Hypervalent iodine reagents are commonly used for the development of novel transformations. As they are highly reactive and biocompatible, they have been employed more recently for the functionalization of biomolecules. This Minireview discusses the development of hypervalent iodine reagents for the modification of peptides and proteins as well as their application, such as labeling and peptide stapling.

Nachhaltige Energiesysteme können nicht ohne die Speicherung von schwankendem erneuerbarem Strom existieren. Für geringe Energiemengen sind elektrische Batterien geeignet, große Mengen erfordern hierfür chemische Batterien. Die Hydrierung von CO₂ ist eine vielversprechende Option. Die komplizierte Materialwissenschaft von Cu-Katalysatoren, die die Selektivität dieser Reaktion steuern, wird in diesem Aufsatz erörtert.

This Review provides an overview of recent developments in the synthesis of chiral (enantioenriched or racemic) secondary and tertiary alkyl fluorides by monofluoroalkylation catalyzed by transition-metal complexes. Strategies to access alkyl fluorides by C−C bond formation (monofluoroalkylation) are inherently convergent and complexity-generating, but they have been studied less than strategies to access alkyl fluorides by C−F bond formation (fluorination).

“Truly” two-dimensional (2D) nanobots based on graphene oxide and powered by enzymes have been fabricated by facile noncovalent interactions. The 2D nanobots can be propelled at ultralow H₂O₂ concentrations and show chemotactic behavior. Furthermore, in the presence of fuel, they showed an excellent capability for “on-the-fly” removal of methylene blue (MB) dye for environmental remediation.

Modifications of DNA/RNA impact their properties including susceptibility to oxidation. 5-Methylcytosine and N⁶-methyladenine were competed for photooxidation by riboflavin, anthraquinone, or Rose Bengal against dA, dG, dC, and dT in DNA. This confirmed dG is more oxidation prone, representing collateral damage during photosensitized probing for the base methylations.

Various metal 5-oxaporphyrinium cations were synthesized, and a cobalt(II) 5-oxaporphyrinium cation was successfully incorporated into the heme-acquisition protein (HasA) secreted by Pseudomonas aeruginosa. The reconstructed protein strongly inhibited the growth of P. aeruginosa and multidrug-resistant P. aeruginosa.

The biosynthetic pathway of amino/nitro-cyclopropylalanine moieties in hormaomycin and belactosin was fully elucidated. The pathway involves six-electron oxidation of the ϵ-amino group of l-lysine by heme oxygenase-like dinuclear iron enzymes (HrmI/BelK) and C−C bond formation by iron- and α-ketoglutarate-dependent oxygenases (HrmJ/BelL). This is the first example of Fe/α-KG oxygenase-catalyzed cyclopropane formation.

Calixarene-like polyoxoniobates: Two unprecedented giant calixarene-like polyoxoniobate (PONb) nanocups based on multiple macrocyclic clusters have been made, showing the fusion of two areas of metallacalixarene and PONb chemistry. The two molecular nanocups are by far the largest two inorganic–organic hybrid PONbs and hold promise for developing largely unexplored inorganic–organic hybrid PONb chemistry.

Catalytic N−H/B−H double activation of 1,2-azaborines has been demonstrated. A wide variety of 1,2-azaborines underwent cycloaddition with vinylethylene carbonate through N−H/B−H bond cleavage to produce unique polycyclic oxazaborolidines under mild conditions. Furthermore, highly enantioselective direct functionalization of 1,2-azaborines afforded chiral tricyclic oxazaborolidines.

OpTAG (optical cell tagging) is a novel chemical platform for attaching functional tags onto cell surfaces in a spatially resolved manner. In combination with cell sorting and single-cell RNA sequencing (scRNA-seq), OpTAG-seq enables spatially resolved scRNA-seq.

A new family of lithium-conducting methacrylic polymer electrolytes based on highly delocalized borate groups is discussed. The optimized borate homopolymer shows the highest ionic conductivity reported for a single-ion conducting polymer electrolyte for lithium metal batteries.

The first mechanochemical strategy for highly chemoselective, solvent-free palladium-catalyzed cross-coupling of amides by N−C bond activation is reported. The protocol advances the biorelevant amide bond cross-coupling manifold to solid-state solventless cross-coupling methods.

We report a two-step, one-pot water-compatible and high-yielding radiofluorination approach by the displacement of a labile, inner-sphere water of a seven-coordinate Sc chelate with a ¹⁸F⁻ ion to form the first fully inert and water-compatible Sc–¹⁸F ternary coordination complex. The corresponding complex is fully in vivo compatible and can be the diagnostic PET imaging partner to the corresponding ⁴⁷Sc-labeled endoradiotherapeutic.

Aliphatic and aromatic carboxylic acids are rapidly converted into potassium acyltrifluoroborates (KATs) by copper-catalyzed borylation of their mixed anhydrides. This scalable method is compatible with a broad range of functional groups and allows for the facile preparation of aliphatic and aromatic KATs, including KATs derived from Fmoc- and Boc-protected amino acids.

The efficient catalytic degradation of N₂O to N₂ by well-defined bis(silylene)amido iron complexes under mild conditions involving the cooperative effect between the iron and silylene ligands is reported. Selective reductions of nitro compounds to amino-boranes with good functional-group tolerance and excellent chemo-selectivity have been developed using the same approach.

Catching conformations: Lipophilicity (logP) is a molecular property which is nevertheless the weighted average of the lipophilicities of the individual conformers. The first direct measurement of conformer-specific lipophilicity values is presented, together with the introduction of a new avenue for rational lipophilicity optimization of drug candidates which is focused on modification of conformational equilibria in water and in octanol.

A dynamic system of interconverting helicates and cages was prepared and characterized. The presence of steric bulk on the central ring of the ligand was found to control both the complexity and interconversion mechanism.

A TiO_x/Zn/N-doped carbon inverse opal (TZNC IO) structure is designed through a multi-step method to regulate Zn deposition for Zn metal anodes. Benefitting from the ordered open structure with abundant zincophilic sites, the TZNC host can realize a preferential Zn nucleation and growth in the confined space. As expected, the dendrite-free TZNC@Zn composite anode enables long-term cycling in both symmetric and full cells.

An enantioselective iron-catalyzed cross-[4+2]-cycloaddition of unactivated branched and linear dienes is described. The illustrated process provides a very efficient and atom-economic access to chiral 1,3-substituted vinyl-cyclohexenes under very mild reaction conditions. The development of a chiral bis-dihydroisoquinoline ligand class was essential to obtain excellent levels of chemo-, regio- and enantioselectivity.

Taming the Lewis superacidity of a pyramidal borane by weakly coordinated anion dissociation enabled the activation of inert C−H bonds and resulted in an unusual coordination mode at boron.

Es wurde eine gentechnisch veränderte Variante des Außenmembranproteins F (OmpF) entwickelt, welche die Zellaufnahme von Aminosäurederivaten als Täuschmoleküle fördert. Die Koexpression der OmpF-Mutante mit Wildtyp-P450BM3 ermöglichte es dem auf Escherichia coli beruhenden Ganzzellbiokatalysator Benzol mit Hilfe von Täuschmolekülen effizient zu oxidieren. Darüber hinaus wurde durch Veränderung des Täuschmoleküls eine in ganzen Zellen katalysierte stereoselektive Hydroxylierung erreicht.

Surface gelation on disulfide electrocatalysts in Li–S batteries is identified for the first time. The gel layer, formed through the solvent polymerization triggered by the Lewis acid sites, covers the active electrocatalytic sites and renders reduced redox kinetics. Herein, a Lewis base triethylamine is introduced to suppress the surface gelation and promote the electrocatalytic activity of disulfide electrocatalysts.

The structures of the third polymorph of indomethacin, Form δ, crystallized from both melt and solution are reported. The two crystallization methods were believed to produce the same polymorph since its discovery in 1974. Through combining microdroplet melt crystallization with 3D electron diffraction, we reveal that the two crystallization methods produce two different polymorphs and correct this 47-year-old misunderstanding.

A rapid and effective living cell encapsulation strategy is developed for reversible manipulation of cell–cell interactions. The controllable cell–cell interactions and molecular transportation between cells was achieved by fabricating functional DNA scaffold networks on cell surface. This DNA scaffold network-based strategy holds great potential in cell surface engineering, synthetic biology, and cell-based biomedicine.

Herein, we report a universal boronate-affinity crosslinking-amplified dynamic light scattering immunosensing strategy and demonstrate its potential for the rapid and sensitive field detection of glycoproteins in complex samples.

In vivo “Turn-On” NIR-II FL and NIR-II PA signals by using activated caspases-3 after radiotherapy to proteolytically cleave the peptide sequence of an AuNNP@DEVD-IR1048 nanoprobe, in addition to integrating living imaging information with a radiotherapy effect using the caspase-3 enzyme as “matchmaker” and developing the relationship between each other, enable real-time evaluation and early prediction of radiotherapy effects.

As a proof-of-concept, we proposed a structural model of a spiral MoTe₂ domain to optimize collectively active site and vertical conduction. A single spiral MoTe₂-based electrocatalytic microdevice was fabricated to extract HER activity and displayed exceptional activity with an ultrahigh current density of 3000 mA cm⁻² at an overpotential of 0.4 V.

A variety of renewable polymers has been synthesized from easily accessible biobased hydroxyaldehydes and dihydrosilanes. Using low catalyst loadings of platinum complexes, different polymer architectures were obtained, from random to alternated copolymers. The intrinsic chemical recyclability of these poly(silylether)s is also highlighted.

The in-depth mechanism of electrocatalytic CO₂ reduction on in situ reconstructed Cu₂O microparticles is still ambiguous. Now strong evidence shows that the Cu₂O/Cu interface plays a key role in determining the selectivity of methane production rather than the initial crystal planes of the Cu₂O microparticles.

High-molecular-weight branched poly(aryl piperidinium) membranes with high conductivity (147 mS cm⁻¹ at 80 °C) and excellent mechanical (26 % swelling ratio) and chemical stability have been prepared. Anion-exchange membrane fuel cells (AEMFCs) using these membranes exhibit high peak power density (2.3 W cm⁻²) and durability (500 h).

Amino acid supramolecular recognition in the 2^nd coordination sphere of a bioinspired manganese catalyst allows efficient enzyme-like activation of H₂O₂ by locating the carboxylic acid moiety in proper position to access the 1^st coordination sphere of the metal.

A novel DNA-encoded chemical library (DEL) encoding method featuring a “reversible covalent headpiece (RCHP)” is described, which allows efficient interconversion between double- and single-stranded DNA forms. Hybridization and covalent crosslinking of ssDEL with diversified complementary functionalized DNAs enables multiple DEL applications.

Episulfide-involved self-switchable polymerization to produce well-defined sulfur-rich triblock thermoplastic elastomers has been achieved via an ammonium salt mediated copolymerization of episulfide/isothiocyanate together with an air-assisted oxidative coupling strategy.

A copper-catalyzed asymmetric cascade cyclization/[1,2]-Stevens-type rearrangement is disclosed, affording valuable chiral chromeno[3,4-c]pyrroles bearing a quaternary carbon stereocenter in generally moderate to good yields with excellent enantioselectivities. Importantly, this protocol represents the first catalytic asymmetric [1,2]-Stevens-type rearrangement based on alkynes and the first asymmetric formal carbene insertion into the Si−O bond.

A highly crowded perylene-cored oligoarylene processively transforms into π-extended chiral nanographenes with two helical breaches under Scholl's conditions. The acquisition of various intermediates implies a distinctive reaction pathway mainly involving the regioselective and sequential cyclization in the peri- and bay regions of the perylene core, and the complanation of the 1-phenyl[5]helicene intermediate module via 1,2-phenyl migration.

Half-sandwich scandium catalysts serve as a unique platform for the regio- and diastereoselective [3+2] annulation of aliphatic aldimines with alkenes via β−C(sp³)−H activation, affording a new family of multi-substituted aminocyclopentane derivatives from easily accessible aldimines and alkenes with broad substrate scope, high regio-, diastereoselectivity and 100 % atom-efficiency.

Elaborately designed WSe₂ flakelets decorated on the N-doped graphene (WSe₂/NG) with an abundant active site can not only act as a redox accelerator to promote the bidirectional conversion of lithium polysulfides (LiPSs) and significantly alleviate the shuttling effect, but also as a regulator for enabling uniform Li plating/stripping to mitigate the growth of Li dendrite.

A carbene strategy for the sequential (deutero)hydrodefluorination of fluoroalkyl ketones is reported. This method allowed for the controllable preparation of difluoroalkyl- and monofluoroalkyl ketones from aryl- and alkyl-substituted perfluoroalkyl ketones in high yield with excellent functional group tolerance.

We have described a general energy balance approach by sulfur substitution to transform existing hemicyanine dyes (Cy) into optimized NIRF/PA dual ratiometric scaffolds. Based on this optimized platform, the first dual-ratio NIRF/PA response probe AS-Cy-NO₂ was designed for quantitatively and precisely monitoring of tumor hypoxia levels in vivo.

A concept of self-expanding Li-ion transport channels is demonstrated to construct a fast-charging anode and realize high-performance fast-charging Li-ion batteries. The self-expanded Li-ion transport channels, which are enabled by a self-reversible conversion of chemical bonds with different bond lengths in the anode, allow a fast Li-ion solid-state diffusion kinetics and effectively eliminate Li metal plating under fast-charging conditions.

A short-chain dehydrogenase/reductase family protein, MrqM, was revealed as a cyclase in the biosynthesis of murayaquinone by the in vivo genetic experiment, which is a new strategy used in type II polyketide cyclization. This finding not only broadens the functions of the short-chain dehydrogenase/reductase family proteins, but also paves the way for future work in polyketide cyclization and engineering.

Affinity-to-adsorbent-based sorting of fine particles, including cells, is engineered by minimizing the masking effect of non-specific interactions. Due to a high contact area and hence high detachment energy, even non-specifically and weakly interacting particulates are quasi-irreversibly bound to adsorbents. Microstructured stimuli-responsive dynamic interfaces provide a solution for sorting highly asymmetric cell and particle mixtures.

Recognizing monogenic RNA G-quadruplexes (G4s) in vivo is challenging. We developed a module-assembled multifunctional probes assay (MAMPA) for visualizing endogenous G4s in individual genes in single cells.

An atomically dispersed twisted Zn^I-N₃₊₁ structure was developed to accelerate a proton-feeding process that reduces the energy barrier of, and thereby promotes, the kinetics of the CO₂ reduction reaction.

A new class of axially chiral styrene-based organocatalysts has been rationally designed. They enable the chemo-, diastereo- and enantioselective (2+4) cyclization of 2-benzothiazolimines. This work represents the first design of styrene-based chiral thiourea tertiary amine catalysts and the first catalytic asymmetric (2+4) cyclization of 2-benzothiazolimines, and it gives an in-depth understanding of axially chiral styrene-based organocatalysts.

Concave–convex interactions between negatively and positively curved molecular nanographene with C₆₀ allow the formation of complexes with 1:1, 1:2, and 2:1 stoichiometries. Theoretical calculations predict the photoinduced electron transfer from the curved nanographene to the electron acceptor C₆₀. Transient absorption spectroscopy confirms solvent dependent electron transfer after photo-excitation.

Three new n-type semiconducting polymers, P-0, P-50, and P-75 are developed, in which the lactone group densities were maximized by increasing the benzene content from 0 % benzene (P-0), to 50 % (P-50), and 75 % (P-75), to enable co-planar polymers with deep-lying LUMO energy level. As a result, the polymer of P-75 exhibits a good thermoelectric performance with a maximum electrical conductivity of 12 S cm^-1 and figure of merit power factor of 13.2 μWm^-1 K^-2.

2D LLTO crystal with large-size, oriented, and crystal defect-free structure was obtained by controlling the LLTO crystal growth and arrangement in the confined space of 2D laminar channels, which achieved faster Li⁺ transfer than LLTO Pellet.

A new type of ternary magic-size cluster (MSC), CdTeSe MSC-422 evolved at room temperature while CdTeSe MSC-399 decreased in a mixture of toluene (Tol) and octylamine (OTA). The transformation goes through corresponding precursor compounds (PCs), with step 1 transforming PC-399 to PC-422, which is rate-determining and features first-order reaction kinetics.