Close to the edge : Photoexcitation of alizarin coupled to the surface of mesoporous TiO2 films leads to ultrafast electron transfer to the TiO2 conduction band (see picture). Complex kinetics after photoexcitation depend on the excitation energy, and indicate a position of the alizarin excited state close to the TiO2 conduction band edge, where the density of acceptor states is reduced.
Easy and direct : Regioselective Mizoroki–Heck‐coupling reactions using heteroaromatic tosylates as electrophiles were achieved, thus providing direct and easy access to highly functionalized α‐heteroarylvinyl amides and ethers.
Shape‐persistent micelles consisting of exactly 12 molecules (see picture), which coexist with rodlike micelles, are formed by the self‐labeled amphicalixarene at pH 7. In contrast to other examples of structurally defined micelles, this new type of amphiphile serves as a fluorescence reporter and provides an extended cavity structure in the hydrophilic part, thereby facilitating the inclusion of guest molecules.
Cohesion matters! The correlation between the conformational rigidity of the polyelectrolyte and the size and stability of the globular assembly is discussed in this review article. Some examples of models for the association of polyelectrolytes to globular assemblies are shown here.
Stack them helically : A self‐assembled helically stacked array of up to 11 porphyrin (Po)‐modified uridines (red and blue in the double strand shown) is based on the supramolecular scaffold of duplex DNA and shows promising optical properties. Such architectures could find application as functional molecules for photoactive nanomaterials and photonic nanostructures.
The next generation : The grafting of titanocene complexes on the surfaces of MCM‐41 and SBA‐15 led to a new generation of anticancer drugs, which are very active against human cancer cells.
Eradicating hedgehogs : The title molecule has been previously identified as a potent inhibitor of the Hedgehog signaling pathway, which gives embryonic cells information needed to develop properly. This molecule is shown to modulate Hedgehog target gene expression by depolymerizing microtubules, thus revealing dual roles of the cytoskeleton in pathway regulation (see figure).
Two very distinct chemical reactions, yet a single catalyst : A gold complex promotes the formation of tertiary enamines from a variety of terminal and internal alkynes. Subsequent addition of a terminal alkyne to the reaction mixture affords allenes (see scheme).
A simple addition with a large impact : Addition of aromatic amines such as phenanthroline and 4‐DMAP (4‐dimethylaminopyridine) increases copper(I)‐catalyzed azide alkyne cycloaddition (CuAAC) catalytic activity of [CuCl(SIMes)] at a large range of temperatures in such a way that efficient catalysis can safely take place in hydro‐alcoholic solvents (see scheme).
Two photons are better than one : This principle applies to a wide range of applications, ranging from engineering to physiology. Recent advances in our understanding of the phenomenon of two‐photon absorption (see picture) and in the design of two‐photon dyes are rapidly increasing the scope of this field.
A radical thing : After being obtained unexpectedly in low yields, the synthesis of the first stable triarylgermyl radical .Ge[3,5‐tBu2‐2,6‐(EtO)2C6H]3 ( 1 ; C gray, O blue) was considerably optimized, and the product was investigated by X‐ray analysis and EPR spectroscopy. The results were compared with DFT‐MO studies for the model compound .Ge[2,6‐(MeO)2C6H3].
All in a cluster : The selected sequence has a crucial influence on both the orientation and flexibility of the carbohydrate moiety in mucin‐type glycopeptides (see picture). This feature can be explained through the varied conformational behavior of the glycosidic linkage of the Thr residue when compared with the Ser residue (see figure). On this basis, and taking into account that these carbohydrates presumably interact with components of the immune system, these findings could be helpful in the design of new cancer vaccines.
Assembly language : The programmed sequences of stereochemical building blocks lead to novel biomimetic helices. The rational design approach offers new possibilities for creating periodic secondary structures.
Organolithium chemistry! An overview of the structure formation principles and the strong structure–reactivity relationship of lithium organics is given. By means of the commonly used lithium bases the deaggregation of the oligomeric parent structures to small adducts is presented (see examples) and compared to the related chemistry of lithiosilanes.
Tunable surface: The surface structure of the Fe–Pt bimetallic catalyst can be reversibly modulated between the iron‐oxide‐rich Pt surface and the Pt‐skin structure with subsurface Fe via alternating reduction and oxidation treatments (see figure). The regenerated active Pt‐skin structure is active in reactions involving CO and/or O.
Competition : The electrocyclizations of 1‐ and 3‐hydroxyheptatrienyl cations (see scheme) have been computationally studied at the B3LYP/6‐311G(d) level. The 1‐hydroxy system clearly favors a 4e? over a 6e? process, while for the 3‐hydroxy isomer these mechanisms compete.
