Guanidine‐Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases

Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2‐hydroxypropyl para‐nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts.     

Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

Synthesis and Characterization of Silica@Copper Core–Shell Nanoparticles: Application for Conjugate Addition Reactions

Silica@copper (SiO₂@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO₂@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity.     

Titanium nanocarbides: Synthesis and modeling

The present state of research on the production and modeling of nanostructures based on titanium carbide-a typical representative of an extensive class of carbides of d-and f-metals-is reviewed. Methods for the synthesis of various Ti-C nanostructures (molecular clusters, nanocrystallites, nanospheres, nanofibers, nanowires) are examined, and their morphology, atomic structure, and known physicochemical characteristics are described. Theoretical models of the atomic structure and properties of new types of nanostructures in the titanium-carbon system (endo-and exohedral titanofullerenes, “hybrid” structures based on carbon nanotubes, the so-called peapods, nanocables, and a number of others) and the prospects for their application as components of nanoceramics, hydrogen accumulators, materials for spintronics, etc. are discussed. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 1, pp. 1–23, January–February, 2007.     

Strain-induced modification of magnetic structure and new magnetic phases in rare-earth epitaxial films

Rare earths exhibit complex magnetic phase diagrams resulting from the competition between various contributions to the magnetic energy: exchange, anisotropy and magnetostriction. The epitaxy of a rare-earth film on a substrate induces (i) a clamping to the substrate and (ii) pseudomorphic strains. Both these effects are shown to lead to modifications of the magnetic properties in (0 0 1)Dy, (0 0 1)Tb and (1 1 0)Eu films. In Dy and Tb films, spectacular variations of the Curie temperature have been evidenced. Additionally, Tb films exhibit a new large wavelength magnetic modulation. In Eu films, one of the helical magnetic domains disappears at low temperature whereas the propagation vectors of the other helices are tilted. The link between structural and magnetic properties is underlined via magnetoelastic models. Moreover, molecular beam epitaxy permits the growth of Sm in a metastable dhcp phase. The magnetic structure of dhcp Sm has been elucidated for the first time. In this review, neutron scattering is shown to be a powerful technique to reveal the magnetic structures of rare-earth films.     

Optical bistability of planar metal/dielectric nonlinear nanostructures

We study theoretically a nonlinear response of the planar metal/dielectric nanostructures constituted from periodical array of ultra thin silver layers and the layers of Kerr-like nonlinear dielectric. We predict hysteresis-type dependences of the components of the tensor of effective dielectric permittivity on the field intensity allowing the change in material transmission properties from transparent to opaque and back at extremely low intensities of the light. It makes possible to control the light by light in all-optical nanoscale devices and circuits.     

Photonic crystals--a step towards integrated circuits for photonics.

The field of photonic crystals has, over the past few years, received dramatically increased attention. Photonic crystals are artificially engineered structures that exhibit a periodic variation in one, two, or three dimensions of the dielectric constant, with a period of the order of the pertinent light wavelength. Such structures in three dimensions should exhibit properties similar to solid-state electronic crystals, such as bandgaps, in other words wavelength regions where light cannot propagate in any direction. By introducing defects into the periodic arrangement, the photonic crystals exhibit properties analogous to those of solid-state crystals. The basic feature of a photonic bandgap was indeed experimentally demonstrated in the beginning of the 1990s, and sparked a large interest in, and in many ways revitalized, photonics research. There are several reasons for this attention. One is that photonic crystals, in their own right, offer a proliferation of challenging research tasks, involving a multitude of disciplines, such as electromagnetic theory, nanofabrication, semi-conductor technology, materials science, biotechnology, to name a few. Another reason is given by the somewhat more down-to-earth expectations that photonics crystals will create unique opportunities for novel devices and applications, and contribute to solving some of the issues that have plagued photonics such as large physical sizes, comparatively low functionality, and high costs. Herein, we will treat some basics of photonic crystal structures and discuss the state-of-the-art in fabrication as well give some examples of devices with unique properties, due to the use of photonic crystals. We will also point out some of the problems that still remain to be solved, and give a view on where photonic crystals currently stand.