Ágnes Szegedi

Carboxylic modified spherical mesoporous silicas аs drug delivery carriers.

The present study deals with the development and functionalization of mesoporous silica nanoparticles as drug delivery platforms. Spherical MCM-41 and SBA-15 silicas with different pore sizes (2.7 nm and 5.5 nm, respectively) were post-synthesis modified applying a new, two step process. The initial step was the modification with 3-amino-propyltriethoxysilane, and the next was the reaction with succinic anhydride in toluene in order to obtain carboxylic modified mesoporous carriers. The carboxylic-functionalized mesoporous materials were characterized by XRD, nitrogen physisorption, TEM, ATR FT-IR spectroscopy. The successful carboxylic functionalization was proved by the changes of the zeta potential of the mesoporous materials before and after modification. The parent and the carboxylic-modified MCM-41 and SBA-15 materials showed high adsorption capacity (approximately 50 wt.%, except for non-functionalized MCM-41) for sulfadiazine that possesses amino functional groups. Mesoporous structure peculiarities lead to different adsorption capacities on the carriers. In vitro release studies showed slower release rate of sulfadiazine from carboxylic modified MCM-41 and SBA-15 mesoporous particles compared to the non modified ones. Both non loaded and drug-loaded silica materials demonstrated no cytotoxicity on Caco-2 cell line. The functionalized mesoporous systems are appropriate drug delivery platforms due to their biocompatibility and the possibility to modify drug release.

Toluene oxidation on titanium- and iron-modified MCM-41 materials

Iron- and titanium-modified MCM-41 materials, prepared by direct synthesis at ambient temperature or wet impregnation technique, were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), UV-vis diffuse reflectance, Mössbauer and FT-IR spectroscopies. Their catalytic behavior was studied in total oxidation of toluene. Materials with high surface area and well-ordered pore structure were obtained. The increase of the titanium content (up to 50%) in the bisubstituted, iron and titanium containing materials leads to partial structure collapse of the silica matrix. Finely dispersed anatase particles were also formed during the impregnation procedure. The catalytic activity of the bisubstituted materials was influenced by the method of their preparation, but higher catalytic stability could be achieved, compared to iron monosubstituted one. The nature of the catalytic active sites is discussed.

Low temperature oxidation of CO over tin-modified Pt/SiO2 catalysts

Abstract Low temperature oxidation of CO over alloy type Sn–Pt/SiO 2 catalysts with different Sn/Pt ratios has been investigated at different CO partial pressure using thermal programmed oxidation (TPO) technique and time on stream (TOS) experiments. The introduction of tin into platinum strongly increased the activity of the catalyst. The activity had a maximum, which depended on both the Sn/Pt (at./at.) ratio and the CO partial pressure. TOS experiments revealed the aging of the Sn–Pt/SiO 2 catalysts. FTIR and Mossbauer spectroscopy has been used to follow compositional and structural changes of Sn–Pt/SiO 2 catalysts during the catalytic run. The results show that the in situ formed, highly mobile “Sn n + –Pt” ensemble sites are responsible for high activity, while formation of relatively stable SnO x type surface species are involved in the catalyst deactivation.

Comparison of the Redox Properties of Iron Incorporated in Different Amounts into MCM-41

Mesoporous Fe-MCM-41 samples with different framework iron contents were tested as catalysts in CO oxidation and characterized by TPR,Mössbauer and FTIR spectroscopies after heat treatment in high vacuum and reductive or oxidative atmospheres. In samples with Si/Fe ratiosof 20 and 12 all of the iron was found to be reducible with H2, but only a part of Fe(III) species could be reduced to Fe(II) in materialswith lower iron content. In neither of the materials could Fe(III) be fully converted with CO to the divalent oxidation state. A significant part ofiron can be reversibly reduced and reoxidized in successive redox cycles. Large Fe-O clusters could not be detected.

Silver- and sulfadiazine-loaded nanostructured silica materials as potential replacement of silver sulfadiazine

Silver sulfadiazine (AgSD) is the leading topical antibacterial agent for the treatment of burn wound infections. Antibacterial effect of AgSD is limited by its poor aqueous solubility, and antibacterial activity develops only by decomposition of AgSD to silver ions and sulfadiazine. In this study, it is for the first time that application of silver-modified nanoporous silica carriers (MCM-41 or SBA-15) loaded with sulfadiazine (SD), instead of silver sulfadiazine, overcoming the abovementioned disadvantages has been demonstrated. By direct or post synthesis methods, 5-15 nm sized silver nanoparticles can be stabilized in the channels or on the outer surface of nanoporous silica supports; moreover, the empty channels can be loaded by SD molecules. The SD-loaded, silver-modified materials show sustained release properties and similar or even better antimicrobial properties than AgSD. Adsorption of AgSD on nanoporous silica particles significantly improves its water solubility.

Glycerol acetylation on mesoporous KIL-2 supported sulphated zirconia catalysts

Zirconia nanomaterials were prepared by impregnation of KIL-2 type silica with 4, 8 and 12 wt.% ZrO2 and were modified by sulphate groups in order to vary the type and strength of acidity. Samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and N2 physisorption methods. Acidic properties of adsorbed pyridine were investigated by FT-IR spectroscopy. The catalytic performance of ZrKIL-2 and SO42−/ZrKIL-2 in glycerol esterification with acetic acid was studied and compared to that of pure zirconia varieties. It was found that silica-supported zirconia samples are more active than pure zirconia ones. With increasing ZrO2 content, KIL-2-supported catalysts showed increasing catalytic activity and selectivity in producing valuable fuel additives, di- and triacetyl glycerols. Sulphated analogues showed even higher activity and selectivity compared to non-sulphated ones due to their strong Bronsted acidity.

Characterization of Trimetallic Pt-Pd-Au/CeO2 Catalysts Combinatorial Designed for Methane Total Oxidation

In the present work, the role and the effect of platinum and gold on the catalytic performance of ceria supported tri-metallic Pt-Pd-Au catalysts have been studied. The optimum composition of these tri-metallic supported catalysts has been discovered using methods and tools of combinatorial catalyst library design. Detailed catalytic, spectroscopic and physico-chemical characterization of catalysts in the vicinity of the optimum in the given compositional space has been performed. The temperature-programmed oxidation of methane revealed that the addition of Pt and Au to Pd/CeO2 catalyst resulted in higher conversion values in the whole investigated temperature range compared to the monometallic Pd catalyst. The time-on-stream experiments provided further evidence for the high-stability of tri-metallic catalysts compared to the monometallic one. Kinetic studies revealed the stronger adsorption of methane on Pt-Pd/CeO2 catalysts than over Pd/CeO2. XPS analysis showed that Pt and Au stabilize Pd in a more reduced form even under condition of methane oxidation. FTIR spectroscopy of adsorbed CO and hydrogen TPD measurements provided indirect evidences for alloying of Pt and Au with Pd. CO chemisorption data indicated that tri-metallic catalysts have increased accessible metallic surface area. It is suggested that advantageous catalytic properties of tri-metallic Pt-Au-Pd/CeO2 catalysts compared to the monometallic one can be attributed to (i) suppression of the formation of ionic forms of Pd(II), (ii) reaching an optimum ratio between Pd0 and PdO species, and (iii) stabilization of Pd in high dispersion. The results also indicate that Pd0 - PdO ensemble sites are required for methane activation.

Photocatalytic WO3/TiO2 nanowires: WO3 polymorphs influencing the atomic layer deposition of TiO2

50–70 nm hexagonal (h-) and 70–90 nm monoclinic (m-) WO3 nanoparticles (NPs) were prepared by controlled annealing of (NH4)xWO3 in air at 470 and 600 °C, respectively. In addition, 5–10 nm thick and several micrometer long h-WO3 nanowires (NWs) were obtained by microwave hydrothermal synthesis at 160 °C with Na2WO4, HCl and (NH4)2SO4 as starting materials. TiO2 was deposited on h-WO3 NWs by atomic layer deposition (ALD) at 300 °C using Ti(iOPr)4 and H2O as precursors. The as-prepared materials were studied by TG/DTA-MS, XRD, Raman, SEM-EDX, TEM, ellipsometry, UV-Vis, and their photocatalytic activity was also tested by the photodecomposition of aqueous methyl orange. Our study is the first evidence of diverse ALD nucleation on various WO3 polymorphs, since on h-WO3 NWs TiO2 nucleated only as particles, whereas on m-WO3 conformal TiO2 film was formed, explained by the different surface OH coverage of h- and m-WO3. The h-WO3 NWs had significantly higher photocatalytic activity compared to h-WO3 NPs, and similar performance as m-WO3 NPs. By adding TiO2 to h-WO3 NWs by ALD method, the photocatalytic performance increased by 65%, showing clearly the uniqueness of ALD to obtain superior oxide composite photocatalysts.

Coordination and oxidation states of iron incorporated into MCM-41

Low iron content Fe-MCM-41 (Si/Fe=139) samples are characterized under in situ redox conditions by TPR, IR and Mossbauer spectroscopy. In the mesoporous structure full reversibility of the Fe 3+ ↔Fe 2+ transition is found. Different types of low coordinations are suggested for Fe 2+ . Reductions in hydrogen and carbon monoxide are compared, the possible role of silanolic-OH groups is discussed and propagation of reduction via (H 2 ) + ions is also suggested. A comparison is made with samples of higher iron contents (Si/Fe=77, 20 and 12).

Preparation of efficient quercetin delivery system on Zn-modified mesoporous SBA-15 silica carrier

Mesoporous silica material type SBA-15 was modified with different amounts of Zn (2 and 4wt.%) by incipient wetness impregnation method in ethanol. The parent, Zn-modified and quercetin loaded samples, were characterized by XRD, N2 physisorption, TEM, thermal gravimetric analysis, UV-vis and FT-IR spectroscopies and in vitro release of quercetin at pH5.5 which is typical of dermal formulations. By this loading method anhydrous quercetin was formed on the silica carrier It was found that the different hydrate forms of quercetin (dihydrate, monohydrate, anhydrite) significantly influence the physico-chemical properties of the delivery system. It was found that hydrate forms of quercetin can be differentiated by XRD and by FT-IR spectroscopic methods. Thus, by evaluating the interaction of the drug with the silica carrier the changes due to its hydration state always have to be taken into account. Formation of Zn-quercetin complex was evidenced on zinc modified SBA-15 silica by FT-IR spectroscopy. High quercetin loading capacity (over 40wt.%) could be achieved on the parent and Zn-containing SBA-15 samples. The in-vitro release process at pH=5.5 showed slower quercetin release from Zn-modified SBA-15 samples compared to the parent one. Additionally, the comparative cytotoxic experiments evidenced that quercetin encapsulated in Zn-modified silica carriers has superior antineoplastic potential against HUT-29 cells compared to free drug. Zn-modified SBA-15 silica particles could be promising carriers for dermal delivery of quercetin.