BON-BONs: cyclic molecules with a boron-oxygen-nitrogen backbone. Computational studies of their thermodynamic properties

Although they were first reported in 1963, molecules with a boron-oxygen-nitrogen dimeric backbone do not seem to have been investigated seriously in terms of thermodynamic properties. Here we report on the calculated structures and properties, including thermodynamics, of several so-called “BON-BON” molecules. With the popularity of nitrogen-containing substituents on new high-energy materials, nitro-substituted BON-BONs were a focus of our investigation. A total of 42 BON-BON molecules were evaluated, and thermochemical analysis shows a decrease in the specific enthalpy of combustion or decomposition with increasing NO₂ content, consistent with other systems.     

Xylem hydraulic and photosynthetic function of Gnetum (Gnetales) species from Papua New Guinea

Gnetum (Gnetales) species are suggested to be unique extant gymnosperms that have acquired high photosynthetic and transpiration capacities as well as greater xylem hydraulic capacity and efficiency compared with all other extant gymnosperms. This is because Gnetum is the only extant gymnosperm lineage that combines vessels, broad pinnate-veined leaves and an ecological distribution in wet, productive lowland tropical rainforest habitats. Yet, field-based observations on the group's ecophysiological performance are lacking. To test a hypothesis that Gnetum species are ecophysiologically analogous to light-demanding woody tropical angiosperms, stem xylem hydraulic performance, photosynthesis and stomatal conductance were investigated in Gnetum as compared with a diverse group of co-occurring woody plants in a lowland tropical rainforest. It was found that Gnetum species combined low photosynthetic capacity and low stomatal conductances with a low stem water transport ability. The physiological observations are consistent with the general occurrence of Gnetum species in shady, primary forest habitats. These results on Gnetum ecophysiology indicate that the coupling of vessels, broad pinnate-veined leaves and the liana habit do not signal the evolution of a highly opportunistic, light-demanding life history in gymnosperms.     

The evolution of angiosperm lianescence without vessels--climbing mode and wood structure-function in Tasmannia cordata (Winteraceae)

? The lack of extant lianescent vessel-less seed plants supports a hypothesis that liana evolution requires large-diameter xylem conduits. Here, we demonstrate an unusual example of a lianoid vessel-less angiosperm, Tasmannia cordata (Winteraceae), from New Guinea. ? Wood mechanical, hydraulic and structural measurements were used to determine how T. cordata climbs and to test for ecophysiological shifts related to liana evolution vs 13 free-standing congeners. ? The tracheid-based wood of T. cordata furnished low hydraulic capacity compared with that of vessel-bearing lianas. In comparison with most nonclimbing relatives, T. cordata possessed lower photosynthetic rates and leaf and stem hydraulic capacities. However, T. cordata exhibited a two- to five-fold greater wood elastic modulus than its relatives. ? Tasmannia cordata provides an unusual example of angiosperm liana evolution uncoupled from xylem conduit gigantism, as well as high plasticity and cell type diversity in vascular development. Because T. cordata lacks vessels, our results suggest that a key limitation for a vessel-less liana is that strong and low hydraulically conductive wood is required to meet the mechanical demands of lianescence.     

The biosynthesis, processing, and secretion of laminin by human choriocarcinoma cells

Laminin, a glycoprotein component of basal laminae, is synthesized and secreted in culture by a human malignant cell line (JAR) derived from gestational choriocarcinoma. Biosynthetically labeled human laminin subunits A (Mr approximately 400,000) and B (Mr = 200,000 doublet) are glycoslyated with asparagine-linked high mannose oligosaccharides that are processed to complex oligosaccharides before the laminin molecule is externalized by the cell. The rate-limiting step in the processing of the asparagine-linked glycans of laminin is at the point of action of alpha-mannosidase I since the principal laminin forms that accumulate in JAR cells contain Man9GlcNAc2 and Man8GlcNAc2 oligosaccharide units. The combination of subunits to form the disulfide-linked laminin molecule (Mr approximately 950,000) occurs rapidly within the cell at a time when the subunits contain these high mannose oligosaccharides. The production of laminin is limited by the availability of the A subunit such that excess B subunit forms accumulate intracellularly as uncombined B and a disulfide-linked B dimer. Pulse-chase kinetic studies establish these B forms as intermediates in the assembly of the laminin molecule. The fully assembled laminin undergoes further oligosaccharide processing and translocation to the cell surface, but uncombined B and B dimer are neither processed nor secreted to any significant extent. Therefore, laminin subunit combination appears to be a prerequisite for intracellular translocation, processing, and secretion. The mature laminin that contains complex oligosaccharides does not accumulate intracellularly but is rapidly externalized upon completion, either secreted into the culture medium (25%) or associated with the cell surface (75%) as determined by susceptibility to degradation by trypsin. About one-third of the laminin molecules secreted or shed by JAR cells into the chase medium contain a smaller A subunit form that appears to have been modified by limited proteolytic cleavage. The putative proteolytic event is closely timed to the release of the laminin into the culture medium.     

Introducing NOB-NOBs: nitrogen-oxygen-boron cycles with potential high-energy properties

As a follow-up on a study of a family of boron-oxygen-nitrogen compounds composed of two datively bonded B-O-N backbones, we investigate a similar series of compounds that have similar fragments but are covalently bonded. B3LYP/6-31G(d,p) quantum mechanical calculations have been performed to determine the minimum-energy geometries, vibrational frequencies, and thermochemical properties of the parent compound and a series of nitro-substituted derivatives. Our results indicate that some of the derivatives have at least appropriate thermodynamics for possible high-energy materials, in some cases being favorable over similar dimeric compounds with coordinate covalent B-N bonds.