• tetra(4-N-methylpyridyl)porphine MeSH Prohlížeč

New functionalities were added to biocompatible polycaprolactone nanofiber materials through the co-encapsulation of chlorin e6 trimethyl ester (Ce6) photogenerating singlet oxygen and absorbing light both in the blue and red regions, and using 4-(N-(aminopropyl)-3-(trifluoromethyl)-4-nitrobenzenamine)-7-nitrobenzofurazan, NO-photodonor (NOP), absorbing light in the blue region of visible light. Time-resolved and steady-state luminescence, as well as absorption spectroscopy, were used to monitor both photoactive compounds. The nanofiber material exhibited photogeneration of antibacterial species, specifically nitric oxide and singlet oxygen, upon visible light excitation. This process resulted in the efficient photodynamic inactivation of E. coli not only close to nanofiber material surfaces due to short-lived singlet oxygen, but even at longer distances due to diffusion of longer-lived nitric oxide. Interestingly, nitric oxide was also formed by processes involving photosensitization of Ce6 during irradiation by red light. This is promising for numerous applications, especially in the biomedical field, where strictly local photogeneration of NO and its therapeutic benefits can be applied using excitation in the "human body phototherapeutic window" (600-850 nm). Generally, due to the high permeability of red light, the photogeneration of NO can be achieved in any aqueous environment where direct excitation of NOP to its absorbance in the blue region is limited.

• Klíčová slova
• Antibacterial properties, Nanofibers, Nitric oxide, Polycaprolactone, Red light, Singlet oxygen,
• MeSH
• antibakteriální látky * chemie   farmakologie   MeSH
• chlorofylidy MeSH
• Escherichia coli * účinky léků   účinky záření   MeSH
• fotosenzibilizující látky chemie   farmakologie   MeSH
• nanovlákna * chemie   MeSH
• oxid dusnatý * chemie   metabolismus   MeSH
• polyestery chemie   MeSH
• porfyriny * chemie   farmakologie   MeSH
• singletový kyslík * chemie   metabolismus   MeSH
• světlo * MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• antibakteriální látky * MeSH
• chlorofylidy MeSH
• fotosenzibilizující látky MeSH
• oxid dusnatý * MeSH
• phytochlorin MeSH Prohlížeč
• polycaprolactone MeSH Prohlížeč
• polyestery MeSH
• porfyriny * MeSH
• singletový kyslík * MeSH

Anionic cyclopentadienyl (Cp) and its pentamethyl-substituted derivative (Cp*) serve as crucial ligands for creating stable π-coordinated materials, including catalysts. From a structural perspective, the π-extended analog of Cp, known as an N-fused porphyrin (NFP), is recognized as an intriguing 18π aromatic chromophore, offering near-infrared (NIR) optical properties that can be fine-tuned through metal complexation. When coordinated with rhodium at the central NFP core, it forms a sandwich binuclear rhodium(III) complex along with terminal and bridging chloride ligands, denoted as Rh-1, and its bromo derivative, Rh-1-Br. In contrast to the bis-NFP complex of iron(II) reported previously by our team, both Rh-1 and Rh-1-Br complexes exhibit strong NIR optical properties and narrow HOMO-LUMO energy gaps, attributed to minimal orbital interactions between the two co-facial NFP ligands. Leveraging these NIR absorption properties, we assessed the photothermal conversion properties of Rh-1 and ligand 1, revealing high conversion efficiency. This suggests their potential application as photothermal agents for use in photothermal therapy.

• Klíčová slova
• N-fused porphyrin, NIR absorption, Photothermal conversion, Rhodium, Sandwich metal complex,
• MeSH
• chloridy MeSH
• katalýza MeSH
• ligandy MeSH
• porfyriny * chemie   MeSH
• rhodium * chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• chloridy MeSH
• ligandy MeSH
• porfyriny * MeSH
• rhodium * MeSH

The strong antifungal effect of sulfonated polystyrene nanoparticles (NPs) with an encapsulated tetraphenylporphyrin (TPP) photosensitizer is reported here. TPP is activated by visible light, resulting in the generation of singlet oxygen. Its antifungal action is potentiated in the presence of potassium iodide, yielding I2/I3⁻, another antifungal species. The NPs exhibit no dark toxicity, but a broad spectrum of antifungal photodynamic effects. The efficiency of this rapid killing (on the order of minutes) depends on the concentration of TPP NPs, potassium iodide, yeast species and temperature. A strong antifungal activity of TPP NPs is demonstrated on eleven pathogenic and opportunistic pathogenic yeast species (six Candida species and other yeast species, including melanized Hortaea werneckii). The composition and architecture of yeast cell envelope structures clearly influence the efficacy of photodynamic therapy. Candida krusei is the most sensitive to photodynamic therapy. Despite expectations, melanin does not provide Hortaea cells with marked resistance compared to white yeast species. The kinetics of the interaction of NPs with yeast cells is also described. This study may inspire and promote the fabrication of a new type of antiseptic for various skin injuries in clinical medicine.

• Klíčová slova
• Candida, Nanoparticles, Photodynamic therapy, Porphyrin, Singlet oxygen, Yeast,
• MeSH
• antifungální látky farmakologie   terapeutické užití   MeSH
• fotochemoterapie * MeSH
• fotosenzibilizující látky farmakologie   chemie   terapeutické užití   MeSH
• jodid draselný chemie   farmakologie   MeSH
• nanočástice * chemie   MeSH
• porfyriny * farmakologie   chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• antifungální látky MeSH
• fotosenzibilizující látky MeSH
• jodid draselný MeSH
• porfyriny * MeSH

The synthesis of two-dimensionally extended polycyclic heteroatomic molecules keeps attracting considerable attention. In particular, frameworks bearing planar cyclooctatetraenes (COT) moieties can display intriguing properties, including antiaromaticity. Here, we present an on-surface chemistry route to square-type porphyrin tetramers with a central COT ring, coexisting with other oligomers. This approach employing temperature-induced dehydrogenative porphyrin homocoupling in an ultrahigh vacuum environment provides access to surface-supported, unsubstituted porphyrin tetramers that are not easily achievable by conventional synthesis means. Specifically, monomeric free-base (2H-P) and Zn-metalated (Zn-P) porphines (P) were employed to form square-type free-base and Zn-functionalized tetramers on Ag(100). An atomic-level characterization by bond-resolved atomic force microscopy and scanning tunneling microscopy and spectroscopy is provided, identifying the molecular structures. Complemented by density functional theory modeling, the electronic structure is elucidated, indeed revealing antiaromaticity induced by the COT moiety. The present study thus gives access, and insights, to a porphyrin oligomer, representing both a model system for directly fused porphyrins and a potential building block for conjugated, extended two-dimensional porphyrin sheets.

• MeSH
• magnetická rezonanční spektroskopie MeSH
• molekulární struktura MeSH
• porfyriny * chemie   MeSH
• rastrovací tunelová mikroskopie MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• porfyriny * MeSH

Biomimetic chiral optoelectronic materials can be utilized in electronic devices, biosensors and artificial enzymes. Herein, this work reports the chiro-optical properties and architectural arrangement of optoelectronic materials generated from self-assembly of initially nonchiral oligothiophene-porphyrin derivatives and random coil synthetic peptides. The photo-physical- and structural properties of the materials were assessed by absorption-, fluorescence- and circular dichroism spectroscopy, as well as dynamic light scattering, scanning electron microscopy and theoretical calculations. The materials display a three-dimensional ordered helical structure and optical activity that are observed due to an induced chirality of the optoelectronic element upon interaction with the peptide. Both these properties are influenced by the chemical composition of the oligothiophene-porphyrin derivative, as well as the peptide sequence. We foresee that our findings will aid in developing self-assembled optoelectronic materials with dynamic architectonical accuracies, as well as offer the possibility to generate the next generation of materials for a variety of bioelectronic applications.

• Klíčová slova
• circular dichroism, oligothiophene, porphyrin, self-assembly, synthetic peptides,
• MeSH
• biomimetické materiály * MeSH
• mikroskopie elektronová rastrovací MeSH
• peptidy chemie   MeSH
• porfyriny * chemie   MeSH
• sekvence aminokyselin MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• peptidy MeSH
• porfyriny * MeSH

Metal-organic frameworks (MOFs) have been widely used as porous nanomaterials for different applications ranging from industrial to biomedicals. An unpredictable one-pot method is introduced to synthesize NH2-MIL-53 assisted by high-gravity in a greener media for the first time. Then, porphyrins were deployed to adorn the surface of MOF to increase the sensitivity of the prepared nanocomposite to the genetic materials and in-situ cellular protein structures. The hydrogen bond formation between genetic domains and the porphyrin' nitrogen as well as the surface hydroxyl groups is equally probable and could be considered a milestone in chemical physics and physical chemistry for biomedical applications. In this context, the role of incorporating different forms of porphyrins, their relationship with the final surface morphology, and their drug/gene loading efficiency were investigated to provide a predictable pattern in regard to the previous works. The conceptual phenomenon was optimized to increase the interactions between the biomolecules and the substrate by reaching the limit of detection to 10 pM for the Anti-cas9 protein, 20 pM for the single-stranded DNA (ssDNA), below 10 pM for the single guide RNA (sgRNA) and also around 10 nM for recombinant SARS-CoV-2 spike antigen. Also, the MTT assay showed acceptable relative cell viability of more than 85% in most cases, even by increasing the dose of the prepared nanostructures.

• Klíčová slova
• COVID-19, CRISPR, MOF, biomedicine, biosensor, gene delivery,
• MeSH
• buňky Hep G2 MeSH
• buňky PC12 MeSH
• COVID-19 diagnóza   MeSH
• CRISPR-Cas systémy MeSH
• dusík chemie   MeSH
• HEK293 buňky MeSH
• HeLa buňky MeSH
• jednovláknová DNA MeSH
• krysa rodu Rattus MeSH
• lidé MeSH
• limita detekce MeSH
• nanokompozity MeSH
• nanostruktury MeSH
• porézní koordinační polymery chemie   MeSH
• poréznost MeSH
• porfyriny chemie   MeSH
• povrchové vlastnosti MeSH
• RNA virová metabolismus   MeSH
• SARS-CoV-2 MeSH
• senzitivita a specificita MeSH
• testování na COVID-19 MeSH
• vodící RNA, systémy CRISPR-Cas MeSH
• vodíková vazba MeSH
• zvířata MeSH
• Check Tag
• krysa rodu Rattus MeSH
• lidé MeSH
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• dusík MeSH
• jednovláknová DNA MeSH
• porézní koordinační polymery MeSH
• porfyriny MeSH
• RNA virová MeSH
• vodící RNA, systémy CRISPR-Cas MeSH

Photodynamic inactivation (PDI) is a promising approach for the efficient killing of pathogenic microbes. In this study, the photodynamic effect of sulfonated polystyrene nanoparticles with encapsulated hydrophobic 5,10,15,20-tetraphenylporphyrin (TPP-NP) photosensitizers on Gram-positive (including multi-resistant) and Gram-negative bacterial strains was investigated. The cell viability was determined by the colony forming unit method. The results showed no dark cytotoxicity but high phototoxicity within the tested conditions. Gram-positive bacteria were more sensitive to TPP-NPs than Gram-negative bacteria. Atomic force microscopy was used to detect changes in the morphological properties of bacteria before and after the PDI treatment.

• MeSH
• Bacteria účinky léků   účinky záření   MeSH
• fotochemické procesy * MeSH
• fotochemoterapie metody   MeSH
• mikroskopie atomárních sil MeSH
• nanočástice * chemie   MeSH
• polystyreny * chemie   MeSH
• porfyriny aplikace a dávkování   chemie   MeSH
• příprava léků * MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• polystyreny * MeSH
• porfyriny MeSH
• tetraphenylporphyrin MeSH Prohlížeč

A three-step postprocessing functionalization of pristine electrospun polystyrene nanofiber membranes was used for the preparation of nanostructured biotinylated materials with an externally bonded porphyrin photosensitizer. Subsequently, the material was able to strongly bind biologically active streptavidin derivatives while keeping its photosensitizing and antibacterial properties due to the generation of singlet oxygen under the exclusive control of visible light. The resulting multifunctional materials functionalized by a streptavidin-horseradish peroxidase conjugate as a model bioactive compound preserved its enzymatic activity even in the presence of a porphyrin photosensitizer with some quenching effect on the activity of the photosensitizer. Prolonged kinetics of both singlet oxygen luminescence and singlet oxygen-sensitized delayed fluorescence (SODF) were found after irradiation by visible light. The above results reflected less effective quenching of the porphyrin photosensitizer triplet state by ground state oxygen and indicated hindered oxygen transport (diffusion) due to surface functionalization. We found that SODF could be used as a valuable tool for optimizing photosensitizing efficiency as well as a tool for confirming surface functionalization. Full photosensitizing and enzyme activity could be achieved by a space separation of photosensitizers and enzyme/biomolecules in the nanofiber composites consisting of two layers. The upper layer contained a photosensitizer that generated antibacterial singlet oxygen upon irradiation by light, and the bottom layer retained enzymatic activity for biochemical reactions.

• Klíčová slova
• biotin, delayed fluorescence, nanofibers, singlet oxygen, streptavidin,
• MeSH
• antibakteriální látky chemie   farmakologie   MeSH
• biotin chemie   MeSH
• Escherichia coli účinky léků   MeSH
• fluorescenční barviva chemie   MeSH
• fluorescenční spektrometrie MeSH
• fotosenzibilizující látky MeSH
• membrány umělé MeSH
• nanokompozity chemie   MeSH
• nanovlákna chemie   MeSH
• polystyreny chemie   MeSH
• porfyriny chemie   MeSH
• singletový kyslík chemie   MeSH
• streptavidin MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• antibakteriální látky MeSH
• biotin MeSH
• fluorescenční barviva MeSH
• fotosenzibilizující látky MeSH
• membrány umělé MeSH
• polystyreny MeSH
• porfyriny MeSH
• singletový kyslík MeSH
• streptavidin MeSH

Purpurin 18 derivatives with a polyethylene glycol (PEG) linker were synthesized as novel photosensitizers (PSs) with the goal of using them in photodynamic therapy (PDT) for cancer. These compounds, derived from a second-generation PS, exhibit absorption at long wavelengths; considerable singlet oxygen generation and, in contrast to purpurin 18, have higher hydrophilicity due to decreased logP. Together, these properties make them potentially ideal PSs. To verify this, we screened the developed compounds for cell uptake, intracellular localization, antitumor activity and induced cell death type. All of the tested compounds were taken up into cancer cells of various origin and localized in organelles known to be important PDT targets, specifically, mitochondria and the endoplasmic reticulum. The incorporation of a zinc ion and PEGylation significantly enhanced the photosensitizing efficacy, decreasing IC50 (half maximal inhibitory compound concentration) in HeLa cells by up to 170 times compared with the parental purpurin 18. At effective PDT concentrations, the predominant type of induced cell death was apoptosis. Overall, our results show that the PEGylated derivatives presented have significant potential as novel PSs with substantially augmented phototoxicity for application in the PDT of cervical, prostate, pancreatic and breast cancer.

• Klíčová slova
• PEGylated purpurin 18, apoptosis, cancer cells, cytotoxicity, flow cytometry, live-cell fluorescence microscopy, photodynamic therapy, photosensitizer, phototoxicity, singlet oxygen,
• MeSH
• fluorescenční mikroskopie MeSH
• fotochemoterapie metody   MeSH
• lidé MeSH
• nádorové buněčné linie MeSH
• porfyriny chemie   MeSH
• průtoková cytometrie MeSH
• rozpustnost MeSH
• singletový kyslík chemie   MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• porfyriny MeSH
• purpurin 18 MeSH Prohlížeč
• singletový kyslík MeSH