Let's couple together! The multicomponent reactions involving arynes offer direct access to unusual heterocyclic scaffolds and 1,2-disubstituted arenes. This transition-metal-free, one-pot construction of molecular complexity is likely to play a pivotal role in various carbon–carbon and carbon–heteroatom bond-forming reactions.

Lewis adducts between N-heterocyclic carbenes and fullerenes have been isolated and their structures confirmed by X-ray crystallography. This work shows that simple fullerenes such as C₆₀ or C₇₀ can act as Lewis acids. This result not only opens new perspectives in fullerene chemistry but might also have strong implications in emerging fields such as the metal-free activation of small molecules.

Twin set: Our obsession for (enantio)selectivity in catalysis means we tend to analyze and graphically communicate our findings in the form of single-handed cycles. However, dual-cycle racemic catalysts are of distinct utility in polymerization, prediction of stereoselectivity, and mechanistic study.

Drying out: The evaporation of solutions of nonvolatile solutes is one way to generate complex ordered structures. An array of facile and robust preparative strategies based on controlled evaporative self-assembly (CESA) of confined solutions have been exploited to rationally assemble various soft and hard materials into spatially ordered structures (see picture) with engineered properties and functionality over large surface areas.

A face off: Diisobutylaluminum hydride (DIBAL-H) has been found to be an effective O-desilylating reagent at the primary face of cyclodextrins. This methodology shows high chemo- and regioselectivity and provides an effective route to orthogonally protected, multisubstituted cyclodextrin derivatives.

Jacketed supramolecular strand: Meter-long supramolecular strands were obtained by encapsulating them in polymer gels using a microfluidic channel (see picture). The nanofibers in the strands are self-assembled and aligned under the laminar flow conditions. Their mechanical strength was sufficiently high to allow their patterning onto a substrate and use them as a template for synthesizing an insoluble, conductive polymer.

Proteins in focus: Dynamically tunable protein microdevices were built up by a simple “top-down”, maskless, femtosecond laser direct writing approach with bovine serum albumin. This technique was used to produce biocompatible microlenses that swell and shrink reversibly in response to changes in the pH of the surrounding solution. These responses to environmental stimuli can be used to focus the microlenses.

On the right path: The mechanisms of endocytosis of cetuximab (C225) and its nanoconjugates have been elucidated in a pancreatic cancer cell line. By using gold nanoparticles as a scaffold, it is possible to switch the pathway for endocytosis from a Dyn-2-dependent caveolar mechanism to Cdc42-dependent pinocytosis/phagocytosis. Tailoring endocytotic mechanisms may enable specific intracellular pathways to be targeted.

Carbon in charge: A straightforward method is presented for the synthesis of carbon nanotube (CNT)/porous carbon composite electrodes with uniform distribution of the CNTs and high surface area of the carbon material. The crystallinity of the CNTs is not affected by the high-temperature activation process. Monolithic CNT/activated carbon composite electrodes that do not need binder or current collector were also developed.

Calculated answer: First-principles calculations have been applied to calculate the energy barrier for the key step in CO formation on a Pt surface (see picture; Pt blue, Pt atoms on step edge yellow) to understand the low CO₂ selectivity in the direct ethanol fuel cell. The presence of surface oxidant species such as O (brown bar) and OH (red bar) led to an increase of the energy barrier and thus an inhibition of the key step.

Learn about Alzheimer: The molecular conformation of a toxic β-amyloid oligomer structure was determined by NMR spectroscopy (see picture). The measurements show a N-terminal β strand that controls the partitioning between oligomer and protofibril formation. Targeting the N-terminus of the peptide neutralizes Aβ-dependent neuronal dysfunctions. The data have important implications for understanding the structural basis of Alzheimer's disease.

Picky cage: A dicopper(II)-paddle-wheel-based metal–organic framework (PCN-80, see picture) with a rare (3,3,4)-connected topology has been synthesized by using a unique octatopic ligand featuring 90° bridging-angle dicarboxylate moieties. PCN-80 has Brunauer-Emmett-Teller (BET) and Langmuir surface areas of 3850 and 4150 m² g⁻¹, respectively. It exhibits high gas-uptake capacity for H₂ and large adsorption selectivity of CO₂ over N₂.

Molecular shuttlecocks: The introduction of tripodal ternary acids (red; see picture) to the cobalt/calixarene (green) systems led to the formation of four unprecedented calixarene-based nanoscale coordination cages through a [6+8] condensation. The overall periphery diameters of the nanocages ranged from 3.3 to 4.7 nm, and there were two sizes for the internal cavities (1.1 and 1.7 nm).

Ball and plane: The structure of La@C₈₂ was clarified by single-crystal X-ray diffraction of samples co-crystallized with [Ni^II(OEP)] (OEP=octaethylporphyrin; see structure La red, N blue, Ni yellow, H pink). The charge-carrier mobility of the co-crystal was determined using flash-photolysis time-resolved microwave conductivity measurements. The material exhibited an anisotropic and high electron mobility of up to 0.9 cm² V⁻¹ s⁻¹.

Electromagnetic vacuum fields are omnipresent in our universe, inducing many events such as spontaneous emission, Lamb shift, and Van der Waals forces. As demonstrated here, a chemical reaction can be influenced by strongly coupling the energy landscape governing the reaction pathway to vacuum fields in an optical cavity (see picture; MC=merocyanine).

A void in the issue: A one-step self-assembly of γ-Keggin sandwich-type silicotungstates with M₂Zn₂ (M=Co, Ni, Zn) tetranuclear cores and tetrabutylammonium cations gave porous ionic crystals. These porous crystals are hollow frameworks containing large voids (ca. 38×38×38 ų, see picture, voids yellow), between which guest molecules can be exchanged through the connecting channels.

Still elusive: The reduction of dimethylimidazol-2-ylidene dichloroborane by sodium naphthalenide has been suggested to provide a borylene that cycloadds to naphthalene to make a borirane. Evidence has been provided that this borirane instead arises from coupling of a boryl radical and sodium naphthalenide. In contrast, reduction of 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene dichloroborane and the related dimesityl derivative provide novel CH insertion products that may have arisen from a borylene.

Magnetic moments: The orientation of the title single-molecule magnet was investigated by magnetic single crystal and luminescence characterization, supported by ab initio calculations, and was found to be governed by the position of the hydrogen atoms of the apical water molecules. This finding suggests that simple magneto-structural correlations can give misleading clues for research in molecular magnetism as well as in the design of MRI contrast agents.

Something to remember: A rotaxane could be operated as a bistable memory element under kinetic control (see picture). Data was written on the molecule by an oxidation stimulus and locked by UV light irradiation. After the writing session, the oxidized species was reduced back to the original form without losing the written data for a few hours. Light irradiation also protects nonoxidized rotaxanes from accidental writing.

Who can split water? Two polymorphs of nanocrystalline cubic spinel and rhombohedral layered lithium cobalt oxides have been prepared and their application in the photocatalytic oxidation of water examined. The main factor that determines the catalytic activity of the different phases is the presence of a Co₄O₄ cubic core, which is present in the cubic form of the catalyst, but not in the layered structure (see scheme).

A cooperative catalyst that features urea H-bonding and a cobalt center was developed for anti-selective asymmetric Henry reactions (see scheme). The H-bonds of urea play a crucial role in the improvement in yield (from 30 % to 84 %), enantioselectivity (from 78 % to 96 %), and anti diastereoselectivity (from 3:1 to 48:1). A short synthesis of (1R,2S)-methoxamine hydrochloride was also accomplished with this catalyst.

Turn off the lights! A universal nanoquencher that quenches a broad range of visible to near-infrared dyes by using a series of dark quenchers incorporated into a cell-permeable mesoporous silica nanoparticle has been developed. In combination with dye-labeled substrates, this nanoquencher boosts multiple fluorescence signals upon specific proteolysis, which allows real-time imaging of proteolytic cascades (see scheme).

Select an isoform: Linking of cosubstrate and substrate binding sites enables highly selective inhibiton of isoforms of human histone lysine demethylases. The results should provide a basis for the development of potent and selective JmjC inhibitors, possibly suitable for clinical use.

Highly selective CO₂ sorption and inverse CO₂/C₂H₂ sorption selectivity (4.8 at 278 K, 100 kPa) were achieved with an organic–inorganic ionic crystal. The key for the high affinity toward CO₂ is the combination of structural flexibility and strong binding sites (K⁺) characteristic of organic–inorganic ionic crystals.

Good combination: Enantioselective enzymatic hydrolysis was combined with a mechanically facilitated racemization process to prepare (S)-1,1′-binapthol ((S)-binol) in high yield and enantiopurity from a racemic precursor in a single step (see scheme). The enzyme cholesterol esterase stereoselectively hydrolyzes esters of (S)-binol and ultrasound was applied to achieve mechanically facilitated racemization of the precursor material.

Battling the flu: Zanamivir (Relenza) is widely prescribed as an anti-influenza drug. It contains a vicinal amino alcohol, which is in an anti orientation, and is readily accessed by an anti-selective catalytic asymmetric nitroaldol (Henry) reaction promoted by a heterobimetallic complex (see scheme; PMB=p-methoxybenzyl). Additional synthetic manipulation of the nitroaldol product allowed the enantioselective synthesis of zanamivir.

It takes two: Xantphos ligands that contain amidate groups are selective for the linear versus the branched-chain products in the rhodium-catalyzed hydroformylation of 1-octene. However, the catalyst only undergoes CO₂-mediated phase switching in the presence of amidine-substituted triphenylphosphine (see scheme).

On the sunny side: A homogeneous system for H₂ production and hydrocarbon oxidation was developed in the absence of any sacrificial reagent. This system consists of [Ru(TPA)(H₂O)₂]²⁺ and [Fe₃(CO)₁₂] as catalysts and [Ru(bpy)₃]²⁺ and [Ir(bpy)(ppy)₂]⁺ as photosensitizers (PS). Water is the oxygen source as well as the source for H₂ formation (see picture; Sub=organic substrate).

Into the fold: Intramolecular CH⋅⋅⋅O hydrogen bonding has been utilized to create new aromatic triazole foldamers. Remarkably, all the triazole units of the foldamers are guided to orientate inward to form a nitrogen ring. As a result, they can efficiently bind neutral tri- and didentate organohalogens through multiple N⋅⋅⋅X (X=Cl, Br, I) halogen bonds to form stable 1:1 complexes.

It takes two: For the reduction of amides to amines iron catalysts were developed. A combination of two different iron catalysts made possible the challenging reduction of primary amides (see picture).

A question of nobility: A biomimetic nickel thiolate complex (see scheme; TEA=triethylamine) exhibits unprecedented activity for the title reaction. By using a low concentration of a sacrificial donor, the system maintains significant activity for at least 60 hours. The enhanced stability of the system is ascribed to the ability to proceed through an oxidative quenching pathway.

One and two: The C₂ compound pinBOCH₂OCHO (see scheme; HBpin=pinacolborane) and several C₁ compounds have been obtained from the borane-mediated reduction of CO₂ under mild conditions with the catalyst precursor [RuH₂(H₂)₂(PCy₃)₂]. Mechanistic investigation highlights the role of a series of new carbonyl ruthenium complexes that were characterized by multinuclear NMR spectroscopy, IR spectroscopy, and X-ray diffraction studies.

N-heterobicyclic scaffolds: Highly efficient palladium-catalyzed cyclizations of oxime esters with cyclic alkenes were used as a general entry to perhydroindole and related scaffolds. The chemistry is reliant upon the use of P(3,5-(CF₃)₂C₆H₃)₃ for the key C(sp³)N bond-forming process and this facilitates cyclizations with enhanced levels of efficiency across a range of sterically and electronically distinct substrates.

Rings with a twist: The highly enantioselective construction of five-membered spiroindolenines has been realized by the iridium-catalyzed intramolecular allylic dearomatization of indoles. The stereospecific migration of these spiro cyclopentane-1,3′-indole products provides enantioenriched 2,3,4,9-tetrahydro-1H-carbazoles.

Dissolving platinum: A noncorrosive, basic ionic liquid has been developed as a solvent system for the electrodissolution of platinum (see image). The metal was dissolved at an ultrahigh rate, and the facile recovery of pure platinum and platinum alloys from the same solution was achieved without any additional treatment of the solution or exchange of the medium.

Uracil is a common form of DNA damage resulting from hydrolysis of cytosine, and cellular uracil DNA glycosylases (UDG) have evolved to remove it specifically. The use of nonnatural pyrene deoxyriboside in short DNA oligomers to directly report on UDG enzymatic activity is described. The mechanism relies on the use of uracil as a strong quencher of pyrene, and enzyme repair activity can be directly imaged with bacterial cells in real time.

Good migrations: The highly regioselective migration of a sulfonyl group for the synthesis of functionalized pyrroles is reported (see scheme; DMF=N,N-dimethylformamide). The migration of the sulfonyl group to different positions can be controlled with high selectivity, thus allowing the formation of both α- and β-(arylsulfonyl)methyl pyrroles with high yields.

Unsupported catalyst for green chemistry: The aerobic oxidation and coupling of primary alcohols (methanol, ethanol, n-butanol) to give the corresponding aldehydes and esters at temperatures below 100 °C is facilitated by unsupported nanoporous gold catalysts. The experimental conditions employed allow a close comparison to model experiments and open the door to a molecular-level understanding of the reaction.

Now we are six: Planar B₆ rings embedded in one-dimensional Ti₇ wheels have been found in the crystal structure of a solid-state phase (Ti₇Rh₄Ir₂B₈) for the first time. First-principles calculations indicated strong BB bonding but also significant interactions with the surrounding titanium atoms (see picture).

Malaria is a serious global health issue. Artemisinin combination treatments are the first-line drugs, but supplies are limited because artemisinin is obtained solely by extraction from Artemisia annua. A continuous-flow process that converts dihydroartemisinic acid into artemisinin (see scheme) was shown to be an inexpensive and scalable process that can ensure a steady, affordable supply of artemisinin.

H₂-O-T! Aromatic O-heterocycles are a challenging substrates for asymmetric hydrogenation (H₂). An in situ formed chiral N-heterocyclic carbene (NHC) ruthenium complex allows the high yielding, completely regioselective, and highly asymmetric hydrogenation of substituted benzofurans at room Temperature, giving valuable 2,3-dihydrobenzofurans (see scheme).

One to two and back again: A disulfide–thiolate interconversion process in a dinuclear copper complex is induced by chloride ions (see scheme). Within this compound, the coordinating copper atoms serve either as electron source or as electron sink and thus oscillate between the oxidation states +I and +II.

A shot in the arm for anticancer vaccines: Synthetic MUC1 glycopeptides bearing the STn and 2,6-ST antigens were conjugated covalently to BSA (see scheme). The obtained synthetic vaccines induced very strong immune responses in Balb/c mice. Predominant IgG isotype antibodies were induced. The antibodies exhibited strong binding to breast cancer cells of the MCF-7 cell line.

A complete set of 2-nitrobenzyl-modified reversible terminators have been developed, which upon exposure to UV light generate natural hydroxymethyl nucleotides (see scheme). The combination of a stereospecific (S)-tert-butyl group (R) at the benzylic carbon and a 5-OMe group (R′) on the 2-nitrobenzyl ring substantially increase the rate of photochemical cleavage. For 7-deaza-7-hydroxymethyl-2′-deoxyguanosine, these modifications led to a rate increase of more than one order of magnitude.