Curcumin and Capsaicin-Loaded Ag-Modified Mesoporous Silica Carriers: A New Alternative in Skin Treatment.

Biologically active substances of natural origin offer a promising alternative in skin disease treatment in comparison to synthetic medications. The limiting factors for the efficient application of natural compounds, such as low water solubility and low bioavailability, can be easily overcome by the development of suitable delivery systems. In this study, the exchange with the template procedure was used for the preparation ofa spherical silver-modified mesoporous silica nanocarrier. The initial and drug-loaded formulations are fully characterized by different physico-chemical methods. The incipient wetness impregnation method used to load health-promoting agents, curcumin, and capsaicin in Ag-modified carriers separately or in combinationresulted in high loading efficiency (up to 33 wt.%). The interaction between drugs and carriers was studied by ATR-FTIR spectroscopy. The release experiments of both active substances from the developed formulations were studied in buffers with pH 5.5, and showed improved solubility. Radical scavenging activity and ferric-reducing antioxidant power assays were successfully used for the evaluation of the antiradical and antioxidant capacity of the curcumin or/and capsaicin loaded on mesoporous carriers. Formulations containing a mixture of curcumin and capsaicin were characterized bypotentiation of their antiproliferative effect against maligning cells, and it was confirmed that the system for simultaneous delivery of both drugs has lower IC50 values than the free substances.The antibacterial tests showed better activity of the obtained delivery systems in comparison with the pure curcumin and capsaicin. Considering the obtained results, it can be concluded that the obtained delivery systems are promising for potential dermal treatment.

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.

Low-Temperature Toluene Oxidation on Fe-Containing Modified SBA-15 Materials.

Transition metals as catalysts for total VOC oxidation at low temperatures (150-280 °C) are a big challenge nowadays. Therefore, iron-modified SBA-15, AlSBA-15, and ZrSBA-15 materials with 0.5 to 5.0 wt.% Fe loading were prepared and tested for toluene oxidation. It was found that increasing Fe loading significantly improved the rate of oxidation and lowered the temperature of achieving 100% removal of toluene from above 500 °C for the supports (AlSBA-15 and ZrSBA-15) to below 400 °C for 5FeZrSBA-15. The formation of finely dispersed iron oxide active sites with a particle size less than 5 nm was observed on all the SBA-15, AlSBA-15, and ZrSBA-15 supports. It was found that the surface properties of the mesoporous support due to the addition of Al or Zr predetermined the type of formed iron oxide species and their localization on the support surface. Fe-containing SBA-15 and AlSBA-15 showed activity in total toluene oxidation at higher temperatures (280-450 °C). However, 5 wt. % Fe-containing ZrSBA-15 showed excellent activity in the total oxidation of toluene as a model VOC at lower temperatures (150-380 °C) due to the synergistic effect of Fe-Zr and the presence of accessible and stable Fe2+/Fe3+ active sites.

Evolution of Surface Catalytic Sites on Bimetal Silica-Based Fenton-Like Catalysts for Degradation of Dyes with Different Molecular Charges.

We present here important new findings on the direct synthesis of bimetal Cu-Mn containing porous silica catalyst and the effects of structure-directing agent removal from the prepared nanomaterial on the evolution of surface catalytic sites. The extraction-calcination procedure of the structure-directing agent removal led to the formation of Cu and Mn oxo-clusters and Cu and Mn oxide nanoparticles smaller than 5 nm, while the solely calcination procedure led to the mentioned species and in addition to the appearance of CuO nanoparticles 20 nm in size. Catalysts were tested in the Fenton-like catalytic degradation of dyes with different molecular charge (cationic, anionic, and zwitterionic) as model organic pollutants in wastewater at neutral pH. Significantly faster degradation of cationic and anionic dyes in the first 60 min was observed with the catalyst containing larger CuO nanoparticles (>20 nm) due to the less hindered generation of •OH radicals and slower obstructing of the active sites on the catalysts surface by intermediates. However, this was not found beneficial for zwitterionic dye with no adsorption on the catalysts surface, where the catalyst with smaller Cu species performed better.

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.

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.