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Excitation wavelength-dependent Raman spectra of single-layer graphene-phtalocyanine hybrid systems
Uhlířová, Tereza ; Vlčková, Blanka (advisor) ; Němec, Ivan (referee)
A systematic chemical and spectroscopic approach to evaluation of the effect of single-layer graphene (SLG) on Raman spectra of free-base phthalocyanine (H2Pc) in glass/SLG/H2Pc hybrid systems has been developed. By a combi- nation of electronic absorption spectra, Raman spectra at five excitation wave- lengths (532, 633, 647, 785 and 830 nm) and excitation profiles of H2Pc Raman spectral bands, the constitution of the three prepared hybrid sysems has been es- tablished in the following manner: Hybrid system I comprises probably a bilayer of H2Pc molecules, system VI approximately a monolayer of H2Pc, and system X a slightly reorganized monolayer of H2Pc molecules. Micro-Raman spectral map- ping of all three hybrid systems yielded H2Pc spectral bands (together with the SLG spectral bands) at all five excitation wavelengths. By contrast, for all three HOPG/H2Pc reference systems (HOPG = highly oriented pyrolytic graphite), prepared by the same procedure as the corresponding samples, H2Pc signal was detected only at 633 and 647 nm excitations. A selective increase of normalized Raman intensities of H2Pc spectral bands for the glass/SLG/H2Pc monolayer hybrid systems at 830 nm was revealed on the basis of a mutual comparison of Raman excitation profiles of all three samples of glass/SLG/H2Pc hybrid systems....
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Time-resolved potentiometry on liquid-liquid interface
Mansfeldová, Věra
MSc. Věra Mansfeldová Dissertation thesis: Time-resolved potentiometry on liquid-liquid interface Abstract The aim of this work is to explore the method of temporal resolution in potentiometry as a new prospective electrochemical analytical technique. In connection with interface of two immiscible electrolyte solutions (ITIES) it may find utilization in analytical chemistry. This technique up to my knowledge has not been published yet. Potential response of analyte on liquid/liquid interface includes both distribution processes, their temporal resolution and redox processes, which specificity can modified by changing the composition of individual phases. Unlike "classic" potentiometric techniques, limited just to potential determination, this method, which I have given the working name "time resolved potentiometry at liquid-liquid interface" utilizes time development of potential response, which was found to be an analyte-specific function. The time resolved potentiometry presented in this work includes time course of potential response to analytical parameters specific for particular analyte. It brings series of data characterizing the analyte in given environment in a similar manner as spectra and may allow creating analyte-specific data package - fingerprint. Combination with ITIES allows, unlike...
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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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STM study of adsorption and mobility of phtalocyanine molecules on passivated silicon surfaces at lower temperatures
Szabo, Michal ; Ošťádal, Ivan (advisor) ; Matvija, Peter (referee)
The thesis deals with an experiment for studying adsorption of phthalocyanin molecules on silicon surface passivated by a tin reconstruction. The main technique used for imaging surface is scanning tunneling microscopy (STM). The work contains a brief introduction to the studied problem. It deals with the STM method and STM construction. The used ultra-vacuum experimental system is characterized together with particular steps at sample preparation for STM measurements. During the sample preparation all necessary operations were tested on the newly modified system and calibration measurements of sample annealing and tin deposition were performed. A structure of the prepared surface Si(111) 7×7 was investigated by STM and conditions for the preparation in the new system were specified. STM images were used for an evaluation of results at optimizing preparation of the passivated surface. Obtained results are important for further experiments in frame of a research focused on growing molecular structures on silicon surfaces.
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Modification of silicon surfaces for selective adsorption
Doležal, Jiří ; Ošťádal, Ivan (advisor) ; Matvija, Peter (referee)
This thesis is focused on adsorption of phthalocyanines on tin and indium passivated silicon Si(111) surfaces with the √3 × √3 reconstruction at room temperature. Scanning tunneling microscopy was used for obtaining atomically resolved surface images. Molecules on these surfaces predominantly adsorb on Si-substitutional defects. Local density of states (LDOS) of strongly adsorbed molecules was obtained by scanning tunneling spectroscopy. The origin of fuzzy imaging of molecules sitting on Si-substitutional double defects was probed. Voltage dependence of mean lifetime of two observed states, between which the "fuzzy" molecule is switching, was measured by analysis of tunneling current fluctuations. We discussed the influence of external parameters on the switching between the two states. We attribute the fuzzy behaviour of the molecule and resulting tunneling current fluctuations to the motion of the molecule in a double-well potential and propose two most likely kinds of the motion which most closely agree with the obtained data.
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Design and characterization of advanced polymer-coated upconversion nanoparticles
Kostiv, Uliana ; Horák, Daniel (advisor) ; Kaman, Ondřej (referee) ; Brožek, Jiří (referee)
Lanthanide-based upconversion nanoparticles are able to absorb low-energy near-infrared (NIR) photons and emit visible or ultraviolet light. This unique optical property enables luminescent detection without autofluorescence from biological samples that is crucial for bioimaging and diagnostics. Moreover, NIR irradiation allows to deliver light deep into the tissue, which can be used for drug or gene delivery and NIR-induced photodynamic therapy (PDT) of tumors. Despite huge effort during the last 10 years devoted to the upconversion nanoparticle synthesis and their surface engineering, preparation of the particles suitable for biomedical applications still remains a big challenge. The current work is focused on synthesis of the upconversion nanoparticles with controllable morphology, size, distribution, crystallinity, and high upconversion efficiency, as well as on desirable surface modification by biocompatible inorganic or organic polymers. Neat and functionalized homogeneous silica shell was introduced on the NaYF4:Yb3+ /Er3+ and NaGdF4:Yb3+ /Er3+ nanoparticles to enhance their biocompatibility and colloidal stability in water. To render the nanoparticles with targeting moieties, their surface was decorated with cell-adhesive RGD or cell-penetrating TAT peptides. The RGD- and TAT- conjugated...
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Excitation wavelength-dependent Raman spectra of single-layer graphene-phtalocyanine hybrid systems
Uhlířová, Tereza ; Vlčková, Blanka (advisor) ; Němec, Ivan (referee)
A systematic chemical and spectroscopic approach to evaluation of the effect of single-layer graphene (SLG) on Raman spectra of free-base phthalocyanine (H2Pc) in glass/SLG/H2Pc hybrid systems has been developed. By a combi- nation of electronic absorption spectra, Raman spectra at five excitation wave- lengths (532, 633, 647, 785 and 830 nm) and excitation profiles of H2Pc Raman spectral bands, the constitution of the three prepared hybrid sysems has been es- tablished in the following manner: Hybrid system I comprises probably a bilayer of H2Pc molecules, system VI approximately a monolayer of H2Pc, and system X a slightly reorganized monolayer of H2Pc molecules. Micro-Raman spectral map- ping of all three hybrid systems yielded H2Pc spectral bands (together with the SLG spectral bands) at all five excitation wavelengths. By contrast, for all three HOPG/H2Pc reference systems (HOPG = highly oriented pyrolytic graphite), prepared by the same procedure as the corresponding samples, H2Pc signal was detected only at 633 and 647 nm excitations. A selective increase of normalized Raman intensities of H2Pc spectral bands for the glass/SLG/H2Pc monolayer hybrid systems at 830 nm was revealed on the basis of a mutual comparison of Raman excitation profiles of all three samples of glass/SLG/H2Pc hybrid systems....
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Time-resolved potentiometry on liquid-liquid interface
Mansfeldová, Věra ; Nesměrák, Karel (advisor) ; Opekar, František (referee) ; Gál, Miroslav (referee)
Věra Mansfeldová: Time-resolved potentiometry on liquid-liquid interface (Dissertation thesis) Abstract The aim of this work is to explore the method of temporal resolution in potentiometry as a new prospective electrochemical analytical technique. In connection with interface of two immiscible electrolyte solutions (ITIES) it may find utilization in analytical chemistry. This technique up to my knowledge has not been published yet. Potential response of analyte on liquid/liquid interface includes both distribution processes, their temporal resolution and redox processes, which specificity can modified by changing the composition of individual phases. Unlike "classic" potentiometric techniques, limited just to potential determination, this method, which I have given the working name "time resolved potentiometry at liquid-liquid interface" utilizes time development of potential response, which was found to be an analyte-specific function. The time resolved potentiometry presented in this work includes time course of potential response to analytical parameters specific for particular analyte. It brings series of data characterizing the analyte in given environment in a similar manner as spectra and may allow creating analyte-specific data package - fingerprint. Combination with ITIES allows, unlike...
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Preparation and photophysical evaluation of tetra-3,4-pyridoporphyrazines suitable for the photodynamic therapy
Čermák, Pavel ; Nováková, Veronika (advisor) ; Roh, Jaroslav (referee)
Charles University in Prague, Faculty of Pharmacy in Hradec Králové Department: Department of Biophysics and Physical Chemistry Candidate: Pavel Cermak Supervisor: Assoc. Prof. Veronika Novakova, PhD. Title of Thesis: Preparation and photophysical evaluation of tetra-3,4- pyridoporphyrazines suitable for the photodynamic therapy Tetra-3,4-pyridoporphyrazines (TPyPz) are aza-analogues of phthalocyanines. Their large system of conjugated bonds enables them to absorb light in the red part of the absorption spectrum. Due to their ability to produce singlet oxygen, they can be potentially used as photosensitizers in photodynamic therapy (PDT). Its mechanism is based on co-functioning of three elements - photosensitizer, light and oxygen. Photosensitizer excited by light absorption transfers its energy into tissue oxygen, thus, creating cytotoxic singlet oxygen. This method is beneficial for its high selectivity, low toxicity, minimal invasion and fast effect. The aim of this work was to synthetize and study water-soluble TPyPz suitable for PDT. Water solubility was achieved by quarternized amines, forming of salts or using suitable delivery systems (hydrophilic emulsion). Hydrophilicity was also increased by introduction of hydrophilic non-charged substituents (OH). At first, appropriate precursors for...
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Synthesis and photophysical study of hydrophilic tetrapyridoporphyrazines bearing charged substituents on the periphery
Demuth, Jiří ; Nováková, Veronika (advisor) ; Vávrová, Kateřina (referee)
Charles University in Prague, Faculty of Pharmacy in Hradec Králové Department Department of Biophysics and Physical Chemistry Candidate Jiří Demuth Supervisor Assoc. Prof. Veronika Nováková, PhD. Title of Thesis Synthesis and photophysical study of hydrophilic tetrapyridoporphyrazines bearing charged substituents on the periphery Phthalocyanines are planar organic molecules, which have a metal cation coordinated in their centre. This work deals with their aza-analogues - tetra-3,4-pyridoporphyrazines (TPyPz). TPyPz can absorb light in red part spectrum and then produce singlet oxygen. Due to this ability, they may be used in photodynamic therapy (PDT) of cancer. PDT's mechanism is based on three components: photosensitizer, light and singlet oxygen. Photosensitizer transfers energy of absorbed light to oxygen making, thus, cytotoxic singlet oxygen. The goal of this thesis was to synthesize water soluble TPyPzs absorbing in red part of absorption spectrum. TPyPzs bearing different charged substituents will be compared within the series. The synthesis consisted of preparation of 2-chloro-5,6-dimethylpyridine-3,4-dicarbonitrile (1), which was the starting precursor for other reactions. Nucleophilic substitution of 1 was used for the introducing of various hydrophilic substituents. Prepared precursors...
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