Fast and efficient preparation of Baylis-Hillman-derived (E)-allylic azides and related compounds in aqueous medium

A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated.     

Using a Conic Formulation for Finding Steiner Minimal Trees

We present a new mathematical programming formulation for the Steiner minimal tree problem. We relax the integrality constraints on this formulation and transform the resulting problem (which is convex, but not everywhere differentiable) into a standard convex programming problem in conic form. We consider an efficient computation of an ε-optimal solution for this latter problem using an interior-point algorithm.     

Determination of degree of conversion as a function of depth of a photo-initiated dental restoration composite—III application to commercial Prodigy Condensable™

In this third work, we evaluated the degree of conversion (DC) versus depth of dental filling composite named Prodigy Condensable™ using infrared spectroscopy. Confirming previous results, there was a gradual reduction of DC with increasing depth but the composite exhibited extreme values of DC, an upper value (45.9%) on the surface and a lower one (6.1%) at a depth of 5 mm. The composite presented the worst performance among materials studied. The composite formulation was 80% of inorganic fillers and BisfenolA/dimethacrylate (BisGMA) (18%)/triethyleneglycoldimethacrylate (TEGDMA) (2.0%) as monomers. As stated before, type/ratio/viscosity of monomers and type, amount, size and size distribution of fillers all together had an important role in the cure reaction contributing to the final performance of the composite.     

Unusual solid-state behavior in a neutral [2]catenane bearing a hydrolyzable component

A template-directed strategy to forming a bis(diimide) macrocycle through an intermediate asymmetric [2]catenane is reported. Saponification of the ester linkages within the crown ether component is much slower in the mechanically interlocked structure when compared to the free crown. The predominance of a single translational isomer leads to a dimeric structure, resulting in the generation of infinite channels within the crystal lattice. [structure: see text]     

Preparation and crystal structure ofexo-2,exo-6-dihydroxy-2,6-dimethyl-9-oxabicyclo[3.3.1]nonane

In a further exploration of the structural factors causing alicyclic diols such asexo-2,exo-6-dihydroxy-2,6-dimethylbicyclo[3.3.1]nonane (1) to adopt the helical tubuland inclusion host structure, the title compound (8) has been synthesized and its crystal structure determined. This 9-oxa analogue of (1) has a totally different structure [C₁₀H₁₈O₃; orthorhombic;P2₁2₁2;a 18.989(4),b 19.064(3),c 14.256(3) Å;Z 20; with finalR 0.065] due to involvement of the ether oxygen atom in the hydrogen bonding network. The structure of the diol (8) approximatesP¯42₁ c symmetry, and 16 of the 20 molecules per cell create a hostlike structure of this symmetry, which consists of tightly bound hydrogen bonded pillars parallel toc. The remaining guestlike molecules occupy inequivalent pseudo ¯4 sites separated byc/2 to form weakly bound columns parallel toc. Hydrogen bonds also occur between the pillars and columns. An ordered structure with sensible intermolecular contacts can be formed inP2₁2₁2₁ with thec axis doubled. A difference betweena andb axial lengths correlates with a difference in occupancies of pseudo-¯4-related sites for the guest-like component of the structure.     

Helical tubulate inclusion compounds of ferrocene and squalene

The inclusion compounds of 2,8-dimethyltricyclo[5.3.1.1^3,9]dodecane-syn-2,syn-8-diol,3, with ferrocene and with squalene have been prepared. The crystal structures of these helical tubulate compounds: (3)₃·(ferrocene)_0.75 [P3₁21,a=b=13.7480(6),c=7.0312(5) Å,Z=1,R=0.038] and (3)₃·(squalene)_0.23 [P3₁21,a=b=13.677(1),c=7.0533(9) Å,Z=1,R=0.042] are described. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82151 (16 pages).     

Interrelations between the parasitophorous vacuole of Toxoplasma gondii and host cell organelles.

Toxoplasma gondii, the causative agent of toxoplasmosis, is capable of actively penetrating and multiplying in any nucleated cell of warm-blooded animals. Its survival strategies include escape from fusion of the parasitophorous vacuole with host cell lysosomes and rearrangement of host cell organelles in relation to the parasitophorous vacuole. In this article we report the rearrangement of host cell organelles and elements of the cytoskeleton of LLCMK2 cells, a lineage derived from green monkey kidney epithelial cells, in response to infection by T. gondii tachyzoites. Transmission electron microscopy made on flat embedded monolayers cut horizontally to the apical side of the cells or field emission scanning electron microscopy of monolayers scraped with scotch tape before sputtering showed that association of mitochondria to the vacuole is much less frequent than previously described. On the other hand, all parasitophorous vacuoles were surrounded by elements of the endoplasmic reticulum. These data were complemented by observations by laser scanning microscopy using fluorescent probes from mitochondria and endoplasmic reticulum and reinforced by three-dimensional reconstruction from serial sections observed by transmission electron microscopy and labeling of mitochondria and endoplasmic reticulum by fluorescent probes.     

Reactivity of singlet oxygen toward strained substrates and a novel non-photochemical method for determination of quenching constants of singlet oxygen.

Rate constants for quenching of ¹O₂ by a number of strained molecules have been determined by the competitive rubrene photooxidation method; the rate constant for quenching by Q may be evaluated by adaption of a kinetic analysis already in the literature for the rubrene photooxidation method.     

NMR detection of intermolecular NH.OP hydrogen bonds between guanidinium protons and bisposphonate moieties in an artificial arginine receptor

Hydrogen bonding plays a major role in the selective recognition of guanidinium groups by receptor molecules. The present NMR investigation provides direct experimental evidence of hydrogen bonds in an artificial arginine receptor complex consisting of alpha-N-benzoylarginine ethyl ester and a bisphosphonate tweezers molecule. trans-Hydrogen bond 2hJHP couplings between the phosphonate moieties and individual guanidinium protons as well as the amide proton have been detected by [1H,31P]-HMBC and [31P,1H]-INEPT experiments. The detected hydrogen bonding network in the investigated artificial arginine receptor shows a symmetrical end-on interaction of the guanidinium moiety, which enables concerted rotations and deviates from the structure proposed for the biological arginine fork.