Interaction of metal and oxide surfaces with thin films of polar phthalocyanines

In the first part of this thesis, interface properties of polar phthalocyanines (Pc’s): chloroaluminum(III) phthalocyanine (AlClPc) and fluoroaluminum(III) phthalocyanine (AlFPc) are investigated in form of thin films deposited on two types of silver surfaces: a single crystal and a foil. The samples were analyzed with X-ray and ultraviolet photoemission spectroscopy (XPS and UPS). A strong interaction between the organic material and silver surface has been found, which is independent of silver substrate type used. The molecules undergo a loss of their central atom ligand, with the molecule ring staying intact. After de-attachment, the central atom ligand forms a bond with silver surface leading to the formation of Ag-Cl and Ag-F bonds on the surface of silver. What is more, roughness of the substrate surface influences the interface properties. An additional intensity is formed close to the Fermi edge for monolayer thick films. It is present only on substrates with high roughness and is an indication of gap states formation. In the second part of thesis, interface properties of chloroaluminum(III) phthalocyanine (AlClPc) at the interface to two rutile titanium dioxide single crystal surfaces: (001) and (100) surface, have been studied with XPS and UPS. Additionally, the substrates were characterized with low energy electron diffraction (LEED) to provide information on surface structure and reconstruction. A strong interaction has been found between nitrogen atoms of phthalocyanine ring and titanium dioxide surface. The interaction is stronger on the (001) surface than the (100) surface due to their different surface structure, leading to the lower reactivity of the latter one. The reactivity can be varied with number of defects in the crystal structure. The interaction was found to depend on the amount of defects present. As a consequence, using oxygen during preparation steps decreases the amount of defects and allows to quench the interaction. Furthermore, investigation of film growth on TiO2 substrates was performed using mainly microscopy methods: atomic force microscopy and scanning electron microscopy (AFM, SEM). Decrease of substrate signal intensity observed in XPS provided complementary information on film growth. It has been found that the surface type has a strong influence on the AlClPc growth mode since the organic films have a layer-island growth on the (001) surface and possible island-only growth on the (100) surface. Introduction of defects influences the film morphology since the islands are more dense and smaller in size on oxygen treated (“defect-free”) surface, while the island distribution on a reduced (defect-rich) (100) surface is scarce, and the islands are bigger in size. Based on the results of experiments presented in this thesis, it was found that the interaction of phthalocyanines can be controlled with the substrate surface type: although charge transfer from the molecule to the substrate is observed on both surfaces, the interaction with silver influences the phthalocyanine center, while interaction with titanium dioxide influences the phthalocyanine ring. Additionally, the reactivity of phthalocyanine molecules towards the titanium dioxide single crystals is dependent on the amount of defects present, thus can be controlled through adjustment of sample preparation conditions. The type and preparation of TiO2 surface has influence on film growth mode as well

Anti-atherosclerotic properties of fruiting bodies and mycelium from in vitro cultures of selected edible mushrooms

Agaricus bisporus, Boletus edulis, Cantharellus cibarius, Imleria badia, Lactarius deliciosus, Lentinula edodes oraz Pleurotus ostreatus są jednymi z najbardziej popularnych jadalnych grzybów w Polsce. Grzyby jadalne odgrywają w organizmie człowieka rolę przeciwutleniającą, przeciwnowotworową, przeciwdrobnoustrojową, przeciwzapalną oraz są użyteczne w zapobieganiu chorobom, takim jak nadciśnienie, hipercholesterolemia czy miażdżyca.W części teoretycznej pracy opisano właściwości lecznicze badanych gatunków grzybów jadalnych oraz lowastatyny, która była oznaczana w tych gatunkach. W części doświadczalnej opisano proces hodowli kultur in vitro, wytrawianie materiału w sztucznych sokach trawiennych, ekstrakcję pod wpływem ultradźwięków oraz proces oznaczania lowastatyny. Stwierdzono, że lowastatyna jest obecna w każdym z badanych gatunków. W największych ilościach oznaczono ją w owocnikach gatunku C. cibarius (67,89 mg/100 g s.m.), a w najmniejszych w owocnikach L. edodes (0,95 mg/100 g s.m.). Zawartość lowastatyny w ekstraktach z soków trawiennych badanych gatunków grzybów oznaczono na stosunkowo niskim poziomie. Największą zawartość po inkubacji w sztucznym soku żołądkowym wykryto w L. deliciosus (0,3 mg/100 g s.m.), a po inkubacji w soku jelitowym w L. edodes in vitro (0,51 mg/100 g s.m.).Oznaczenie lowastatyny w sokach trawiennych po ekstrakcji owocników grzybów jadalnych zostało wykonane po raz pierwszy. Przeprowadzone doświadczenie wykazało niską dostępność lowastatyny po ich spożyciu. W związku z tym, aby uzyskać działanie przeciwmiażdżycowe grzybów, należy stosować wyciągi alkoholowe.Agaricus bisporus, Boletus edulis, Cantharellus cibarius, Imleria badia, Lactarius deliciosus, Lentinula edodes and Pleurotus ostreatus are among the most popular edible mushrooms in Poland. Edible mushrooms have antioxidant, antitumour, antimicrobial, anti-inflammatory effects on the human body and they can be useful in the prevention of diseases such as hypertention, hypercholesterolemia or atherosclerosis.The theoretical part of the work describes the medicinal properties of the studied species of edible mushrooms and lovastatin, which was identified in these species. The experimental part describes the process of cultivation in vitro culture, incubation the material in artificial digestive juices, extraction using the ultrasounds and the process of determination of lovastatin. It was found that lovastatin was released from all species studied. The largest amounts was determined in the fruiting bodies of C. cibarius (67,89 mg/100 g d.m.) and the smallest in the fruiting bodies of L. edodes (0,95 mg/100 g d.m.). The content of lovastatin in extracts from digestive juices of examined species was determined at a relatively low level. The highest content after incubation in artificial gastric juice was detected in L. deliciosus (0,3 mg/100 g d.m.) and after incubation in intestinal juice in L. edodes in vitro (0,51 mg/100 g d.m.).Determination of lovastatin in digestive juices after extraction of fruiting bodies of edible mushrooms was performed for the first time. This experiment proved low availabilyty of lovastatin after comsumption. Therefore, in order to achieve the antiatherosclerotic effect of mushrooms, alcoholic extracts should be used

FePc and FePcF16 on Rutile TiO2(110) and (100): Influence of the Substrate Preparation on the Interaction Strength

Interface properties of iron phthalocyanine (FePc) and perfluorinated iron phthalocyanine (FePcF16) on rutile TiO2(100) and TiO2(110) surfaces were studied using X-ray photoemission spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and low-energy electron diffraction (LEED). It is demonstrated that the interaction strength at the interfaces is considerably affected by the detailed preparation procedure. Weak interactions were observed for all studied interfaces between FePc or FePcF16 and rutile, as long as the substrate was exposed to oxygen during the annealing steps of the preparation procedure. The absence of oxygen in the last annealing step only had almost no influence on interface properties. In contrast, repeated substrate cleaning cycles performed in the absence of oxygen resulted in a more reactive, defect-rich substrate surface. On such reactive surfaces, stronger interactions were observed, including the cleavage of some C–F bonds of FePcF16