Hyaluronic Acid Nanoparticles with Parameters Required for In Vivo Applications: From Synthesis to Parametrization.

Hyaluronic acid is an excellent biocompatible material for in vivo applications. Its ability to bind CD44, a cell receptor involved in numerous biological processes, predetermines HA-based nanomaterials as unique carrier for therapeutic and theranostic applications. Although numerous methods for the synthesis of hyaluronic acid nanoparticles (HANPs) are available today, their low reproducibility and wide size distribution hinder the precise assessment of the effect on the organism. A robust and reproducible approach for producing HANPs that meet strict criteria for in vivo applications (e.g., to lung parenchyma) remains challenging. We designed and evaluated four protocols for the preparation of HANPs with those required parameters. The HA molecule was cross-linked by novel combinations of carbodiimide, and four different amine-containing compounds resulted in monodisperse HANPs with a low polydispersity index. By a complex postsynthetic characterization, we confirmed that the prepared HANPs meet the criteria for inhaled therapeutic delivery and other in vivo applications.

Epoxidation of Methyl Esters as Valuable Biomolecules: Monitoring of Reaction.

The paper is focused on the epoxidation of methyl esters prepared from oil crops with various profiles of higher fatty acids, especially unsaturated, which are mainly contained in the non-edible linseed and Camelina sativa oil (second generation). The novelty consists in the separation and identification of all products with oxirane ring formed through a reaction and in the determination of time course. Through the epoxidation, many intermediates and final products were formed, i.e., epoxides with different number and/or different position of oxirane rings in carbon chain. For the determination, three main methods (infrared spectroscopy, high-pressure liquid chromatography and gas chromatography with mass spectrometry) were applied. Only gas chromatography enables the separation of individual epoxides, which were identified on the base of the mass spectra, molecule ion and time course of products. The determination of intermediates enables: (i) control of the epoxidation process, (ii) determination of the mixture of epoxides in detail and so the calculation of selectivity of each product. Therefore, the epoxidation will be more environmentally friendly especially for advanced applications of non-edible oil crops containing high amounts of unsaturated fatty acids.

The effect of the zeolite pore size on the Lewis acid strength of extra-framework cations.

The catalytic activity and the adsorption properties of zeolites depend on their topology and composition. For a better understanding of the structure-activity relationship it is advantageous to focus just on one of these parameters. Zeolites synthesized recently by the ADOR protocol offer a new possibility to investigate the effect of the channel diameter on the adsorption and catalytic properties of zeolites: UTL, OKO, and PCR zeolites consist of the same dense 2D layers (IPC-1P) that are connected with different linkers (D4R, S4R, O-atom, respectively) resulting in the channel systems of different sizes (14R × 12R, 12R × 10R, 10R × 8R, respectively). Consequently, extra-framework cation sites compensating charge of framework Al located in these dense 2D layers (channel-wall sites) are the same in all three zeolites. Therefore, the effect of the zeolite channel size on the Lewis properties of the cationic sites can be investigated independent of other factors determining the quality of Lewis sites. UTL, OKO, and PCR and pillared 2D IPC-1PI materials were prepared in Li-form and their properties were studied by a combination of experimental and theoretical methods. Qualitatively different conclusions are drawn for Li(+) located at the channel-wall sites and at the intersection sites (Li(+) located at the intersection of two zeolite channels): the Lewis acid strength of Li(+) at intersection sites is larger than that at channel-wall sites. The Lewis acid strength of Li(+) at channel-wall sites increases with decreasing channel size. When intersecting channels are small (10R × 8R in PCR) the intersection Li(+) sites are no longer stable and Li(+) is preferentially located at the channel-wall sites. Last but not least, the increase in adsorption heats with the decreasing channel size (due to enlarged dispersion contribution) is clearly demonstrated.

Transition Metal-Promoted Mg-Fe Mixed Oxides for Conversion of Ethanol to Valuable Products.

The conversion of ethanol into petrochemicals, such as ethyl and butyl acetate, butanol, hexanol, and so forth was studied. The conversion was catalyzed by Mg-Fe mixed oxide modified with a second transition metal (Ni, Cu, Co, Mn, or Cr). The main aim was to describe the influence of second transition metal on (i) the catalyst itself and (ii) reaction products such as ethyl acetate, butanol, hexanol, acetone, and ethanal. Moreover, the results were compared with the results of pure Mg-Fe. The reaction was carried out in the gas phase in a flow reactor with a weight hour space velocity of 4.5 h-1 for 32 h at three reaction temperatures (280, 300, and 350 °C). The metals Ni and Cu in Mg-Fe oxide enhanced the ethanol conversion due to the population of active dehydrogenation sites. Despite the lower acido-basicity, Cu, Co, and Ni supported the yield of ethyl acetate, and Cu and Ni also promoted the yield of higher alcohols. Ni was related to the extent of the gasification reactions. Moreover, long-term stability (by leaching of metals) test was carried out for all catalysts (128 h).

Transesterification of Camelina sativa Oil Catalyzed by Mg/Al Mixed Oxides with Added Divalent Metals.

This paper is focused on the heterogeneously catalyzed transesterification (in a batch reactor) of vegetable oil, including the determination of leached metals. The oil was obtained from the short-season crop Camelina sativa. The reaction was catalyzed by mixed oxides, which were synthesized from Mg/Al hydrotalcites with built-in different types of divalent cations such as Mn, Ca, Co, Ni, and Fe. The various physicochemical properties like the structure by X-ray diffraction, acidity, basicity, and textural properties were measured and the effect of the added cation type on catalyst properties and activity was compared. A noticeable relationship between the cation type and catalytic activity in the transesterification reaction was observed. The highest ester content of 96.6 wt % after 7 h of transesterification was observed for catalysts with nickel and iron. The statistical analysis of results showed that the catalyst activity was mainly influenced by middle-temperature basic sites. The novelty lies in transesterification over five different heterogeneous catalysts-mixed oxides with added divalent metals at the same reaction conditions of C. sativa oil.