Facile synthesis and characterization of monocrystalline cubic ZrO2 nanoparticles

Crystalline ZrO₂ nanoparticles were prepared from zirconium isopropoxide by slow hydrolysis and subsequent hydrothermal treatment of solutions containing various amounts of sodium hydroxide at 180 °C. Whereas moderately basic solutions lead to the formation of nanoparticles of monoclinic ZrO₂ with plate-like morphology, and nanoparticles of the cubic ZrO₂ high-temperature polymorph with diameters of approx. 5 nm were obtained from strongly basic solutions. The morphology, structure and properties of as-synthesized nanoparticles were characterized using HRTEM, XRD, Raman spectroscopy, UV–vis, PL spectroscopy and BET measurements. The formation of both, the monoclinic and the cubic polymorph, was confirmed by electron microscopy and Raman spectroscopy. The crystallinity and morphology of the resulting ZrO₂ nanoparticles can be adjusted by the choice of the reaction conditions. The cubic ZrO₂ nanoparticles have a high surface area (300 m²/g) and exhibit a strong photoluminescence in the UV region.     

Structure and dynamics of highly PEG-ylated sterically stabilized micelles in aqueous media

Molecular assemblies of highly PEG-ylated phospholipids are important in many biomedical applications. We have studied sterically stabilized micelles (SSMs) of self-assembled DSPE–PEG2000 in pure water and isotonic HEPES-buffered saline solution. The observed SSM sizes of 2–15 nm largely depend on the solvent and the lipid concentration used. The critical micelle concentration of DSPE–PEG2000 is 10 times higher in water than in buffer, and the viscosity of the dispersion dramatically increases with the lipid concentration. To explain the experimentally observed results, we performed atomistic molecular dynamics simulations of solvated SSMs. Our modeling revealed that the observed assemblies have very different aggregation numbers (N(agg) ≈ 90 in saline solution and N(agg) < 8 in water) because of very different screening of their charged PO4(–) groups. We also demonstrate that the micelle cores can inflate and their coronas can fluctuate strongly, thus allowing storage and delivery of molecules with different chemistries.     

Photochemical control of bacterial gene expression based on trans encoded genetic switches

Controlling gene expression by light with fine spatiotemporal resolution not only allows understanding and manipulating fundamental biological processes but also fuels the development of novel therapeutic strategies. In complement to exploiting optogenetic tools, photochemical strategies mostly rely on the incorporation of photo-responsive small molecules into the corresponding biomacromolecular scaffolds. Therefore, generally large synthetic effort is required and the switching of gene expression in both directions within a single system remains a challenge. Here, we report a trans encoded ribo-switch, which consists of an engineered tRNA mimicking structure (TMS), under control of small photo-switchable signalling molecules. The signalling molecules consist of two amino glycoside molecules that are connected via an azobenzene unit. The light responsiveness of our system originates from the photo-switchable noncovalent interactions between the signalling molecule and the TMS switch, leading to the demonstration of photochemically controlled expression of two different genes. We believe that this modular design will provide a powerful platform for controlling the expression of other functional proteins with high spatiotemporal resolution employing light as a stimulus.

Controlling gene expression by light with fine spatiotemporal resolution not only allows understanding and manipulating fundamental biological processes but also fuels the development of novel therapeutic strategies.     

Xe nuclear magnetic resonance line shapes in channels decorated with paramagnetic centers

To make predictions of the Xe NMR line shapes for Xe in channels decorated with paramagnetic centers, we consider a model system using the O(2) molecule as the paramagnetic center. The previously calculated quantum mechanical Xe@O(2) hyperfine tensor for various configurations of Xe in the presence of O(2) provides a model for the hyperfine response of Xe atom to the presence of a paramagnetic center. The averaging is carried out using the same grand canonical Monte Carlo methodology as for calculating NMR line shapes for Xe in diamagnetic channels, modified to include the effects of the hyperfine tensor response. We explore the temperature dependence of the Xe line shapes, the dependence on the concentration, and the symmetry of distribution of embedded paramagnetic centers, on the orientation of the paramagnetic center axis with respect to the channel axis, and on the radial distance of the paramagnetic center from the axis of the channel. We predict Xe line shape signatures of the presence and orientation of paramagnetic centers and deduce which tensor elements provide measures of concentration and radial distance of paramagnetic centers from the channel axis.     

Nanoscale rotary motors driven by electron tunneling

We examine by semiclassical molecular dynamics simulations the possibility of driving nanoscale rotary motors by electron tunneling. The model systems studied have a carbon nanotube shaft with covalently attached "isolating" molecular stalks ending with "conducting" blades. Periodic charging and discharging of the blades at two metallic electrodes maintains an electric dipole on the blades that is rotated by an external electric field. Our simulations demonstrate that these molecular motors can be efficient under load and in the presence of noise and defects.     

Dendron-mediated self-assembly of highly PEGylated block copolymers: a modular nanocarrier platform

PEGylated dendron coils (PDCs) were investigated as a novel potential nanocarrier platform. PDCs self-assembled into micelles at lower CMCs than linear copolymer counterparts by 1-2 orders of magnitude, due to the unique architecture of dendrons. MD simulations also supported thermodynamically favourable self-assembly mediated by dendrons.     

Path of an RNA ligand around the surface of the vaccinia VP39 subunit of its cognate VP39-VP55 protein heterodimer

VP39 is a vaccinia virus-encoded RNA modifying protein with roles in the modification of both mRNA ends. At the 3' end it acts as a processivity factor for the vaccinia poly(A) polymerase (VP55), promoting poly(A) tail elongation. Despite VP39's three-dimensional structure having been elucidated along with details of its mode of mRNA 5' end binding, the VP39-VP55 heterodimer's molecular mechanism of processivity is largely unknown. Here, the area immediately above almost the entire surface of the VP39 subunit was probed using chemical reporters, and the path of a previously unidentified RNA binding site was revealed. The path was indicated to fall within a cleft formed by the intersubunit interface and was consistent with both a previously reported model of the heterodimer-nucleic acid ternary complex and the known function of the heterodimer in processive poly(A) tail elongation.