Rotaxanes and Catenanes Derived from Tetra-Urea Calix[4]arenes

Summary: Calix[4]arenes, substituted by four urea groups at their wide rim, form dimeric capsules in apolar solvents, which are held together by a seam of intermolecular hydrogen bonds. The heterodimerisation of tetra-aryl and tetratosyl ureas was used to synthesize various derivatives, in which adjacent urea residues are connected to form two, three or four loops. The aliphatic connections were tied by olefin metathesis between adjacent alkenyl residues followed by hydrogenation. Heterodimers of tetra-alkenyl substituted tetra-ureas and bis- or tetraloop derivatives were converted analogously to multiple catenanes. Tetra[2]rotaxanes were obtained in a similar manner. In addition to the spectroscopic evidence (NMR, MS) several compounds were confirmed by crystal structures.     

The evolution of the nanoscale dissipative structures in a distribution of defects within the isothermally irradiated f.c.c. crystal

A kinetic model for the influence of external noises such as fluctuations of the vacancies’ generation rate and inhomogeneity of irradiated f.c.c. crystal on the formation of nanoscale modulated dissipative structure in a spatial distribution of vacancies is considered. The generation rate of vacancies all over the sites and a density of their dislocation-type sinks are modelled as independent random uniform stationary fields and with certain defined parameters of fluctuation correlations – spatial and temporal ones. Such stochastic fields can induce a spatial redistribution of vacancies that can lead to their density stationary uniform field or stochastic one. By the average value and correlation functions of these fluctuations, the conditions are determined for interacting fluctuations of the vacancies’ density, under which this homogeneous random field becomes unstable in relation to the stochastic field with a spatially periodic mean distribution of vacancies’ density. For instance, with f.c.c. nickel as a model of the irradiated functional material, the temperature dependence of spatial period d(T) of the modulated dissipative structure of vacancies’ subsystem in f.c.c. crystal is numerically forecasted and analysed, taking into account the total (‘electrochemical’?+?‘strain-induced’) interaction between vacancies. Such d(T)-dependence is also determined by the kinetic characteristics of vacancies’ redistribution.     

Dielectric‐loaded plasmonic waveguide components: Going practical

Surface plasmon propagating modes supported by metal/dielectric interfaces in various configurations can be used for radiation guiding similarly to conventional dielectric waveguides. Plasmonic waveguides offer two attractive features: subdiffraction mode confinement and the presence of conducting elements at the mode‐field maximum. The first feature can be exploited to realize ultrahigh density of nanophotonics components, whereas the second feature enables the development of dynamic components controlling the plasmon propagation with ultralow signals, minimizing heat dissipation in switching elements. While the first feature is yet to be brought close to the domain of practical applications because of high propagation losses, the second one is already being investigated for bringing down power requirements in optical communication systems. In this review, the latest application‐oriented research on radiation modulation and routing using thermo‐optic dielectric‐loaded plasmonic waveguide components integrated with silicon‐based photonic waveguides is overviewed. Their employment under conditions of real telecommunications is addressed, highlighting challenges and perspectives.     

Coherent control of the population transfer in complex solvated molecules at weak excitation. An experimental study

We performed a series of successful experiments for the optimization of the population transfer from the ground to the first excited state in a complex solvated molecule (rhodamine 101 in methanol) using shaped excitation pulses at very low intensities (1 absorbed photon per 100-500 molecules per pulse). We found that the population transfer can be controlled and significantly enhanced by applying excitation laser pulses with crafted pulse shapes. The optimal shape was found in feedback-controlled experiments using a genetic search algorithm. The temporal profile of the optimal excitation pulse corresponds to a comb of subpulses regularly spaced by approximately 150 fs, whereas its spectrum consists of a series of well-resolved peaks spaced apart by approximately 6.5 nm corresponding to a frequency of 220 cm(-1). This frequency matches very well with the frequency modulation of the population kinetics (period of approximately 150 fs), observed by excitation with a short (approximately 20 fs) transform-limited laser pulse directly after excitation. In addition, an antioptimization experiment was performed under the same conditions. The difference in the population of the excited state for the optimal and antioptimal pulses reaches approximately 30% even at very weak excitation. The results of optimization are reproducible and have clear physical meaning.     

Features of 3-amino-5-methylisoxazole in heterocyclizations involving pyruvic acids

Chemistry of Heterocyclic Compounds - The chemical properties of 3-amino-5-methylisoxazole in the reactions involving pyruvic acid derivatives are reported. The multicomponent condensation of...     

Determination and tailoring the pore entrance size in ordered silicas with cage-like mesoporous structures

A practical approach to the determination of the pore entrance size in ordered silicas with cage-like mesoporous structures (OSCMSs) is proposed. A fundamental insight into the OSCMS pore connectivity is gained, including the control of the pore entrance size by post-synthesis surface modification, and by selection of appropriate synthesis temperature. These findings show a new promise for the synthesis of mesoporous solids with molecular size- and shape-selective properties.     

Localization and waveguiding of surface plasmon polaritons in random nanostructures

We propose to use channels in strongly scattering nonabsorbing random media for guiding electromagnetic waves, and demonstrate this concept using near-field microscopy of surface plasmon polaritons (SPP's) propagating along the gold film surface covered with randomly located scatterers. In the wavelength range of 725-765 nm, we observe complete inhibition of the SPP propagation inside the random structures composed of approximately 50-nm-wide gold bumps and their clusters with the density of 50 microm(-2), as well as well-defined SPP guiding along corrugation-free 2- and 4-microm-wide channels.     

1-Allyl-3-propylthiourea modified mesoporous silica for mercury removal

1-Allyl-3-propylthiourea modified mesoporous silica has high adsorption capacity for mercury ions and its regeneration can be accomplished by washing with 10% thiourea in aqueous 0.05 M HCl.