Protein native-state stabilization by placing aromatic side chains in N-glycosylated reverse turns

N-glycosylation of eukaryotic proteins helps them fold and traverse the cellular secretory pathway and can increase their stability, although the molecular basis for stabilization is poorly understood. Glycosylation of proteins at na?ve sites (ones that normally are not glycosylated) could be useful for therapeutic and research applications but currently results in unpredictable changes to protein stability. We show that placing a phenylalanine residue two or three positions before a glycosylated asparagine in distinct reverse turns facilitates stabilizing interactions between the aromatic side chain and the first N-acetylglucosamine of the glycan. Glycosylating this portable structural module, an enhanced aromatic sequon, in three different proteins stabilizes their native states by -0.7 to -2.0 kilocalories per mole and increases cellular glycosylation efficiency.     

Iron-stabilized carbocations as intermediates for organic synthesis

Attachment of a transition metal moiety to an olefinic ligand presents the organic chemist with unequaled opportunities to control the regio- and stereospecificities of bond formation. Applications of cationic dienyliron-carbonyl complexes to a range of natural product syntheses have been developed. These applications show how the iron-carbonyl unit directs the regio- and stereochemistry of nucleophile addition. They also show that the iron-carbonyl unit can be used to stabilize otherwise inaccessible carbocations, thereby making them readily available as synthetic intermediates.     

5-coordinate si compounds as intermediates in the synthesis of silicates in nonaqueous media

Sodium silicoglycolate, an organosilicon compound in which silicon is in 5-coordination with respect to oxygen, is shown to be a reaction intermediate in the synthesis of a purely siliceous sodalite with ethylene glycol as solvent. The presence of silicon-29 nuclear magnetic resonances at -105.5 +/- 0.3 parts per million in solution and -102.7 parts per million in the solid state as well as x-ray powder diffraction patterns demonstrate that 5-coordinate silicon is intimately involved in the synthesis. Silicon compounds of the 5-coordinate type are highly reactive and are promising starting materials for the synthesis of novel silicone polymers, molecular sieves, glasses, semiconductors, and ceramics. We have used sodium silicoglycolate to prepare the molecular sieve silicalite as well as sodalites of different compositions.     

Damselfish as keystone species in reverse: intermediate disturbance and diversity of reef algae

Substrates located within the defended territories of Hawaiian damselfish for 1 year were subjected to intermediate grazing intensity and, as a result, showed greater diversity of algae than substrates either protected within fish-exclusion cages or exposed to intense fish grazing outside territories. Thus, this damselfish enhances local diversity on reefs through "intermediate-disturbance" effects, and is a keystone species that decreases rather than increases overall predation intensity relative to areas where it is absent.