Silica@zirconia Core@shell Nanoparticles for Nucleic Acid Building Block Sorption.

The development of delivery systems for the immobilization of nucleic acid cargo molecules is of prime importance due to the need for safe administration of DNA or RNA type of antigens and adjuvants in vaccines. Nanoparticles (NP) in the size range of 20-200 nm have attractive properties as vaccine carriers because they achieve passive targeting of immune cells and can enhance the immune response of a weakly immunogenic antigen via their size. We prepared high capacity 50 nm diameter silica@zirconia NPs with monoclinic/cubic zirconia shell by a green, cheap and up-scalable sol-gel method. We studied the behavior of the particles upon water dialysis and found that the ageing of the zirconia shell is a major determinant of the colloidal stability after transfer into the water due to physisorption of the zirconia starting material on the surface. We determined the optimum conditions for adsorption of DNA building blocks, deoxynucleoside monophosphates (dNMP), the colloidal stability of the resulting NPs and its time dependence. The ligand adsorption was favored by acidic pH, while colloidal stability required neutral-alkaline pH; thus, the optimal pH for the preparation of nucleic acid-modified particles is between 7.0-7.5. The developed silica@zirconia NPs bind as high as 207 mg dNMPs on 1 g of nanocarrier at neutral-physiological pH while maintaining good colloidal stability. We studied the influence of biological buffers and found that while phosphate buffers decrease the loading dramatically, other commonly used buffers, such as HEPES, are compatible with the nanoplatform. We propose the prepared silica@zirconia NPs as promising carriers for nucleic acid-type drug cargos.

Monometallic Cerium Layered Double Hydroxide Supported Pd-Ni Nanoparticles as High Performance Catalysts for Lignin Hydrogenolysis.

Monometallic cerium layered double hydroxides (Ce-LDH) supports were successfully synthesized by a homogeneous alkalization route driven by hexamethylenetetramine (HMT). The formation of the Ce-LDH was confirmed and its structural and compositional properties studied by XRD, SEM, XPS, iodometric analyses and TGA. HT-XRD, N2-sorption and XRF analyses revealed that by increasing the calcination temperature from 200 to 800 °C, the Ce-LDH material transforms to ceria (CeO2) in four distinct phases, i.e., the loss of intramolecular water, dehydroxylation, removal of nitrate groups and removal of sulfate groups. When loaded with 2.5 wt% palladium (Pd) and 2.5 wt% nickel (Ni) and calcined at 500 °C, the PdNi-Ce-LDH-derived catalysts strongly outperform the PdNi-CeO2 benchmark catalyst in terms of conversion as well as selectivity for the hydrogenolysis of benzyl phenyl ether (BPE), a model compound for the α-O-4 ether linkage in lignin. The PdNi-Ce-LDH catalysts showed full selectivity towards phenol and toluene while the PdNi-CeO2 catalysts showed additional oxidation of toluene to benzoic acid. The highest BPE conversion was observed with the PdNi-Ce-LDH catalyst calcined at 600 °C, which could be related to an optimum in morphological and compositional characteristics of the support.

Thickness Characterization Toolbox for Transparent Protective Coatings on Polymer Substrates.

The thickness characterization of transparent protective coatings on functional, transparent materials is often problematic. In this paper, a toolbox to determine the thicknesses of a transparent coating on functional window films is presented. The toolbox consists of a combination of secondary ion mass spectrometry and profilometry and can be transferred to other transparent polymeric materials. A coating was deposited on designed model samples, which were characterized with cross-sectional views in transmission and in scanning/transmission electron microscopy and ellipsometry. The toolbox was then used to assess the thicknesses of the protective coatings on the pilot-scale window films. This coating was synthesized using straightforward sol-gel alkoxide chemistry. The kinetics of the condensation are studied in order to obtain a precursor that allows fast drying and complete condensation after simple heat treatment. The shelf life of this precursor solution was investigated in order to verify its accordance to industrial requirements. Deposition was performed successfully at low temperatures below 100 °C, which makes deposition on polymeric foils possible. By using roll-to-roll coating, the findings of this paper are easily transferrable to industrial scale. The coating was tested for scratch resistance and adhesion. Values for the emissivity (ε) of the films were recorded to justify the use of the films obtained as infrared reflective window films. In this work, it is shown that the toolbox measures similar thicknesses to those measured by electron microscopy and can be used to set a required thickness for protective coatings.

Pair Distribution Function Analysis of ZrO2 Nanocrystals and Insights in the Formation of ZrO2-YBa2Cu3O7 Nanocomposites.

The formation of superconducting nanocomposites from preformed nanocrystals is still not well understood. Here, we examine the case of ZrO2 nanocrystals in a YBa2Cu3O7−x matrix. First we analyzed the preformed ZrO2 nanocrystals via atomic pair distribution function analysis and found that the nanocrystals have a distorted tetragonal crystal structure. Second, we investigated the influence of various surface ligands attached to the ZrO2 nanocrystals on the distribution of metal ions in the pyrolyzed matrix via secondary ion mass spectroscopy technique. The choice of stabilizing ligand is crucial in order to obtain good superconducting nanocomposite films with vortex pinning. Short, carboxylate based ligands lead to poor superconducting properties due to the inhomogeneity of metal content in the pyrolyzed matrix. Counter-intuitively, a phosphonate ligand with long chains does not disturb the growth of YBa2Cu3O7−x. Even more surprisingly, bisphosphonate polymeric ligands provide good colloidal stability in solution but do not prevent coagulation in the final film, resulting in poor pinning. These results thus shed light on the various stages of the superconducting nanocomposite formation.