Like mapping other worlds In their Communication on page 4667 ff., A. P. de Silva et al. describe proton concentration maps of detergent micelles obtained by the fluorescent multiplexing sensors (space-filling model). These sensors can change their positions and report information comprised of pK_a values and emission wavelengths. These sensors serve as nanosized robot vehicles, as they send detailed data from humanly inaccessible environments.

Nanodonuts form from hierarchical self-organization of a melamine featuring π-conjugated oligo(para-phenyleneethynylene)s with a cyanurate. The toroidal nanostructures, with a diameter of 40 nm (see AFM image), form in decane under dilute conditions. S. Yagai, A. Ajayaghosh et al. propose in their Communication on page 4691 ff. that a hydrogen-bonded rosette is an essential intermediate supramolecular species for such a hierarchical self-organization process. The background picture shows a “bubble ring” made by a scuba diver.

Big step, small molecule: Although acetaldehyde is the simplest of enolizable carbonyl compounds, and low-molecular-weight enamine/iminium-ion organocatalysis is the more elegant and most economical way to introduce chirality into a molecule, the first reports of the direct catalytic asymmetric reactions of acetaldehyde with electrophiles have just recently appeared (see scheme; Boc=tert-butyloxycarbonyl). Elaboration of the obtained adducts provides precursors for the synthesis of pharmaceuticals.

MOF Tuning: Recent progress on postsynthetic covalent modification of MOF (metal–organic framework) materials has led to the discovery of exciting new porous inorganic materials. These results involve transformation of the organic groups of MOFs without altering the three-dimensional structure.

As Bernini's David, in the prime of adolescence, fought Goliath armed only with a sling and a stone, organocatalysis uses simple organic molecules to address some fundamental issues of organic synthesis. Important questions concern the chemical efficiency of such processes and the development of viable and simple routes to natural products and drug candidates.

Please release me: Dumbbell-shaped rod amphiphiles self-assemble into hollow spheres (see picture) with gated nanopores in the shell. These pores undergo reversible transitions from the open state to the closed state upon heating, and are capable of entrapping the cargos with preservation of their hollow spherical structure, in a manner similar to viral capsids.

Hi-fi mapping: Multiplexing fluorescent sensors that simultaneously target proton concentration and polarity move to micellar nanospaces, self-regulate their positions, and report their pK_a values and wavelengths, which are controlled by their local environments. Such sensory functions enable maps of proton gradients near micellar membranes to be drawn.

Protect your back: Chiral wedges (red, see scheme) at the wingtips of bis(2-pyridylimino)isoindole (bpi) pincer ligands with an appropriate protective hedge (green), to block the metal center from backside attack, in the backbone represent a new class of efficient 3d-metal catalysts. These catalysts gave excellent enantioselectivities in the iron-catalyzed hydrosilylation of arylketones and in the cobalt-catalyzed cyclopropanation of alkenes.

Hydrogen peroxide generation at a liquid|liquid interface occurs with a yield of 20 % with respect to the concentration of reducing agent (decamethylferrocene). The liquid|liquid interface supplies electrons from the reducing agent and protons from the aqueous phase to drive the reduction of O₂ into H₂O₂, which is extracted into the aqueous phase during the course of reaction (see picture; DCE=1,2-dichloroethane).

Small and effective: The pathological aggregation of amylin (IAPP), which leads to type II diabetes mellitus, is effectively inhibited by small-molecule rhodanine-based inhibitors at nanomolar concentrations. The prevention of aggregation by treatment with the inhibitor is demonstrated by AFM (see image).

Getting on top of things: DFT calculations have been used to study the adsorption energies of O, OH, S, SH, N, NH, and NH₂ on transition metal oxide, sulfide, and nitride surfaces. A scaling relationship was found between the adsorption energies of the intermediates and the adsorption energies of the atoms which is independent of the metal and depends only on the number of H atoms in the molecule (see graph).

A good starting point: Optically pure γ-lactams have been prepared by organocatalytic enantioselective vinylic substitution. The parent lactam structure allows logical and systematic introduction of functionality around the periphery to access new derivatives of this important class of molecules. Bn=benzyl, PG=protecting group.

Nanodonuts! A hydrogen-bonded cyclic assembly (rosette, left) of a melamine featuring π-conjugated oligo(p-phenyleneethynylene) hierarchically self-organizes with a cyanurate in decane under dilute conditions to form toroidal nanostructures (right) with a diameter of 40 nm.

One of the most general systems for the cross-coupling of aryl and heteroaryl bromides and chlorides with 2-pyridyl-derived nucleophiles has been developed, for which catalysts comprising [Pd₂(dba)₃] and either diaryl (1) or dialkyl phosphine oxide (2) supporting ligands were found to be ideal (see scheme).

More than a one-trick pony: Postsynthetic modification of metal–organic frameworks (MOFs) permits stepwise, “tandem” modification of the lattice. An MOF bearing reactive functional groups can be subjected to a controllable, heterogeneous transformation sequence while retaining its structural integrity and microporosity. This approach allows the synthesis of MOFs bearing multiple functional groups (represented in the scheme by green and pink spheres).

Director's cut: The poor directing ability of the dimethylamino group in directed ortho metalation is altered by complexation to BF₃, which makes it more strongly activating than methoxy and chloro groups. DFT calculations of simplified lithiated intermediates reveal a small role of the inductive effect, but a distinctive F⋅⋅⋅Li interaction that leads to a F–Li distance which is remarkably similar to the C–Li distance.

Tuning to the terminals: Controlled tuning of protein–substrate interactions induces a transition from native to non-native protein crystals (see AFM images) as—depending on m, the chain-length difference, which determines whether surface protrusions are hydroxy or methyl functionalized—the underlying non-ion-mediated interactions are gradually transformed from mainly associative (H-bonding) to hydrophobic.

Tied up nicely: A novel tandem reaction involving an intramolecular Heck reaction with subsequent functionalization of an unactivated CH bond to generate spiro-fused indane-oxindoles is described (see scheme; PMB=p-methoxybenzyl).

The active ingredient: The bis(μ-imido) tantalum dimer {[ONO^red]Ta(μ-N-p-tolyl)(py)}₂ releases the aryl diazene (p-tolyl)NN(p-tolyl) upon four-electron oxidation with PhICl₂ (see scheme; py=pyridine). Studies suggest that the redox-active [ONO^red]³⁻ ligands act to collect single-electron oxidation equivalents for the multielectron reaction.

Acetaldehyde, now a big contender: A silyl prolinol derivative was found to catalyze the first Michael addition of acetaldehyde with both aromatic and aliphatic nitroolefins in excellent enantioselectivities (see scheme, TMS=trimethylsilyl). The utility of the reaction is illustrated in the synthesis of three current pharmaceuticals and in the synthesis of an enantiopure 3-monosubstituted pyrrolidine.

An acetaldehyde breakthrough: The catalytic asymmetric Michael addition reaction of acetaldehyde and various nitroalkenes in the presence of a chiral diphenylprolinol silyl ether organocatalyst is described (see scheme; TMS=trimethylsilyl). The desired 1,4-addition products, α-unsubstituted γ-nitro aldehydes, were obtained in good yields with excellent enantioselectivities.

One seed for two: Microspheres with patterned surfaces were obtained by modifying the surface of microspheres of a self-assembled colloidal crystal and redispersion of the colloidal crystal into individual particles. With these surface-patterned spheres as seeds, two types of nonspherical particles were fabricated by the seeded particle growth method.

What leaving group? Organic halides and allylic esters undergo efficient Pd-catalyzed Heck reactions under mild conditions in air to form a new CC bond without elimination of the β-OAc group in the intermediate palladium complex. Instead a highly regioselective β-H elimination takes place to provide substituted derivatives of allylic alcohols (see scheme).

O₂-coupled allylic CH amination: A first general palladium-mediated intermolecular aerobic oxidative allylic amination was developed to synthesize linear (E)-allylimides with high regioselectivity (see scheme; MA=maleic anhydride). The proposed mechanism involves an allylic CH activation with subsequent nitrogen nucleophile substitution. The catalytic system allows efficient dioxygen-coupled turnover without additional cocatalysts.

Rapid elaboration: (+)-Neopeltolide, a novel marine metabolite with potent cytotoxicity against several cancer cell lines, was the target of an efficient total synthesis (see scheme). The construction of the 2,4,6-trisubstituted tetrahydropyran substructure is based on a Suzuki–Miyaura coupling/ring-closing metathesis sequence. BOM=benzyloxymethyl, MPM=4-methoxyphenylmethyl, TIPS=triisopropylsilyl.

I am ligand: A pentadentate bispidine ligand with two tertiary amine and three pyridine donors stabilizes the uncommon intermediate-spin electronic configuration of Co^III (S=1; see picture: C gray, N blue, O red, Co violet). Dissociation of the monodentate coligand yields a catalytically active pentacoordinate complex.

CH insertion: Borylnitrenes, which are generated in situ by photoylsis of azides, convert unactivated alkanes by intermolecular CH insertion into aminoboranes (see scheme), which in turn can be reacted further to give amines or amides. The boryl group serves two purposes: it converts the nitrene into a highly reactive BN vinylidene analogue, and it is easily cleaved from the product.

Specific cell recognition: Magnetic γ-Fe₂O₃ nanoparticles (MNPs) functionalized with a fluorescently labeled polymer and polyinosinic-polycytidylic acid [poly(I:C)] allow the specific visualizion of the TLR3 receptors on the the surface of Caki-1 cells. The expression of TLR3 on the Caki-1 cells was demonstrated independently by RT-PCR and immunostaining techniques.

Crystals of the photoreceptor phytochrome were studied nondestructively by resonance Raman spectroscopy. The spectra of the chromophore-binding domains (CBD) of phytochrome from Deinococcus radiodurans, from which three-dimensional structures have been determined, demonstrate the same chromophore structure in the parent Pr state as in solution. Unlike CBD, crystals of phytochrome from Agrobacterium tumefaciens including the CBD and the PHY domain can be photoconverted to a Meta-Rc-like state.