Impact of Ce/Zr Ratio in the Nanostructured Ceria and Zirconia Composites on the Selective CO2 Adsorption.

High surface-area, mesoporous CeO2, ZrO2, and Ce-Zr composite nanoparticles were developed using the hydrothermal template-assisted synthesis method. Samples were characterized using XRD, N2 physisorption, TEM, XPS, and FT-IR spectroscopic methods. The CO2 adsorption ability of the obtained materials was tested under dynamic and equilibrium conditions. A high CO2 adsorption capacity in CO2/N2 flow or CO2/N2/H2O was determined for all studied adsorbents depending on their composition flow. A higher CO2 adsorption was registered for Ce-Zr composite nanomaterials due to the presence of strong O2- base sites and enriched surface oxygen species. The role of the Ce/Zr ratio is the process of the formation of highly active and selective adsorption sites is discussed. The calculated heat of adsorption revealed the processes of chemisorption and physisorption. Experimental data could be appropriately described by the Yoon-Nelson kinetic model. The composites reused in five adsorption/desorption cycles showed a high stability with a slight decrease in CO2 adsorption capacities in dry flow and in the presence of water vapor.

Ni-Cu and Ni-Co-Modified Fly Ash Zeolite Catalysts for Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone.

Monometallic (Ni, Co, Cu) and bimetallic (Ni-Co, Ni-Cu) 10-20 wt.% metal containing catalysts supported on fly ash zeolite were prepared by post-synthesis impregnation method. The catalysts were characterized by X-ray powder diffraction, N2 physisorption, XPS and H2-TPR methods. Finely dispersed metal oxides and mixed oxides were detected after the decomposition of the impregnating salt on the relevant zeolite support. Via reduction intermetallic, NiCo and NiCu phases were identified in the bimetallic catalysts. The catalysts were studied in hydrodeoxygenation of lignocellulosic biomass-derived levulinic acid to γ-valerolactone (GVL) in a batch system by water as a solvent. Bimetallic, 10 wt.% Ni, and 10 wt.% Cu or Co containing fly ash zeolite catalysts showed higher catalytic activity than monometallic ones. Their selectivity to GVL reached 70-85% at about 100% conversion. The hydrogenation activity of catalysts was found to be stronger compared to their hydration ability; therefore, the reaction proceeds through formation of 4-hydroxy pentanoic acid as the only intermediate compound.

Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over Mesoporous Silica-Supported Cu-Ni Composite Catalysts.

Monometallic (Cu, Ni) and bimetallic (Cu-Ni) catalysts supported on KIT-6 based mesoporous silica/zeolite composites were prepared using the wet impregnation method. The catalysts were characterized using X-ray powder diffraction, N2 physisorption, SEM, solid state NMR and H2-TPR methods. Finely dispersed NiO and CuO were detected after the decomposition of impregnating salt on the silica carrier. The formation of small fractions of ionic Ni2+ and/or Cu2+ species, interacting strongly with the silica supports, was found. The catalysts were studied in the gas-phase upgrading of lignocellulosic biomass-derived levulinic acid (LA) to γ-valerolactone (GVL). The bimetallic, CuNi-KIT-6 catalyst showed 100% LA conversion at 250 °C and atmospheric pressure. The high LA conversion and GVL yield can be attributed to the high specific surface area and finely dispersed Cu-Ni species in the catalyst. Furthermore, the catalyst also exhibited high stability after 24 h of reaction time with a GVL yield above 80% without any significant change in metal dispersion.

Hydrodemethoxylation/Dealkylation on Bifunctional Nanosized Zeolite Beta.

Mono-, and bimetallic Ni-, Ru-, and Pt-modified nanosized Beta zeolite catalysts were prepared by the post synthesis method and characterized by powder X-ray diffraction (XRD), nitrogen physisorption, HRTEM microscopy, temperature-programmed reduction (TPR-TGA), ATR FT-IR spectroscopy, and by solid-state MAS-NMR spectroscopy. The presence of nanosized nickel-oxide, ruthenium-oxide, and platinum species was detected on the catalysts. The presence of Brønsted and Lewis acid sites, and incorporation of nickel ions into zeolite lattice was proven by FT-IR of adsorbed pyridine. The structural changes in the catalyst matrix were investigated by solid state NMR spectroscopy. The catalysts were used in a gas-phase hydrodemethoxylation and dealkylation of 2-methoxy-4-propylphenol as a lignin derivative molecule for phenol synthesis.

Selective Production of Phenol on Bifunctional, Hierarchical ZSM-5 Zeolites.

Mono- and bimetallic Ni-, Ru- and Pt-modified hierarchical ZSM-5 materials were prepared by impregnation technique and characterized by X-ray diffraction (XRD), N2 physisorption, temperature-programmed reduction (TPR-TGA), ATR-FTIR and solid state NMR spectroscopy. Formation of finely dispersed nickel, ruthenium and platinum species was observed on the bimetallic catalysts. It was found that the peculiarity of the used zeolite structure and the modification procedure determine the type of formed metal oxides and their dispersion and reducibility. The samples' acidity was studied via FTIR spectroscopy of adsorbed pyridine. The changes in the zeolite structure were studied via solid-state NMR spectroscopy. The catalysts were investigated in a gas-phase hydrodeoxygenation, transalkylation and dealkylation reaction of model lignin derivative molecules for phenol production.

Tamoxifen Delivery System Based on PEGylated Magnetic MCM-41 Silica.

Magnetic iron oxide containing MCM-41 silica (MM) with ~300 nm particle size was developed. The MM material before or after template removal was modified with NH2- or COOH-groups and then grafted with PEG chains. The anticancer drug tamoxifen was loaded into the organic groups' modified and PEGylated nanoparticles by an incipient wetness impregnation procedure. The amount of loaded drug and the release properties depend on whether modification of the nanoparticles was performed before or after the template removal step. The parent and drug-loaded samples were characterized by XRD, N2 physisorption, thermal gravimetric analysis, and ATR FT-IR spectroscopy. ATR FT-IR spectroscopic data and density functional theory (DFT) calculations supported the interaction between the mesoporous silica surface and tamoxifen molecules and pointed out that the drug molecule interacts more strongly with the silicate surface terminated by silanol groups than with the surface modified with carboxyl groups. A sustained tamoxifen release profile was obtained by an in vitro experiment at pH = 7.0 for the PEGylated formulation modified by COOH groups after the template removal. Free drug and formulated tamoxifen samples were further investigated for antiproliferative activity against MCF-7 cells.

Verapamil delivery systems on the basis of mesoporous ZSM-5/KIT-6 and ZSM-5/SBA-15 polymer nanocomposites as a potential tool to overcome MDR in cancer cells.

ZSM-5/KIT-6 and ZSM-5/SBA-15 nanoparticles were synthesized and further modified by a post-synthesis method with (CH2)3SO3H and (CH2)3NHCO(CH2)2COOH groups to optimize their drug loading and release kinetic profiles. The verapamil cargo drug was loaded by incipient wetness impregnation both on the parent and modified nanoporous supports. Nanocarriers were then coated with a three-layer polymeric shell composed of chitosan-k-carrageenan-chitosan with grafted polysulfobetaine chains. The parent and drug loaded formulations were characterized by powder XRD, N2 physisorption, thermal analysis, AFM, DLS, TEM, ATR-FT-IR and solid state NMR spectroscopies. Loading of verapamil on such nanoporous carriers and their subsequent polymer coating resulted in a prolonged in vitro release of the drug molecules. Quantum-chemical calculations were performed to investigate the strength of the interaction between the specific functional groups of the drug molecule and (CH2)3SO3H and CH2)3NHCO(CH2)2COOH groups of the drug carrier. Furthermore, the ability of the developed nanocomposites to positively modulate the intracellular internalization and thereby augment the antitumor activity of the p-gp substrate drug doxorubicin was investigated in a comparative manner vs. free drug in a panel of MDR positive (HL-60/Dox, HT-29) and MDR negative (HL-60) human cancer cell lines using the Chou-Talalay method.

Unexpected Sequential NH3/H2O Solid/Gas Phase Ligand Exchange and Quasi-Intramolecular Self-Protonation Yield [NH4Cu(OH)MoO4], a Photocatalyst Misidentified before as (NH4)2Cu(MoO4)2.

[NH4Cu(OH)MoO4] as active photocatalyst in the decomposition of Congo Red when irradiated by UV or visible light has been prepared in an unusual ammonia/water ligand exchange reaction of [tetraamminecopper(II)] molybdate, [Cu(NH3)4]MoO4. [Cu(NH3)4]MoO4 was subjected to moisture of open air at room temperature. Light blue orthorhombic [Cu(NH3)(H2O)3]MoO4 was formed in 2 days as a result of an unexpected solid/gas phase ammonia-water ligand exchange reaction. This complex does not lose its last ammonia ligand on further standing in open air; however, a slow quasi-intramolecular (self)-protonation reaction takes place in 2-4 weeks, producing a yellowish-green microcrystalline material, which has been identified as a new compound, [NH4Cu(OH)MoO4], ( a = 10,5306 Å, b = 6.0871 Å, c = 8.0148 Å, ß = 64,153°, C2, Z = 4). Mechanisms are proposed for both the sequential ligand exchange and the self-protonation reactions supported by ab initio quantum-chemical calculations and deuteration experiments as well. The [Cu(NH3)(H2O)3]MoO4 intermediate transforms into NH4Cu(OH)(H2O)2MoO4, which loses two waters and yields [NH4Cu(OH)MoO4]. Upon heating, both [Cu(NH3)4]MoO4 and [Cu(NH3)(H2O)3]MoO4 decompose, losing three NH3 and three H2O ligands, respectively, and stable [Cu(NH3)MoO4] is formed from both. The latter can partially be hydrated in boiling water into [NH4Cu(OH)MoO4. This compound can also be prepared in pure form by boiling the saturated aqueous solution of [Cu(NH3)4]MoO4. All properties of [NH4Cu(OH)MoO4] match those of the active photocatalyst described earlier in the literature under the formulas (NH4)2[Cu(MoO4)2] and (NH4)2Cu4(NH3)3Mo5O20.

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.

A pH dependent delivery of mesalazine from polymer coated and drug-loaded SBA-16 systems.

SBA-16 silica was synthesized and modified by post-synthesis method with amino groups. Wet milling in acidic media was applied for loading of poorly soluble drug mesalazine (5-aminosalicylic acid ­ 5-ASA) in different drug/carrier ratios (1:1; 0.75:1; 0.5:1; 0.25:1). The parent and drug loaded mesoporous silicas were characterized by XRD, TEM,N2 physisorption, thermal analysis, FT-IR and solid state NMR spectroscopy. The drug loaded mesoporous systems were single-coated with Eudragit S or double-coated with Eudragit S and Eudragit RL. The polymer coating significantly modified the rate of mesalazine release fromS BA-16NH2 materials. Applying the double coating method makes possible the sustained delivery of the drug in the intestinal area avoiding the burst release in the gastric fluid. The functionalized, polymer coated mesoporous system could be considered an appropriate oral delivery system for mesalazine. In addition, reduction of mesalazine cytotoxicity on epithelial cells could be achieved by its loading into mesoporous silica particles.

Solid-state encapsulation of Ag and sulfadiazine on zeolite Y carrier.

HYPOTHESIS: A new simplified procedure for encapsulation of antibacterial silver nanoparticles by Solid-state Ion Exchange (SSIE) procedure over zeolite Y, followed by deposition of sulfadiazine (SD) by dry mixing was examined for the preparation of topical antibacterial formulations. The ion-exchange and adsorptive properties of the zeolite matrix were utilized for the bactericidal Ag deposition and loading of antibiotic sulfadiazine. EXPERIMENTS: Assessment of the encapsulation efficiency of both active components loaded by solid and liquid deposition methods was made by X-ray diffraction, TEM, FT-IR spectroscopy and thermogravimetric analysis (TGA). SD release kinetics was also determined. FINDINGS: Sustained delivery of sulfadiazine has been observed from the Ag-modified zeolites compared to the parent HY material. It was found that if SD was loaded in solution, part of the zeolite silver ions was released and interacted with SD, forming AgSD. By solid-state SD deposition, the reaction between the drug and the silver was restricted within the limits of inter-atomic interaction, and total but prolonged drug release occurred.

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.

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.

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.

Low temperature CO oxidation over iron-containing MCM-41 catalysts.

Different MCM-41 samples containing framework iron were prepared and tested in CO oxidation showing unprecedented high activities after reduction in hydrogen above 773 K.

Synthesis and characterization of hyperbranched mesoporous silica SBA-15.

Branched mesoporous silica SBA-15 materials have been prepared in a simple process using non-ionic surfactant in acidic conditions in the presence of metal ions.