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Photoactive chlorophyll nanoparticles
Ludačka, Pavel ; Mosinger, Jiří (advisor) ; Lang, Kamil (referee)
Photoactive sulfonated and non-sulfonated polystyrene nanoparticles (NPs) with encapsulated THF extract from spinach (Spinacia oleracea) were prepared. The preparation of NPs is based on a simple nanoprecipitation method that uses the same solvent (THF) to dissolve the sulfonated or non-sulfonated polystyrene nanofiber membrane and for the extraction itself. Based on spectral and HPLC analysis, it was found that the THF extract and NPs contain chlorophyll a, chlorophyll b, β-carotene and lutein. Time-resolved spectroscopy shows that the extract is a potent source of singlet oxygen O2(1 g) thank to the photosensitizer chlorophyll. The photogeneration of O2(1 g) is partially suppressed by the carotenoids in the extract, which quench O2(1 g). To reduce the quenching effect of carotenoids, it is possible to use dilute extract or pre-irradiated samples with visible light because of carotenoids rapid breakup. A strong photooxidative and antibacterial effect of NPs prepared from an extract generating O2(1 g) was demonstrated on chemical substrates and Escherichia coli. The photoactivity of NPs is initiated by visible light. Key words Chlorophyll, photosensitizer, nanoparticle, singlet oxygen
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Methods of Study of Photosensitizer-Photophysics with Application on Thiazolyl-porphyrins
Scholz, Marek
Title: Methods of Study of Photosensitizer-photophysics with Application on Thiazolyl-porphyrins Author: Marek Scholz Department: Department of Chemical Physics and Optics Supervisor: RNDr. Roman Dědic, Ph.D. Supervisor's e-mail address: Roman.Dedic@mff.cuni.cz Abstract: Photodynamic therapy for oncologic and various chronic diseases is a rapidly emerging method of treatment. It is based on the production of highly reactive singlet oxygen and free radicals by excitation energy transfer from the molecules of photosensitizers. Photosensitizers are preferentially accumulated in the target tissues and locally illuminated. This way produced reactive species cause apoptosis or necrosis of the cells leading to the desired therapeutic effect. Synthesis and subsequent photophysical characterization of photosensitizing dyes is a fundamental part of the development of photodynamic methods. The main aim of the work is to explain the most widely used methods of photophysical study of photosensitizers and apply them to new synthesized photosensitizers: thiazolyl-porphyrins. Methods of absorption and fluorescence spectroscopy, flash- photolysis, time- and spectral-resolved detection of luminescence, optoacoustic spectroscopy and other spectroscopic methods were used. Thiazolyl-porphyrins proved to be promising new...
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Polystyrene photoactive nanomaterials producing singlet oxygen
Henke, Petr
The increasing number of multidrug-resistant strains of bacteria call for alternatives to antibiotic therapy and, more generally, for the antimicrobial material as a component of prevention. Of particular interest is the photodynamic inactivation of bacteria and other pathogens caused by photogenerated singlet oxygen. This work is focused on the field of photoactive polymer nanofiber membranes and nanoparticles, generating singlet oxygen, suitable for medical applications. We prepared different types of photoactive modified polystyrene nanofiber membranes with encapsulated or externally bound porphyrin photosensitizers. These materials efficiently produce highly reactive and cytotoxic singlet oxygen capable of restricted diffusion into to the external environment. Our results demonstrate the crucial role of wettability for materials of this type with a short diffusion length of generated singlet oxygen, illustrate the effect of temperature and indicate their potential use as multifunctional materials. Due to their antimicrobial properties, these materials are suitable alternative to antibiotics and local antiseptics. With good breathability and short diffusion length of singlet oxygen good results can be expect in in vivo tests. From these nanofiber materials we also prepared photoactive extremely...
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Nanofiber materials simultaneously photogenerating NO and 1O2 species; Reversible NO binding on boron-containing clusters
Dolanský, Jiří
This project is concerned with the preparation of electrospun polystyrene (PS) nanofiber materials with covalently bonded NO-photodonor and electrostatically attached tetracationic porphyrinoid photosensitizers. These photofunctional nanofiber materials exhibit effective simultaneous photogeneration of small antibacterial NO and O2(1 ∆g) species under irradiation with daylight creating an antibacterial surface and near surrounding. NO species can be also generated just by gentle heating. Nanofiber materials were analyzed with SEM, FTIR, emission and UV/vis spectroscopy and time-resolved emission and absorption spetroscopy. The antibacterial effect was tested on Escherichia coli. The dual antibacterial action, in combination with the nanoporous character of the material that detains pathogens like bacteria on its surface, is ideal for any application where a sterile environment is neces- sary. The known bimetallic cluster system [(PMe2Ph)4Pt2B10H10] that possesses the propen- sity to reversibly bind small gaseous molecules (O2, SO2, CO) was synthesized in good yields for NO reversible binding investigation. Seven new monometallic precursors (Pt, Pd and Ni) to new bimetallic species were succesfully synthesized with the aim of future study of NO reversible binding. All new compounds were purified by...
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Study of the photodynamic inactivation of prions by phthalocyanines.
Kostelanská, Marie ; Holada, Karel (advisor) ; Zimčík, Petr (referee) ; Kolářová, Hana (referee)
Transmissive spongiform encephalopathies, also called prion disorders, are fatal neurodegenerative diseases affecting mammals. In patients, the pathological prion protein (PrPTSE ) accumulates in CNS and causes death. Prions possess high binding affinity to surfaces. Moreover, they are highly resistant to conventional sterilization procedures which rise the risk of nosocomial transmission from patients in subclinical stage of prion disease through medical tools. In the thesis, we evaluate the efficiency of photodynamic inactivation (PDI) for prion decontamination. The PDI is induced by photoactivation of phthalocyanine (Pc) derivates AlPcOH(SO3)2, SiPc(OH)2(SO3)1-3 or ZnPc(SO3)1-3. Pc exposed to light generate reactive oxygen species, mainly singlet oxygen (O2(1 ∆g)). Production of O2(1 ∆g) in aqueous solution was confirmed by iodide method, quenching by NaN3 and oxidative degradation of uric acid. The photoactivation of Pc in infectious brain homogenate led to elimination of PrPres signal (= proteinase K-resistant PrPTSE fragment) below the detection limit of western blot by using nanomolar AlPcOH(SO3)2 concentration. The complete elimination of PrPres signal was accompanied with total protein concentration decrease by a maximum of 20% in brain homogenate No signs of protein fragmentation or...
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Nanofiber membranes generating singlet oxygen with magnetic separation
Liška, Vojtěch ; Mosinger, Jiří (advisor) ; Kubíček, Vojtěch (referee)
This thesis focuses on the preparation and study of a new type of photoactive polyurethane nanofiber membrane with encapsulated 5,10,15,20-meso-tetraphenylporphyrin (TPP) photosensitizer and maghemite nanoparticles. The membrane was prepared by electrospinning and shows effective photogeneration of O2 (1 Δg) and photoantibacterial effect on the surface. The membrane can be easily separated by a magnetic field. The magnetic behaviour of the maghemite nanoparticles was studied using Mössbauer spectroscopy. Their size was estimated by DLS. The final nanofiber membrane was characterized by UV-VIS, emission spectroscopy, and by electronic microscopy (SEM). The kinetics of O2 (1 Δg) generation was studied by time-resolved spectroscopy and the relative efficiency of photooxidation was studied using external acceptor of O2 (1 Δg). Significant photoantibacterial properties against bacteria strain Escherichia coli were detected on the surface of the membrane functionalized with TPP photosensitizer.
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Polymer nanoparticles generating singlet oxygen
Berzédiová, Veronika ; Mosinger, Jiří (advisor) ; Tyrpekl, Václav (referee)
This theses focuses on preparation and characterisation and comparison of two types of polymer nanoparticles using photophysical methods. The first type was polystyrene nanoparticles prepared by modified nanoprecipitation method from polymeric sulfonated nanofiber membranes with diffrent content of sulfonated groups. The second type was polymer nanoparticles with diferent lenght of hydrophobic polycaprolactone (PCL) and hydrophilic poly(ethyleneglycol) (PEG) blocks. Both types of nanoparticles conteined encapsulated photosensitizer 5,10,15,20-meso-tetraphenylporphyrin with a high quantum singlet oxygen yield. In the prepared nanoparticles with a photosensitizer, the kinetics of singlet oxygen generation was studied using time resolved spectroscopy. The relative efficiency of photooxidation was studied using external akceptor of singlet oxygen. The effect of temperature, size and matrix (type of polymer) of nanoparticles on photooxidation efficiency was also studied. In the next part of this these was studied the influence of time on the size and stability of nanoparticles and also the effect of solution pH and ionic strength on prepared nanoparticles.
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Přítomnost singletového kyslíku v povrchových vodách
KOVAŘÍKOVÁ, Michaela
This master thesis deals with the methods of measurement of singlet oxygen steady state concentrations in surface water and the factors affecting this concentration. The first part of this work shows theoretical background and an introduction to photochemistry of surface water with respect to the reactive oxygen species. The second part describes the methodology of conducted experiments and discuss its results with respect to current literature.
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Functionalized Polystyrene Nanomaterials for Biomedicinal Applications
Dolanský, Jiří ; Mosinger, Jiří (advisor) ; Dědic, Roman (referee) ; Zimčík, Petr (referee)
Nowadays, there is an increasing risk of bacterial infections from bacteria strains resistant towards antibiotics. Thus, it is of utmost importance to research novel therapies which can overcome this difficulty. The presented thesis focuses on the preparation, characterization and antibacterial evaluation of polystyrene polymer nanomaterials (nanofiber membranes and nanoparticles) modified with compounds that can efficiently inhibit bacterial growth either by their nature (polyethyleneimine) or by photoactivation upon visible light excitation (NO- photodonors, photosensitizers) and consequent production of highly reactive inorganic bactericidal species, nitric oxide (NO) and singlet oxygen (O2(1 g)). All materials were fully characterized by several independent methods. The concentrations of NO and O2(1 g) were measured by amperometric and time-resolved spectroscopic techniques and by variety of chemical analytic procedures. Due to the presence of bactericidal species and the efficient photogeneration of NO and O2(1 g) at physiological conditions, all materials exhibit strong antibacterial action tested on a Gram-negative bacterial strain Escherichia coli. Hence, these functionalized polymer nanomaterials may be intriguing systems for medical-, biological-, or environmental- application where a...
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