Volume 86, Issue 9

Cyclodextrins (CDs) – a family of cyclic oligosaccharides – are ideal building blocks for the construction of environmentally benign materials. Herein, we reflect upon the serendipitous discovery of two classes of extended crystalline materials – referred to as cyclodextrin metal-organic frameworks (CD-MOFs) and CD-Bamboo – based on CDs which offer opportunities for potential applications in the world of industry and commerce all the way from sequestering carbon dioxide to extracting gold in an eco-friendly manner. The crucial role of serendipity in scientific research expresses itself two times over at the boundaries between coordination chemistry with materials science.

Structural studies in this laboratory encompass four of the five major classes of plant lectins, including the one discovered by us. In addition to addressing issues specific to individual lectins, the work provided insights into protein folding, quaternary association and generation of ligand specificity. Legume and β-prism fold lectins constitute families of proteins in which small alterations in essentially the same tertiary structure lead to large variations in quaternary structure, including that involving an open structure. Strategies for generating ligand specificity include water bridges, variation in loop length, post translational modification and oligomerization. Three of the structural classes investigated have subunits with three-fold symmetry. The symmetry in the structure is reflected in the sequence to different extents in different sub-classes. The evolutionary implications of this observation have been explored. The work on lectins has now been extended to those from mycobacteria.

Pyranosidic allylic (Ferrier) cations that share dicobalt hexacarbonyl propargyl (Nicholas) stabilization at C -1, can be easily generated by treatment of hexacarbonyldicobalt alkynyl glycals with BF 3 ·OEt 2 , and display a remarkable reactivity leading to a variety of products. The substituent at O -6 in these glycals plays a pivotal role in directing the outcome of the transformations. Accordingly, 6- O -benzyl or 6- O -allyl groups cause a series of transformations resulting in the stereoselective formation of oxepanes through a process that involves an initial hydride transfer step from the allyl or benzyl substituent to the Ferrier–Nicholas cation. On the contrary, 6-OH derivatives undergo an overall ring contraction to branched tetrahydrofuran derivatives. 6- O -Silyl derivatives, in the presence of heteroaryl nucleophiles, were transformed into C -3 branched bis- C - C -glycosides, containing two of such molecules.

Anionic fucose-containing polysaccharides (fucoidans of brown seaweeds, sulfated fucans and fucosylated chondroitin sulfates of invertebrates) are attracting a rapidly growing research interest due to different types of their biological activity discovered in recent years. In particular, algal fucoidans are characterized by large structural variations depending on the species used for their isolation and by the lack of structural regularity due to random distribution of both carbohydrate and non-carbohydrate substituents along the polymer chains. These features make it difficult to find distinct correlations between structural elements and biological properties of polysaccharides. Nevertheless, there is expectation that systematic structural and biochemical studies of fucoidans will form a basis for the development of new drugs. Herewith we summarize our recent results on the influence of fucoidan structure on blood coagulation.

Addition of a carbene to a glycal is the prominent method for the synthesis of 1,2-cyclopropyl carbohydrates. This incorporation of a cyclopropane into a carbohydrate scaffold enables divergent reactivity, with the two main classes being ring expansion and cleavage to 2- C -branched carbohydrates. A wide variety of products are obtained depending on the functionality attached to the cyclopropane (none or ester or halogens) and the promoter (Lewis acid, Brønsted acid, halophile or base) used in the reaction. This article reviews progress in the synthesis and reactions of 1,2-cyclopropyl carbohydrates since 2000 and discloses efforts by our group in the area.

Conformational analysis of unnatural seven-membered sugars, namely, septanoses and septanosides are discussed herein. The conformational properties of these sugars in the solid state, solution phase and computational methods are presented. The analyses reveal that conformations of septanosides are diverse and largely unpredictable, as compared furanosides and pyranosides.

The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios ( 40 Ar/ 36 Ar, 38 Ar/ 36 Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40 Ar, as some samples contain almost pure radiogenic 40 Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36 Ar and 38 Ar. Within this interval, measurements of different isotope ratios ( 40 Ar/ 36 Ar or 38 Ar/ 36 Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.