Zeolite synthesis: In a Communication published in this journal in early 2015, Messinger, Na, Seo, Ryoo, and Chmelka (MNSRC) claim that the formation of zeolite MFI nanosheets proceeds through an intermediate, crystalline layered silicate phase. It is now proposed that the layered silicate phase in the MNSRC work is an artefact rather than a species possibly playing a significant role in MFI nanosheet formation.

Mesostructured MFI zeolite nanosheets are established to crystallize non-topotactically through a nanolayered silicate intermediate during hydrothermal synthesis. Solid-state 2D NMR analyses, with sensitivity enhanced by dynamic nuclear polarization (DNP), provide direct evidence of shared covalent ²⁹Si-O-²⁹Si bonds between intermediate nanolayered silicate moieties and the crystallizing MFI zeolite nanosheet framework.

Homogeneous catalysis has transformed approaches to carbon–carbon bond formation. This Minireview focuses on unusual iron and cobalt complexes that promote olefin polymerization and cycloaddition reactions.

Enzymatic methylation by methyltransferases (MTases) is an important biological process, and most MTases use the cofactor S-adenosyl-l-Methionine (AdoMet) as a methyl source. This Review summarizes the use of AdoMet-dependent MTases and AdoMet analogues for the transalkylation of various biomolecules. Different AdoMet analogues and their application to the functionalization of DNA, RNA, and proteins will be discussed.

Protein semisynthesis was used to investigate the effect of lysine acetylation and phosphorylation, as well as the crosstalk between these modifications on the structure and aggregation of mutant huntingtin exon1 (Httex1). While phosphorylation significantly inhibits the aggregation of Httext1, acetylation has no effect. However, acetylation at K6 reverses the inhibitory effect of T3 phosphorylation.

NMR² can rapidly derive structures of protein–ligand complex binding sites for strong and weak binders. The protein resonance assignment is not required and only simple 2D NMR spectra are used.

A team effort: An asymmetric [4+2] annulation of C1 ammonium enolates with copper–allenylidenes catalytically generated from carboxylic acids and 4-ethynyl dihydrobenzooxazinones, respectively, led to optically active 3,4-dihydroquinolin-2-one derivatives with excellent levels of stereoselectivity.

Double success: A metal-free reductive etherification method using frustrated-Lewis-pair-promoted reduction reactions of carbonyl compounds was developed. The key to success was the deliberate application of recently discovered water-tolerant frustrated Lewis pairs. The developments can be viewed as a double success in FLP catalysis and formation of ether bonds.

A relay formalism is proposed herein for categorizing the interplay among reactants, target product, and catalytic center in transition-metal catalysis, an important factor dictating the overall reaction viability and efficiency. An intriguing associative covalent relay process in Rh^III-catalyzed oxadiazolone-directed alkenyl C−H coupling with alkynes enables efficient access to primary pyridinylamines.

A diversity-oriented approach for the synthesis of naturally occurring 3-amino- and 3-nitro-2,3,6-trideoxypyranose derivatives from simple sugars has been developed. These studies led to the successful synthesis of a tetrasaccharide containing four different 3-aminosugar components by stereoselective glycosylation of ortho-alkynylbenzoate donors.

All about Mie: All-inorganic perovskite films with a porous interface-fused structure are formed by freeze-drying. Mie scattering and interconnection occurring in the porous films significantly enhanced the light harvesting and charge transporting ability. The Mie porous perovskite photodetectors possess a high on/off ratio of more than 10⁴ and the peak external quantum efficiency value of 658 % with a bias of 9 V at 520 nm.

Nanohoops propel ahead: A triptycene-based molecular propeller with three nanohoop blades was synthesized by a three-fold intramolecular bisboronate homocoupling and subsequent reductive aromatization. Such nanopropeller molecules pack into a lamellar hexagonal structure with 11 Å-diameter channels that run perpendicularly to the layers.

The height of sophistication: Asperflavipine A (1), an unprecedented cytochalasan heterotetramer uniquely defined by 5/6/11/5/6/5/6/5/6/5/5/11/6/5 fused tetradecacyclic rings, was isolated from Aspergillus flavipes QCS12 along with a cytochalasan heterotrimer, asperflavipine B. Compound 1 showed moderate cytotoxicity and induced apoptosis in Jurkat, NB4, and HL60 cells through the activation of caspase-3 and degradation of PARP.

Nucleic acid hydrogel sensor: The subnanomolar detection of nucleic acid targets driven by an oligonucleotide-templated reaction between embedded fluorogenic peptide nucleic acid probes is demonstrated. Restricting probe diffusion in physically crosslinked hydrogels significantly increases the detection sensitivity by reducing non-specific reactions between probes in the absence of the target.

Lipid wrap: The main glycoforms of the hydrophobic lysosomal glycoprotein saposin D (SapD) were synthesized by native chemical ligation. In functional assays the lipid-binding properties of three SapD glycoforms S1–S3 were found to be affected by the sugar moiety of SapD and showed a dependency on the size and the type of N-glycan.

Stars within reach: Two- and three-dimensional metallosupramolecules shaped like a Star of David were synthesized by the self-assembly of a tetratopic pyridyl ligand with a 180° diplatinum(II) motif and Pd^II ions, respectively, in one step and high yield. The high stability of the 3D Star of David (see structure) is correlated to its high density of coordination sites.

First the one, then the other: Diaryl- and alkenyl(aryl)iodonium salts react with N-heteroarenes in domino fashion. N-functionalization is followed by ortho-arylation under ruthenium catalysis, capturing the aryl iodide by-product of the first step.

Very active: A novel class of ferrocenyl phosphine ligands for the palladium-catalyzed alkoxycarbonylation of industrially important alkenes is reported. Compared to currently applied catalysts, the resulting palladium complexes showed much higher activity under milder conditions.

Meta is a must: meta-C−H olefination of benzylsulfonic acid and phenyl acetic acid frameworks with the assistance of a para-methoxy-substituted cyano phenol as the directing group is achieved by Xphos-supported rhodium catalysis. Complete mono-selectivity is observed for both scaffolds. COD=1,5-cyclooctadiene, DCE=1,2-dichloroethane, TFA=trifluoroacetic acid.

New on the block: Phosphasalen indium complexes are fast and stereoselective catalysts allowing production of stereoblock polylactide from racemic lactide (rac-LA; P_i=0.92). The catalysts do not feature any chiral additives and operate by chain-end control mechanisms.

Motion of the gate: The Trp41 gate of the M2 proton channel is shown to undergo a spontaneous conformational motion on a timescale of tens to hundreds of microseconds. The time constant of this motion exhibits a sigmoidal dependence on pH with a midpoint that closely matches the electrophysiologically determined conducting pK_a value of the His37 tetrad, suggesting that this motion accompanies proton conduction.

Which is the end? Conjugated polymers based on poly(9,9′-di-n-octylfluorene vinylene) with different end groups were synthesized by combining molybdenum-catalyzed acyclic diene metathesis polymerization with a subsequent Wittig-type coupling. Their fluorescence spectra were influenced by the end groups and the conjugation length.

A pillar[5]arene-based host–guest system is introduced to a nanochannel for constructing temperature-sensitive artificial channels. The channel was switched from cation transport to anion transport by controlling the extent of host bound to the guest using temperature stimuli.

SrTiO₃ mesocrystal superstructures were facilely synthesized by newly developed topotactic epitaxy from TiO₂ mesocrystals by a simple hydrothermal treatment. The synergy of the efficient electron flow along the internal SrTiO₃ nanocube network and efficient collection at the larger external cubes produces remarkably long-lived charges for enhanced photocatalysis.

Let's play BAL(L): Benzaldehyde lyase from Pseudomonas fluorescens biovar I (BAL) can catalyze enantioselective intramolecular benzoin reactions. The structural requirements for the substrate include two benzaldehyde moieties, with or without additional substituents at the 3,3′ and 5,5′ positions of the rings, connected by ether bonds to a C₃ linker at the 2,2′ positions. The synthesis of non-natural macrocycles is now possible through this biocatalytic route.

A new bio-optical hybrid photosynthesis system is developed by coating chloroplasts with conjugated polymer nanoparticles (CPNs). Since CPNs can harvest ultraviolet light that chloroplasts absorb less, chloroplast/CPN complexes capture a broader range of light to accelerate electron transport rates in photosystem II (PS II) and augment photosynthesis beyond natural chloroplasts. DCPIP=2,6-dichlorophenolindophenol dye, PQ=plastoquinone.

Still hungry: A two-coordinate diarylborinium ion undergoes twofold 1,2-carboboration with two equivalents of diphenylacetylene to form an unprecedented divinylborinium ion. NMR spectroscopy and X-ray diffraction analysis, together with theoretical calculations, revealed that the positive charge of the divinylborinium ion is delocalized over the entire π-conjugated system.

Override switch: A bidentate oxazoline-based directing group (DG) allows copper-mediated C−H amination, hydroxylation, thiolation, arylation, alkynylation, and trifluoromethylation. The directing group overrides the directing/poisoning effects of heterocyclic moieties.

Nice and easy: An efficient one-pot synthesis of chiral non-racemic aziridines was achieved by using 1 mol % of a readily available Brønsted acid catalyst. The introduction of an ortho-tert-butoxy group on the N-aryl ring was critical to inducing high levels of optical activity in the products. By using this protocol a simple 4-step synthesis of the antibiotic (+)-chloramphenicol was realized.

Skeleton key: Intermediates in early stages of the biosynthesis of saxitoxin have been identified through a combination of LC-MS and synthesis. Incorporation experiments with ¹⁵N-labeled compounds have shown that these previously proposed intermediates are key precursors of the potent voltage-gated sodium channel blocker. A mechanism for the formation of the tricyclic skeleton of saxitoxin is also put forward.

Crafty: An efficient process involving the catalytic kinetic resolution of racemic spiro-epoxyoxindoles with the simultaneous enantioselective Friedel–Crafts alkylation of indoles has been realized using a chiral phosphoric acid catalyst. The reaction provides two useful intermediates in high yields and excellent enantioselectivities. One of the intermediates was used in the asymmetric formal total synthesis of (+)-gliocladin C.

A neighborhood action group: In an asymmetric palladium-catalyzed intramolecular oxidative aminoarylation of alkenes in the presence of a quinolone–oxazoline chiral ligand and Ag₂CO₃ as the oxidant, the amide N−H bond of the substrate and a neighboring aryl C−H bond were both activated to react with the alkene (see scheme). Various indolines with a quaternary stereogenic center were synthesized in high yield with excellent enantioselectivity.

Amid the methods: Amide σ-C−C arylations were accomplished by versatile ruthenium(II) carboxylate decarbamoylative catalysis, which enabled decarboxylative ipso C−C alkylations by facile organometallic C−C cleavage. The method is versatile, robust, and mild, and mechanistic insights are discussed.

Solvent reorganization is not the sole source of enzymatic accelerations. As is shown in this Communication, two properly placed carboxy groups (see picture) can cause an otherwise nonactivated amide to cleave at enzymatic rates in the absence of any apparent solvent reorganization, thereby reaffirming spatiotemporal notions.

Proximity-based labeling: The poor reaction kinetics of sortase A (SrtA), a bacterial transpeptidase, has been a significant limitation for its use in site-specific protein bioconjugation. Proximity-based sortase-mediated ligation (PBSL) improves ligation efficiency by bringing target proteins in proximity to SrtA with the SpyTag–SpyCatcher peptide–protein pair and allows for protein purification and labeling to be simplified to a single step.

On Q: A copper-mediated decarboxylative coupling of benzamides with ortho-nitrobenzoic acids by a directed C−H cleavage proceeds to deliver the corresponding biaryls in good yields. The products can be readily transformed into various nitrogen-containing heterocycles. Additionally, a decarboxylative C−H arylation and cyclization sequence occurs, by adding a suitable base, to produce phenanthridinone derivatives in one pot.

Structure-guided engineering of a bacterial transketolase yielded enzyme variants capable of using aliphatic oxoacids as non-natural nucleophilic components for stereospecific acyloin synthesis. The double variant H102L/H474S showed high catalytic efficiency toward pyruvate and was able to complement a deletion of the dxs gene coding for 1-deoxyxylulose-5-phosphate synthase, which catalyzes the first step of the terpenoid biosynthesis.

Staying power: A novel class of substituted dibenzosuberones combines high selectivity and potency in vitro with prolonged residence times and act as type I inhibitors of the enzyme p38α MAP kinase. The concept of the additional R-spine interaction was successfully transferred to the already very potent Skepinone-L scaffold.