Light up tomorrow: A photochromic material with excellent fatigue resistance, high thermal stability, and quantitative photoswitching can be used as a linear photoswitching material to replace nonlinear optical materials for encoding optical signals. Therefore, information in one light ray can be directly transmitted to another light ray without converting back to the electronic format.

Making a complement: Modification of the structure of thiopeptides has produced numerous analogues that overcome some of their inherent limitations. The combined use of chemical synthesis, semisynthesis, and biosynthetic pathway engineering will allow the development of future thiopeptide-based drugs.

Order makes a difference: A three-dimensional ordered assembly of thin-shell Au/TiO₂ hollow nanospheres exhibits not only a very high surface area but also photonic behavior and multiple light scattering. The designed materials show significantly enhanced visible-light absorption and a visible-light-driven photocatalytic activity several times higher than those of conventional Au/TiO₂ nanopowders.

(Quick) silver DNA: Hg^II and Ag^I ions were found to specifically trigger DNA polymerase catalyzed primer extension in the absence of a Watson–Crick matched nucleotide through the formation of T–Hg^II–T and newly discovered C–Ag^I–T base pairs. The strict base recognition by the metal ions enabled regulated incorporation of the two different metal ions into programmed sites in duplex DNA.

Setting the record straight: An investigation of an imidazolinopyrimidinone (TIC10) reported to induce expression of the immunosurveillance cytokine TRAIL led to a constitutional reassignment of the active pharmacophore. Analysis of TRAIL induction in macrophages revealed the reported structure to be inactive. The structural identity of the active compound was established. The active compound was then synthesized and its activity confirmed.

Phosphate ions in a bind: The tetrakis(bisurea)-decorated tetraphenylethene (TPE) displays fluorescence “turn-on” over a wide concentration range upon phosphate coordination. The fluorescence enhancement can be attributed to the restriction of the intramolecular rotation of TPE by anion coordination. This “anion-coordination-induced emission” (ACIE) is another approach for fluorescence turn-on.

A new Superacid? The novel Brønsted acid hfipOSO₃H (hfip=C(H)(CF₃)₂) was prepared on the kilogram scale. In the gas phase, it is more acidic than sulfuric acid by ten orders of magnitude. Furthermore, this acid may be used for the synthesis of air- and moisture-stable protic ionic liquids of low viscosity and high conductivity.

Hot pockets: Microtuning of the enzyme active pocket gives a smart library of epoxide hydrolase variants with an expanded substrate spectrum covering a series of typical β-blocker precursors. Improved activities of 6- to 430-fold were achieved by redesigning the active site at two predicted hot spots, and enhanced activity toward bulky substrates was found.

The azavinyl rhodium carbenes derived from N-sulfonyltriazole methylenecyclopropanes were found to be very reactive in the divergent synthesis of N-containing heterocycles. Different types of cycloisomerizations were observed depending on the substrates. Derivatization of the products easily gave a series of diazabicyclo[3.2.1]octane derivatives. Bs=bromobenzenesulfonyl, Ms=methanesulfonyl, Piv=pivalate, Ts=4-toluenesulfonyl.

Indolinone synthesis: A new palladium-catalyzed oxidative difunctionalization reaction of N-arylalkenes with primary, secondary, and tertiary α-carbonyl alkyl bromides proceeds through a radical process and provides indolin-2-ones in moderate to excellent yields. The reaction is initiated by a Heck insertion followed by interception of the σ-alkyl palladium(II) intermediate with aryl C(sp²)H bonds. dppe=1,2-bis(diphenylphosphino)ethane.

Ultrasensitive biosensors for H₂O₂ (1 nM limit of detection) have been developed based on peroxidase-redox polymer modified carbon electrodes (see figure; Os= polymer-bound osmium complex). They allow the monitoring of several regimes of H₂O₂ release by mitochondria. In particular, unprecedented nanomolar-amplitude bursts of H₂O₂ have been detected. The results offer opportunities to study the role of mitochondria as a hub of redox signaling in cells.

Bio-inspired catalyst defeats Pt: A biomimetic electrocatalyst for the oxygen reduction reaction (ORR) has been covalently grafted onto multiwalled carbon nanotubes. Without pyrolysis, this bio-inspired catalyst, in which an axial imidazole-coordinated porphyrin mimics the active site of O₂-activating heme-containing enzymes, shows superior ORR activity and stability compared to the state-of-the-art Pt/C catalyst in both acidic and alkaline solutions.

Twisted: A wire-shaped energy device that can perform photoelectric conversion and electrochemical storage was developed through a simple but effective twisting process. The energy wire exhibited a high energy conversion efficiency of 6.58 % and specific capacitance of 85.03 μF cm⁻¹ or 2.13 mF cm⁻², and the two functions were alternately realized without sacrificing either performance.

Hydrogen fuel cell: The oxygen reduction reaction (ORR) kinetics can be strongly accelerated by changing the solvent and its dielectric constant, a possibly general effect in electrochemical systems. The influence of the solvent dielectric constant on the reaction barriers of the ORR is studied by density functional theory (see picture).

Constructing chiral carbonyls: A simple new chiral sulfinylphosphine ligand L was developed, which promoted excellent 1,4-selectivities and enantioselectivities in the rhodium-catalyzed conjugate addition of arylboronic acids to β,γ-unsaturated α-ketoamides. The desired γ,γ-diaryl-α-ketocarbonyl compounds were afforded with high yields and high optical purities.

Pi redox: Expanded isophlorins can undergo reversible two-electron redox reactions to interconvert between 32π-antiaromatic and 30π-aromatic states. trifluoroacetic acid, Et₃O⁺SbCl₆⁻, or NOBF₄ and triethylamine, zinc, or FeCl₂ can be employed as oxidizing and reducing agents, respectively. This reversible redox process can also regulate the topology between a figure-eight and planar conformation.

Controlled growth: Xanthates were employed as controlling agents in the radical polymerization of ethylene (see scheme). The reversible addition–fragmentation chain-transfer technique proceeds under relatively mild reaction conditions (T = 70 °C, P = 200 bar). AIBN=2,2′-azobisisobutyronitrile.

Sweet protection: Two novel synthetic disialyl hexaoses obtained by highly efficient one-pot multienzyme (OPME) reactions were shown to protect neonatal rats from necrotizing enterocolitis (see scheme; GlcNAC: N-acetylglucosamine; Gal: galactose; Neu5Ac: N-acetylneuraminic acid; DSLNnT: disialyllacto-N-neotetraose; LNT: lacto-N-tetraose; DS'LNT: α2—6-linked disialyllacto-N-tetraose).

Building complexity: Diverse 4-aryl-2-quinolinones such as 1 are prepared from propionamides in one pot by pyridine ligand-promoted triple sequential CH activation reactions and a stereospecific Heck reaction. In these cascade reactions, three new CC bonds and one CN bond are formed to rapidly build molecular complexity from propionic acid.

Three not of a kind: An unprecedented arrangement of three formal multiply bonded ligands to one metal center, where the coordinated heteroatoms derive from different element groups, is found in the uranium(VI) carbene imido oxo complex [U(BIPM^TMS)(NMes)(O)(DMAP)₂] (Mes=2,4,6-Me₃C₆H₂).

Five gold rings: The concise total syntheses of the polyprenylated polycyclic acylphloroglucinols (PPAPs) hyperforin and papuaforins A–C, and the formal synthesis of nemorosone have been realized in 17 steps. Key to the realization of these syntheses is the short and scalable assembly of densely substituted PPAP scaffolds through a gold(I)-catalyzed 6-endo-dig carbocyclization of cyclic silylenol ethers.

Active, selective, and cheap: Mo₂C and cobalt-modified Mo₂C were both shown to be effective catalysts for CO₂ conversion by hydrogen in flow reactor experiments over powder catalysts. In-situ XANES measurements verified that Mo₂C can undergo an oxidation-carburization cycle. Modifying Mo₂C with small amounts of cobalt further improved catalytic performance.

A nanohybrid that consists of carbon nanotubes decorated with CoP nanocrystals (CoP/CNT) was prepared by the low-temperature phosphidation of a Co₃O₄/CNT precursor. As a novel non-noble-metal hydrogen-evolution electrocatalyst that operates in acidic media, this nanohybrid exhibits an onset overpotential of only 40 mV and maintained its catalytic activity for at least 18 hours.

The state of play: Enhanced intersystem crossing (ISC) and singlet fission have been shown to occur in pentacene (Pn) derivatives with stable radical substituents. These effects result in the ultrafast formation of a triplet excited state in the pentacene moiety from a photoexcited singlet state, even in dilute solution. The excited-state dynamics of the derivatives were evaluated in detail through transient absorption measurements.

Little helper: Chemical dimerizers are powerful tools for manipulation of enzyme activities in intact cells. The first rapidly reversible chemical dimerization system is introduced, which permits to determine kinetics of lipid metabolizing enzymes in living cells. This new method was applied to induce and stop phosphatidylinositol 3-kinase activity, allowing to quantitatively measure 3,4,5-trisphosphate turnover.

Following the Curie symmetry principle and Aizu rule, it was discovered there is a paraelectric-to-ferroelectric phase transition in Ca(NO₃)₂(15-crown-5) at T_c=205 K, which was confirmed by calorimetry and second harmonic generation measurements. The ferroelectric mechanism is attributable to distortion of the coordination of the central Ca atom.

Singles only: A single-cell chemical proteomics strategy with an activity-based probe (ABP) enables observation of low-abundance membrane receptors at the single-cell level by discriminating them from the whole proteome. The strategy avoids problems associated with cytometry-based techniques, and could be used to identify low-copy receptors on the primary neurons of animals.

Stability: A modified nucleoside triphosphate is incorporated into DNA sequences using polymerase. The resulting photocaged DNA is resistant against cleavage by restriction endonucleases (REs) and fully replicable by polymerase chain reaction (PCR) or primer extension (PEX).

Changing phases: In the course of solid-state photoreactions, the single crystal of a reactant can be transformed into a single crystal of the product or it can become amorphous. Between these scenarios exist the reconstructive phase transformations, where the single crystal becomes a powder. A detailed description of the latter is given.

Promising returns of gold on the side: In a designed Au–Bi₂S₃ heteronanostructure photocatalyst, Au nanoparticles were located at the center of the semiconductor nanorods (see picture), rather than at the tip, as usually reported. These nanostructures were found to be efficient visible-light photocatalysts and to have excellent photocurrent and photoresponse properties.

Three's Company: The resveratrol trimer vaticanol A, along with a number of diastereomeric congeners, has been synthesized for the first time through an effective strategy utilizing three reactive quinone methide intermediates to forge three critical bonds (highlighted in pink). These events, one of which succeeded only under very specific conditions, expediently generated its [7,5]-carbocyclic core and afforded a unique sequence for dihydrobenzofuran formation.

Two-pronged attack: A cisplatin prodrug was developed with the ability to induce cancer cell death through two distinct pathways, targeted direct cytotoxicity and activation of innate immune cells for cell-mediated cytotoxicity, to realize the concept of a multimodal immuno-chemotherapeutic approach (see figure; m: D-Met).

Turning a negative into a positive: The fully reversible conversion between an anionic six-membered phosphorus–nitrogen heterocycle and a bicyclic diazaphospholenium cation as stable redox states leads to an “umpolung” of the electronic properties which is of interest for smart materials.

A “narcotic” effect of barbital on the Brownian motion of novel [2]rotaxanes with two di(acylamino)pyridine binding sites was observed: The establishment of hydrogen-bond arrays with barbital caused dynamic restraint of the ring shuttling (see picture). The original translational motion was reestablished by a competitive recognition event with an external barbital binder.

When one clamp closes…︁ Single-molecule Förster resonance energy transfer and single-molecule fluorescence polarization were used to monitor the loading of a sliding DNA clamp onto double-stranded DNA by the clamp loader (see picture). Thus, the dynamic features of a DNA clamp in the DNA/DNA-clamp/clamp-loader ternary complex were revealed.

Bull's eye! An activatable photosensitizer capable of specifically inducing the death of β-galactosidase-expressing cells in response to light irradiation was developed. Reaction with the enzyme resulted in a dynamic structural change to the phototoxic open form (see scheme), thus enabling the specific ablation of cells of interest in living tissues.

Concerted action: Allylic alcohols were directly used in the title reaction under mild conditions. The reaction smoothly proceeds by the concerted action of a Pd catalyst, a pyrrolidine co-catalyst, and a hydrogen-bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the π-allylpalladium complex by lowering the activation barrier.

Diselenide bonds are dynamic covalent bonds. Their metathesis can be induced by irradiation with visible light and likely proceeds through a radical mechanism, as the exchange reaction between two different diselenides was suppressed by the addition of the radical scavenger 2,2,6,6-tetramethylpiperidine N-oxide (TEMPO).

All sixes and sevens: A new class of conjugated polycyclic molecules have a nearly flat C₆-C₇-C₆-C₇-C₆ polycyclic framework with a p-quinodimethane core. With a field-effect mobility of up to 0.76 cm² V⁻¹ s⁻¹ as measured from solution-processed thin-film transistors, these molecules are alternatives to the pentacene analogues for application in organic electronic devices.

The nickel-catalyzed α-arylation of ketones with readily available phenol derivatives (esters and carbamates) provides access to useful α-arylketones. The use of 3,4-bis(dicyclohexylphosphino)thiophene (dcypt) as an air-stable ligand enables this transformation. The intermediate of an assumed CO oxidative addition was isolated and characterized by X-ray crystal-structure analysis.

Breaking N-BC News: The first general synthesis of boron-substituted monobenzofused 1,4-azaborines has been developed. As part of the synthetic investigations, a unique κ²-N-η²-BC coordination mode was discovered and investigated.

Algae as feedstock: Crude algae oil from the strain Phaeodactylum tricornutum was transformed into polycondensation-grade purity monomers and thus utilized as feedstock for the production of an algae oil based polyester.

Destruction and reconstruction: The combination of a hypervalent-iodine-mediated oxidative dearomatization and palladium-catalyzed domino reaction provides a practical approach to 3,4-difunctionalized benzofurans and polycyclic benzofurans from 2-alkynylphenols.

Old cytochrome, new tricks: Mutation of the proximal Cys residue in the cytochrome P450 enzyme from Bacillus megaterium (P450-BM3) leads to highly active, oxygen tolerant, and enantioselective catalysts for the cyclopropanation of N,N-diethyl-2-phenylacrylamide. Directed evolution of a histidine-ligated P450-BM3 enabled the enantioselective formal synthesis of levomilnacipran.

The first isolated nitridyl radical (^.N²⁻) complex was obtained by photochemical activation of the rhodium–azide complex [(PNNH)Rh(N₃)] (1), producing N₂, H₂, and the paramagnetic complex 2. Complex 2 reacts selectively with CO to produce complex 3, presumably by N,N-coupling of nitridyl radicals.

Capture and release: The established industrial colorant quinacridone reacts with CO₂ following electrochemical reduction, with an uptake efficiency of 4.6 mmol CO₂/g quinacridone at room temperature. The CO₂ can be released by electrochemical oxidation.

Bridging length scales: A powerful strategy of assembling surface-functionalized nanocrystalline BaTiO₃ particles into a highly porous macroscopic framework is presented. After supercritical drying, the obtained structures show a large surface area and a low density. By starting off with functional building blocks on the nanoscale and ending with a body in the centimeter range, over seven orders of magnitude in length scales are addressed.