Transition-metal-complexed cyclic [3]- and [4]pseudorotaxanes containing rigid ring-and-filament conjugates: synthesis and solution studies

By using the "gathering-and-threading" effect of copper(I) with rigid ring-and-string conjugates, daisy-chain-type [3]- and [4]pseudorotaxanes could be prepared in high yields. The organic fragment used consisted of a 2,9-diphenyl-1,10-phenanthroline (dpp)-containing ring attached to a coordinating filament capable of threading through the ring of another molecule by coordination to copper(I). The bidentate chelate introduced in the axis was also a 1,10-phenanthroline (phen) derivative with two methyl groups ortho to the nitrogen atoms of the phen unit. The organic component was prepared following a multistep strategy, one of the key steps being the attachment of the ring to the lateral axis. This connection was done by a condensation reaction between an ortho dione located at the back of a ring-incorporated phen and an aromatic aldehyde, which was the end-function of the thread. An oxazole nucleus was obtained after the condensation, which provided a rigid connection between the ring and the axis. In this way, the coordination axes of the ring-incorporated bidentate chelate and of the ligand belonging to the lateral filament were approximately orthogonal to one another. The design was such that the tetrameric complex, a [4]pseudorotaxane, seemed to be the most stable species, owing to the mutual geometrical arrangement of the filament and the ring. Various spectroscopic techniques, such as (1)H NMR spectroscopy, including DOSY, and electrospray ionization mass spectroscopy (ESI-MS), clearly demonstrated that a mixture of cyclic [3]- and [4]pseudorotaxane was obtained; the proportions of both components depended on concentration and temperature. Copper(I) was not the only metal center leading to the formation of cyclic pseudorotaxanes. A similar effect was observed with silver(I) as the templating metal: quantitative formation of threaded species was observed, with a higher proportion of trimer over tetramer than in the copper(I) case. Concentration and temperature effects were investigated for both series of Cu(I) - and Ag(I) -complexed threaded species showing that formation of the trimer was favored upon dilution or heating of the solution.     

Low-power light and isolated rat hearts after ischemia of myocardium

We studied the influence of low-intensity red light on restoration of isolated heart contractility, on lipid peroxidation processes and a state of the superoxide dismutase (SOD) activity in myocardial tissues of isolated hearts. It was found that after ischemia modeled and perfusion restored the light illumination results in acceleration of myocardial contractility recovery, rising of the SOD activity and reduction in the amount of molecular products of lipid peroxidation.     

Benzoxazole-based heterometallic dodecanuclear complex [Dy(III)4Cu(II)8] with single-molecule-magnet behavior

Three Cu-Ln (Ln = Dy, Gd, Y) dodecanuclear clusters assembled by a novel ligand of the benzoxazole type are reported. The dysprosium cluster exhibits a frequency dependence of the alternating-current susceptibility and hysteresis loop at low temperature, indicating single-molecule-magnet behavior.     

Ruthenium-catalyzed selective hydrogenation of bis-arylidene tetramic acids. Application to the synthesis of novel structurally diverse pyrrolidine-2,4-diones

Catalytic hydrogenation of 3,5-bis-arylidenetetramic acids, known for their biological activity, has been developed. The chemoselective ruthenium-catalyzed reduction of the exocyclic carbon-carbon double bonds on pyrrolidine-2,4-dione ring system, containing other reducible functions, has been investigated. Depending on the substrate the yield of the hydrogenation process can reach up to 95%. The structural elucidation has been established using NMR and HRMS spectral data.     

Gradient sensing in reactive, ternary membranes

Using computer simulations, we investigate the behavior of reactive ternary ABC membranes that are subjected to an external, spatially nonuniform stimulus, which controls the rate of interconversion between the A and B components. We assume that A and B have different spontaneous curvatures. Furthermore, the C component is taken to be nonreactive and incompatible with both A and B. We find that a gradient in the applied stimulus causes the dynamic reconstruction of the membrane, with a preferential reorientation of the reactive AB domains along the gradient. In addition, the external gradient effectively controls the transport of the nonreactive C component within the membrane. The latter effect could potentially be exploited for cleaning the membrane of the nonreactive C "impurities" or for the targeted delivery of the C component to specific locations.     

Approximation of circular arcs by parametric polynomial curves

In this paper the approximation of circular arcs by parametric polynomial curves is studied. If the angular length of the circular arc is h, a parametric polynomial curve of arbitrary degree \(n \in {\mathbb{N}}\) , which interpolates given arc at a particular point, can be constructed with radial distance bounded by h ²ⁿ . This is a generalization of the result obtained by Lyche and Mørken for odd n.     

On a Unified Theory of Generalized Branes Coupled to Gauge Fields,Including the Gravitational and Kalb–Ramond Fields

We investigate a theory in which fundamental objects are branes described in terms of higher grade coordinates encoding both the motion of a brane as a whole, and its volume evolution. We thus formulate a dynamics which generalizes the dynamics of the usual branes. Geometrically, coordinates and associated coordinate frame fields {} extend the notion of geometry from spacetime to that of an enlarged space, called Clifford space or C-space. If we start from four-dimensional spacetime, then the dimension of C-space is 16. The fact that C-space has more than four dimensions suggests that it could serve as a realization of Kaluza-Klein idea. The “extra dimensions” are not just the ordinary extra dimensions, they are related to the volume degrees of freedom, therefore they are physical, and need not be compactified. Gauge fields are due to the metric of Clifford space. It turns out that amongst the latter gauge fields there also exist higher grade, antisymmetric fields of the Kalb–Ramond type, and their non-Abelian generalization. All those fields are naturally coupled to the generalized branes, whose dynamics is given by a generalized Howe–Tucker action in curved C-space.