A convergent and operationally simple method for the preparation of N-linked glycopeptides (see picture) was highlighted in the preparation of three glycopeptide fragments of erythropoietin. These fragments were assembled by ligation chemistry in the first total synthesis of erythropoietin bearing four glycans. This methodology should find far-reaching applications in the synthesis of a whole range of glycoproteins for biological study.
No, it's not frogspawn! Polymer-coated gold nanoparticles can be assembled into extended mesoscopic chains with precise dimensional control. Here, the conditions can be adjusted to promote the fusion of polymeric ligands into cylindrical micellar aggregates. This type of colloidal polymerization offers a new and versatile route to a variety of mesoscopic assemblies of nanoparticles.
Worth the wait: A new variable, zirconium content, has been added to the already complex amine-supported porous silica systems used for CO2 capture. SBA-15 incorporating Zr ions and loaded with poly(ethyleneimine) was exposed to simulated flue gas (10 % CO2) and ambient air (400 ppm CO2). Not only was the performance of the Zr-doped material significantly better than that of the pristine system, it also displayed improved desorption kinetics.
G protein-coupled receptors with seven transmembrane helices (see picture) are the most important drug targets in medicine. Their molecular and structural characterization has now been honored with the Nobel Prize for Chemistry to Robert J. Lefkowitz and Brian K. Kobilka.
In black and white: The hydrogenation of TiO2 can extend its optical absorption into the visible and infrared region and change its color from white to black. Furthermore, the hydrogenated black TiO2 exhibits excellent photocatalytic activity for the splitting of water to yield H2.
Only water: Phenols have been shown to undergo a ruthenium-catalyzed ortho-alkylation reaction (see scheme; Cy=cyclohexyl). Unactivated alcohols are used as the alkylating agents and water is the only by-product that is generated, making this transformation more atom-economical and greener than traditional methods.
Getting real: Although 1-azidoalkenes are known as important intermediates for the formation of many nitrogen heterocycles, for a long time the existence of the corresponding 1-azidoalkynes could not be proven unequivocally. The recent synthesis and full characterization of 1-azidoethyne have provided incontrovertible verification of this substance class.
Achieving the unachievable: Hard supramolecular materials displaying autonomous self-healing have been considered unachievable because of the mobility required to reconstitute supramolecular interactions after rupture. Now, relatively hard thermoplastic elastomers have been reported that meet these requirements. The picture shows a triblock copolymer containing soft supramolecular “self-healing” domains and hard, structure-giving domains.
A bright future: The realization that a mixture of squaraine derivatives drastically improve quantum efficiency in the visible and near-IR region of organic solar cells, and the synthesis of the first phospharadialene serve as the focus for a short overview of oxocarbons and related heteroorganic compounds.
Cell death by visible light: Photodynamic therapy (PDT) is a relatively underemployed method for treatment of diseases including cancer. Recent improvements in synthetic and analysis methods of metal complexes provide for red-light-activated drugs with potential application in PDT (see picture).
Give a direction: A rationally designed, removable meta-directing group enables the selective, remote functionalization of aromatic substrates (see scheme). The generality of the concept was shown with alkenylation reactions of hydrocinnamic acid derivatives, the selectivities of which were similar to the ones described for benzyl derivatives.
Teamwork: Through relay catalysis by a RuII complex and a chiral phosphoric acid ((S)-BPA in the scheme) recently developed by Zhou's group, hydrogen gas can act as the terminal reductant in the catalytic asymmetric hydrogenation of heterocycles. This is a completely new concept in the area of asymmetric hydrogenation.
Going through the channels: Synthetic scaffolds mimicking natural protein functions have been developed that allow water/proton or only water translocation pathways in bilayer membranes (see picture). The ion-exclusion behaviors of the synthetic systems are based on hydrophobic or dimensional steric effects, while hydrodynamic effects appear to be less important.
Behind the wheel: A 10 nm diameter nanoring, containing 24 porphyrin units, has been created by a Vernier-templating self-organization of hexa- or octadentate templating units and linear covalently linked porphyrin oligomers. Coordination of a bidentate ligand triggers a conversion of the molecular nanocylinder into a molecular nanoannulus to afford the dimeric species, which can adopt a water wheel structure (see picture).
Inspired by nature: Self-assembled peptide nanoparticles have been designed that accelerate ester hydrolysis (see picture; Cbz=carbobenzyloxy, NP=p-NO2-C6H4). The concerted interplay of the multivalent surface with the catalytically active peptide and the substrate at the same time combines several aspects decisive for the catalyst's efficiency, a property characteristic of enzymes.
Sodium bisulfite promotes both the deformylative deamination of 5-formylcytosine (5fC) and the decarboxylative deamination of 5-carboxylcytosine (5caC; see picture). By coupling this bisulfite chemistry with selective oxidations of individual DNA bases, new methods allow, for the first time, the sequencing of 5-hydroxymethylcytosine (5hmC) with single-base-pair resolution.
“Chiral aryl cation” equivalents: The combination of diaryliodonium salts and catalytic amounts of chiral copper complexes provides facile access to “chiral aryl cation” synthons. These reagents offer new possibilities for asymmetric arylation reactions that initiate further domino processes.
Step by step: According to the molecular approach to the production of graphene, precursor molecules are cross-linked to form two-dimensional intermediates, and pyrolysis transforms the intermediates into graphene. This type of highly efficient synthesis of high-quality graphene is crucial to the development of innovative applications.
Switching to solids: Solid-state dye-sensitized solar cells are achieving efficiencies similar to those of their counterparts with liquid electrolytes. The new p-type semiconductor CsSnI3 was found to be an excellent replacement for the traditional I−/I3− redox system. The picture shows a cross section of a dye-sensitized solar cell based on CsSnI3.
Calculations help: Recent work from Schoenebeck's group has demonstrated beyond reasonable doubt that the dimeric LPdIBr catalysts that are widely used in coupling chemistry operate through prior formal reduction to an LPd0 species. Conversely, L2Pd0 catalysts can be activated by oxidation. In other cases a binuclear species can persist through the catalytic cycle.
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