Metal recycling: A sustainable, capacitance-assisted carbon capture and sequestration method can turn scrap metal and CO₂ into metal carbonates at an attractive energy cost.

Only a click away: Nonplanar donor–acceptor (D-A) chromophores can be prepared by click synthesis through [2+2] cycloaddition-retroelectrocyclization (CA-RE). This is a powerful method for producing functional molecular and polymeric systems for use in next-generation electronic and optoelectronic devices.

Multicompartment micelles (MCPs), comprising sequences of repeated elemental discoid parts connected by fasciculus, can be disassembled through consequent release of small spherical micelles using an electrostatic field. During this disassembly process, release of loaded species (MTNT and FITC) can be achieved from the MCPs in chronological order.

Diverse and easy: Structure-guided rational protein engineering resulted in a 2-keto-3-deoxy-l-rhamnonate aldolase variant fused with a maltose-binding protein (MBP-YfaU W23V/L216A), which can provide straightforward access to chiral building blocks and a series of unprecedented proline and pyrrolizidine α-amino acid derivatives.

GN'R light: Narrow thiophene-edged graphene nanoribbons (GNRs) were prepared from polychlorinated thiophene-containing poly(p-phenylene)s using photochemical, metal-free cyclodehydrochlorination (CDHC). The regioselectivity of the CDHC reaction allows the preparation of both longitudinally symmetrical and unsymmetrical GNRs and, consequently, modulation of their optical and electronic properties.

The one-step synthesis of CO₂-based block copolymers with completely alternating polycarbonate segments was achieved by simultaneous ring opening copolymerization of CO₂/epoxides and RAFT polymerization of vinyl monomers. A double chain-transfer effect ensures narrow polydispersities, and a ligand exchange reaction impedes the formation of homopolycarbonates.

The hunt is on: Huntingtin protein (htt) is the key agent of Huntington's disease, but its high-resolution characterization has been impaired due to the presence of a long tract of consecutive glutamines. By combining nonsense suppression and cell-free expression, single glutamines in htt were site-specifically labeled to perform NMR experiments, thus paving the way to understanding the impact of htt structure and dynamics on Huntington's disease.

A nanopore sensing strategy based on a triplex molecular beacon was developed for the detection of specific DNA or multivalent proteins. Upon analyte binding, the loop of the molecular beacon is opened and the stem-forming DNA probe is released for nanopore translocation recording. The frequency of current signatures can be used to quantify the concentrations of the analytes.

No F required: Fluoride-free synthesis of siliceous zeolites remains highly challenging—of the 234 recognized zeolite framework structures, less than 25 have been made in purely siliceous form without using fluoride. The dry gel conversion technique has been used to synthesize two new fluoride-free siliceous zeolites. Systematic studies and analysis reveal mechanistic insights into fluoride-free siliceous zeolite synthesis.

Involvement of a synthetic copper triad in binding and reduction of O₂ is demonstrated. The presence of the third Cu ion is crucial to supplying the third reducing equivalent for O−O bond cleavage and reduces the overpotential.

A general fragmentation method that transforms furans into alkynes, by dual C−C double-bond cleavage, is described. The reaction is proposed to proceed by sequential [4+2] cycloaddition between furan and singlet oxygen, and a formal retro-(3+2) fragmentation of the endoperoxide intermediate. The synthetic utility was demonstrated by a seven-step synthesis of the proposed structure of aglatomin B.

In reverse: A nickel-catalyzed reductive arylation of ambiphilic α-bromoalkyl boronic esters with aryl halides unlocks an opportunity to promote the catalytic cross-electrophile coupling of ambiphilic reagents with aryl halides through a formal reversal of polarity, and is a straightforward alternative for preparing densely functionalized alkyl-substituted organometallic compounds under mild conditions.

NIR-II emission: Activatable nanoprobes with second near-infrared emissions were constructed. The designed probes displayed H₂S-activated ratiometric fluorescence and light-up NIR-II emission and were applied to the specific imaging of H₂S-rich colon tumors and differentiation of cancer type.

A rigid structure: Callyaerin A, an anti-tuberculosis macrocyclic peptide containing a rare (Z)-2,3-diaminoacrylamide moiety, was synthesized in high yield using an uncommon building block, Fmoc-formylglycine-diethylacetal. Variable-temperature NMR studies revealed the high conformational rigidity that the (Z)-2,3-diaminoacrylamide moiety confers on peptide structure, thus highlighting its potential as a novel structural element for conformation constraints.

By mimicking the dynamic and reciprocal interactions between the extracellular matrix and cells, the matrix growth-mediated self-assembly (SA) of organic molecules into higher-order organization has been developed. The dynamic self-assembly of a nanofibrous scaffold facilitates the hierarchical assembly of rigid molecule into a layered structure with up to a ninefold increase in height.

A simple and direct method for the synthesis of aryl ethers by reacting alcohols/phenols with aryl ammonium salts was developed. This reaction proceeds smoothly and rapidly at room temperature in the presence of a commercially available base, and has a broad substrate scope for both reactants, including natural products, pharmaceuticals, and dyes.

Transformation of amides: Using a halogen bond (XB) donor and Schreiner's thiourea as cooperative catalysts, various amides were directly coupled with glycosyl trichloroacetimidates to give unique N-acylorthoamides in good yields. Synthetic applications of N-acylorthoamides, including rearrangement to the corresponding β-N-glycosides, were also demonstrated.

peri useful: Radical cyclization reactions at a peri position were used for the synthesis of polyaromatic compounds. Depending on the choice of reaction conditions and substrate, this flexible approach led to Bu₃Sn-substituted phenalene, benzanthrene, and olympicene derivatives (see scheme). Subsequent reactions with electrophiles provided synthetic access to previously inaccessible functionalized polyaromatic compounds.

An optimum amount (10 wt %) of fluoroethylene carbonate (FEC) as electrolyte additive enables a robust LiF-rich SEI on MoS₂, which significantly suppress the continuous decomposition of electrolytes. As a result, MoS₂ in the FEC-containing electrolyte shows an improved lithium storage performance, with a reversible capacity of about 770 mAh g⁻¹ for 200 cycles at 1 A g⁻¹ and a stable capacity of about 510 mAh g⁻¹ at 20 A g⁻¹.

Locked into position with a Pd key: A palladium-catalyzed atroposelective C−H alkynylation was developed and applied to gram-scale, stereocontrolled formal syntheses of (+)-isoschizandrin (see scheme) and (+)-steganone. tert-Leucine was identified as an efficient catalytic transient chiral auxiliary for this transformation, which enabled the preparation of a wide range of enantiomerically enriched biaryl compounds in good yields.

Helical polymers: A computational methodology on poly(phenylacetylene) oligomers allows assignment of the helical sense of polyene backbones based on their electron circular dichroism (EDC) signature. The calculated ECD spectrum for small oligomers of polyphenylacetylenes (PPAs) shows a very good match with the experimental spectra of the PPA polymers.

Crystal clear: A crystalline sponge (CS)-based method was developed for the prioritization of target analytes present in a methanolic crude extract from a red alga. Subsequent analysis by the CS method enabled the clarification of the structures of six sesquiterpenoid natural products, starting from only around 10 mg of the crude extract.

Nitrogen atom transfer from a lattice-confined Ru₂ nitride to toluene generates benzylamine. The intramolecular deuterium kinetic isotope effect (KIE), determined for the amination of a partially deuterated substrate, was compared with the intermolecular KIE, determined by competitive amination of a mixture of perdeuterated and nondeuterated substrate, to establish the relative rates of substrate diffusion and interstitial chemistry.

Small ′Rh′ings: The asymmetric rhodium-catalyzed arylation of simple achiral nonfunctionalized cyclopropenes provides a variety of arylated cyclopropanes with high diastereo- and enantioselectivities (e.r. from 90:10 to 99:1). The reaction proceeds under mild reaction conditions. cod=1,5-cyclooctadiene.

Amine-terminated CDs reversibly transfer between aqueous and organic solvents switched by CO₂ at atmospheric pressure. This property was used to demonstrate effective homogeneous catalysis and heterogeneous separation. Catalyst recycling was developed and their phase transfer behavior was investigated by fluorescence and ¹³C NMR spectroscopy.

Best of both worlds: Cyclic ketones with α-quaternary centers underwent kinetic resolution with a cyclohexanone monooxygenase (CHMO) to give lactones with tetrasubstituted stereocenters with high enantioselectivity (see scheme). Subsequent SmI₂-mediated cyclization led to complex cycloheptan- and cycloctan-1,4-diols. Enantiomerically enriched cyclic ketones from the resolution were converted into cyclobutanols by SmI₂-mediated cyclization.

Breaking and building: A rare uranium hydride complex is formed by cooperative dihydrogen cleavage by a uranium nitride. Hydride addition to small molecules, such as carbon dioxide, is facilitated.

A surface with controllability in both the surface chemistry and microstructure is constructed by grafting the poly(N-isopropylacrylamide) (PNIPAAm) onto shape memory polymer (SMP) pillars. Based on the excellent controllability, reversible and precise wetting control from superhydrophilicity to superhydrophobicity can be realized, which also allows the surface to be used as a rewritable platform for designing various gradient wettings.

Incompatible interactions: The hydrophobic cavity of a polyaromatic capsule efficiently encapsulated hydrophilic oligo(lactic acid)s in water (see scheme). The X-ray crystallographic and ITC analyses revealed that the unusual host–guest behavior is caused by enthalpic stabilization through multiple CH–π and hydrogen bonding interactions.

By our powers combined: A new strategy based on combinatorial probes immobilized on nanostructured microelectrode sensors enables the analysis of mutant sequences from circulating tumour nucleic acids.

A Fe^II₄L₄ coordination cage enabled complete extraction of ReO₄⁻, a nonradioactive surrogate of TcO₄⁻, from water into an organic phase. In the presence of 10 other anions, 97 % of ReO₄⁻ was selectively removed. The extracted ReO₄⁻ could be released and the cage extractant recycled by a solvent-switching strategy. Rendering the cage water-soluble also allowed complete extraction of ReO₄⁻ from an organic phase into water.

Rattling the cage: A new class of coumarin-based photocaging groups, with an electron-rich styryl moiety at the 3-position, were synthesized. They feature large π-conjugation, carbocation stabilization, and undergo an intramolecular cyclization rearrangement. Their long-wavelength excitation, rapid photolysis, and photobleaching are beneficial for use in high-concentration and thick specimens. D=electron donor, LG=leaving group.

Pores of hands: Two structurally related small-pore AlPO₄ molecular sieves, PST-13 and PST-14, were synthesized. Their structures were solved and refined by electron crystallography, which showed that PST-13 and PST-14 consist of pairs of enantiomeric structural building units, namely, tetrahedral ([4²6²]) 1,5-open and 1,6-open double 4-rings.

In a spin: A benzene-1,3,5-triaminyl radical fused with three Zn^II-porphyrins was synthesized, and was shown to possess a quartet ground state by ESR and superconducting quantum interference device (SQUID) studies. Despite its high-spin nature, this triradical is remarkably stable under ambient conditions. The high stability of the triradical is attributed mainly to effective spin delocalization over the porphyrin segments.

Pushing pillars apart: A new strategy for creating homochiral MOFs was developed through the fusion of pillaring and templating concepts. This dual-concept strategy makes use of the synergy among multiple competing interactions in a tri-organic system, leading to the synthesis of a series of flexible homochiral frameworks.

Put in their places: IFR-type zeolites with tuned Al locations at different tetrahedral sites (T1–T4) are synthesized with different organic structure-directing agents (OSDAs), revealing the Al site-directing ability of OSDAs. The occupancy of Al at each site is strongly correlated with the energies of the zeolite–OSDA complexes, suggesting that the Al locations are primarily governed by the energetic preferences.

High-functioning alcoholic: A method is described for valorization of lignin model compounds. Reductive alcoholysis of aryl ethers catalyzed by palladium in alcoholic solvent is initiated by partial hydrogenation of the arene ring to an enol ether. Cleavage of the strong aryl C−O bond is achieved by alcohol addition to the enol ether and R−OH elimination.

From waste to value: A strategy for converting renewable lignin biomass into value-added nitrogen-containing chemicals is reported. Model compounds of lignin containing a 4-O-5 linker were cross-coupled with amines by dual C(Ar)−O bond cleavages to generate valuable nitrogen-containing derivatives.

Single-nanoparticle photoelectrochemistry: A phototelectrochemical method is used for quantifying the electron transfer of a single N719@TiO₂ nanoparticle and evaluating the nanostructured TiO₂ film by experiment and simulation. These results provide new insights to facilitate the fabrication of photoelectrochemical devices with better performance.

Going through a phase: Counterion-induced asymmetric control of reactions of tetrahedral ammonium cations is useful but remains challenging. Demonstrated here is the use of chiral anion phase-transfer catalysis to achieve ring-opening reactions of readily available tetrahedral azetidiniums with good enantioselectivities. Precise control over the formation and reaction of the key chiral ion pair, as well as inhibition of the background reaction by the biphasic system, is key to the success of this method.

′Az′ is: The enantioselective aza-benzoin reaction of aldehydes with 2H-azirines was developed by utilizing a chiral N-heterocyclic carbene (NHC) as the catalyst. A wide range of corresponding aziridines can be obtained in good yields with high enantioselectivities. The obtained optically active aziridines should be useful in the synthesis of other valuable molecules. MTBE=methyl tert-butyl ether.

A local-curvature-controlled strategy was developed for tailored non-epitaxial growth of hierarchical complex nanostructures. The synthesis of hierarchical nanostructures with novel shapes was achieved through site-selective growth of silica nanorods on non-spherical seeds (red in scheme).

The dynamic duo: A nitrogen atom and the carbonyl group in heterobiaryl ketones form a Lewis pair which is responsible for the labilization of the stereogenic axis, and constitutes the key strategy for developing a zinc-catalyzed asymmetric hydrosilylation by dynamic kinetic resolution. This process simultaneously installs a stereogenic axis and a stereocenter for the highly enantioselective synthesis of heterobiaryl carbinols.

Lewis base activation of iodine: A facile and effective system has been developed for the regio- and chemoselective ring-opening/electrophilic functionalization of cyclopropanes through C−C bond activation by [bis(trifluoroacetoxy)iodo]benzene with the aid of the Lewis base promoter p-toluenesulfonamide.

All-inorganic perovskite films were fabricated by a multistep solution-processed deposition strategy, in which a phase conversion from CsPb₂Br₅ to CsPbBr₃ and then to Cs₄PbBr₆ was achieved upon increasing deposition cycles of a cesium bromide solution. A power conversion efficiency up to 9.72 % was obtained from the CsPbBr₃ solar cells, which are free of hole-transporting layers.

In an impressive show of independence, iodonium ylides underwent direct cyclization with unmodified tertiary aryl amines (see scheme). The transformation, which was developed on the basis of the exceptional finding that iodonium ylides could cleave the C(sp³)−H bonds of tertiary aryl amines, proceeded in the absence of a transition-metal catalyst and without the use of an additional initiator/oxidant.

At a single stroke: A convenient method has been developed for the base-promoted direct amination of β-unsubstituted 5,15-diazaporphyrins (DAP) with secondary and primary amines to produce 3,7,13,17-tetraamino- and 3-amino-DAPs, respectively (see scheme; Ar=2,4,6-Me₃C₆H₂). The palladium complex of the 3,7,13,17-tetrakis(diphenylamino)-DAP generated singlet oxygen in high yield under irradiation with near-infrared light.

Absolutely correct: Iriomoteolide-2a, a cytotoxic 23-membered macrolide natural product of marine origin, was obtained by total synthesis for the first time. The study culminated in a revision of the original stereochemical assignment and the unambiguous determination of the correct absolute configuration.

Give me a ring: A novel method for synthesizing strychnos alkaloids was developed in which a chiral N,N′-dioxide Sc(OTf)₃ complex catalyzes the enantioselective tandem Michael addition of tryptamine-derived oxindoles to alkynones. The reaction enables the facile preparation of enantioenriched spiro[pyrrolidine-3,3′-oxindole] compounds, which provides a novel strategy for the synthesis of monoterpenoid indole alkaloids.

Thinking outside the BOX: A Cu^II-catalyzed asymmetric [3+2] annulation of indoles with quinones provides diverse access to the optically pure benzofuroindolines, including those without 3-substituents that are susceptible to rearomatization, for the first time. The use of a BOX ligand copper hydrate complex in combination with activated molecular sieves for the controlled release of H₂O leads to reproducibly high yields and excellent enantioselectivity.

Merger negotiations: Direct β-arylation of N-protected lactams with simple aryl iodides was developed by merging soft enolization and palladium-catalyzed redox cascade. The reaction is operated under mild reaction conditions, is scalable, and is chemoselective. DIPEA=diisopropylethylamine, PG=protecting group, TFA=trifluoroacetate, Tf=trifluoromethanesulfonyl.

Rapidly paired up: RO₂ radicals in the atmosphere form accretion products according to RO₂+R′O₂→ROOR′+O₂. This pathway is very efficient for functionalized RO₂ radicals, reaching rates that surpass those of the competitive NO+RO₂ and HO₂+RO₂ reactions. Accretion product formation is currently not yet considered in the description of atmospheric oxidation processes.

Cationization is presented as a new strategy for bismuth(III)-mediated CH activation. A (masked) cationic bismuth compound was used for the highly selective, stepwise double CH activation of diphenyl amide, (NPh₂)⁻. Simple procedures for the straightforward functionalization of the activated positions are presented, and mechanistic aspects of these transformations are elucidated.

Activation with iodine: Hypervalent iodine(III) compounds were used as activators or organocatalysts in benchmark reactions. The crucial role of halogen bonding in these processes was demonstrated for the first time by a series of comparative experiments, including with sterically blocked derivatives. The activities of these monodentate Lewis acids match or exceed those of previously used bidentate cationic halogen bond donors.