Themed collection #MyFirstChemSci 2023

Green oxidation reactions performed by organocatalytic activation of hydrogen peroxide.

Recently, the field of intermolecular enantioselective amination of non-acidic C(sp³)–H bonds has witnessed rapid advances, which are discussed in this perspective

This review offers a survey of recent advancements in the modification of mammalian cell surfaces through the use of synthetic molecules and concludes by addressing the present challenges and potential opportunities in this rapidly expanding field.

Complexes of the form [U(η⁶-arene)(BH₄)₃] where arene = C₆H₆; C₆H₅Me; C₆H₃-1,3,5-R₃ (R = Et, iPr, tBu, Ph); C₆Me₆; and triphenylene (C₆H₄)₃ were investigated towards an understanding of the nature of the uranium–arene interaction.

Chemists heavily rely on visual cues for routine tasks. Here, we introduce a computer vision system to automatically monitor and control diverse workup processes based on visual aspects, advancing toward autonomous operations.

PolyNC directly infers properties based on human prompts and polymer structures, enabling an end-to-end learning that encourages the model to autonomously acquire fundamental polymer knowledge, in a multi-task, multi-type unified model manner.

Two supramolecular complexes were prepared using cucurbiturils [CBs] as mediators and a four-armed p-xylene derivative (M1) as a guest molecule.

Presented here are a series of ferrocene-functionalized high-nuclear indium-oxo clusters (InOC), containing thirteen-nuclear and cubane-type heptanuclear InOCs. The self-assembly of them leads to the formation of dimers, tetramers, and one-dimensional extended structures.

An interdisciplinary approach to derive the structure of a disordered supramolecular system.

Using a highly active permethylindenyl-phenoxy (PHENI*) titanium catalyst, high to ultra-high molecular weight ethylene–linear-α-olefin copolymers are prepared in high yields, with exceptional comonomer affinity, and predictable, tuneable composition.

Dynamic nuclear polarization from endogenous metal ions is an efficient route to increase the sensitivity of solid-state NMR for probing host-guest interactions for rational design of metal organic frameworks (MOFs).

Herein, we document the design and development of a novel (3 + 2) cycloaddition reaction aided by the activity of an organic photocatalyst and visible light.

A nonenzymatic reaction converting pyruvate to phosphoenolpyruvate (PEP) is shown to proceed through carboxylate phosphorylation, suggesting that only a single phosphorylation mechanism was needed to initiate metabolic networks.

All coordination bridges in a non-conductive MOF are broken by force to make the material a proton conductor.

Surface contrast solution NMR and reaction kinetic assays reveal an active role for H₂ spillover in the phenol hydrogenation reaction catalyzed by Pd on reducible metal oxides.

Divergent stereoselectivity is rationalised in isothiourea catalysed conjugate additions of β-keto esters.

A paramagnetic chemical exchange saturation transfer (paraCEST) imaging agent based on a homodinuclear Ni(II) complex exhibits enhanced CEST efficiency due to magnetic-coupling induced line sharpening effect.

The homologation of boronic acids with diazoalkanes obtained by photochemical decomposition of N-tosylhydrazones leads to substituted benzylboronates, previously unavailable under thermal conditions. Batch and continuous flow reactions are described.

Intramolecular phosphine-stabilized tetra-coordinated Ge(IV) di-cations are established. Dispersed charges lead to Si–H activation initially at the P-site, which ultimately migrates to the Ge-site due to geometric constraint empowered Lewis acidity.

Fine-tuning of TADF, mechanochromic luminescence (MCL), and second harmonic generation (SHG) properties among three donor–acceptor based regio-isomers have been explored in this research article based on both theoretical and experimental outcomes.

We report the discovery of an ortho regioselective oxidative halodeboronation of N-aryl amides and ureas with wide-ranging applications in pharmaceuticals, materials science, and synthetic organic chemistry.

For the first time, metal–ligand cooperative catalysts were electrified to merge molecular electrocatalytic alcohol oxidation with C–N bond formation (over 30 imines, F.E. up to 99%, energy efficiency increased by order of magnitude).

Net-clipping is a strategy for the topological prediction of MOFs built with reduced-symmetry linkers. It is based on the deconstruction of nets by clipping half of the connectivity in tetrahedral, hexagonal, cubic or hexagonal prismatic nodes.

The conformational control of boronic acid building blocks allows efficient self-assembly into a tetrahedral boroxine cage. The nano-sized cage displays molecular metamorphosis, converting from a boroxine tetrapod to a boronate bipyramid.

A wide-range tunable triplet charge-transfer (³CT) phosphorescence emission is achieved by an intermolecular through-space charge-transfer cocrystallization approach using pyromellitic diimide as the acceptor and different donors.

A phenazine-mediated ambient chemical sodiation strategy is first proposed to controllably synthesize a Na-enriched Na₄V₂(PO₄)₃ cathode, which serves as an endogenous Na⁺ reservoir to compensate for irreversible sodium loss of sodium-ion full cells.

Selective installation of an amino group on heterocyclic ring employing the skeletal editing approach has been explored. We discussed a regioselective denitrogenative amination strategy to access C-3 aminoquinolin-2(1H)-ones utilizing 3-ylideneoxindoles and TMSN₃ as an aminating agent.

N-Acyloxymethyl-phthalimides are esterase-sensitive chemical tools that enable controllable delivery of formaldehyde to human cells.

This work unlocks the use of anilines in the selective trifluoromethylarylation of olefins via a mild protocol that avoids transition metals, expensive photocatalysts and additives, where hexafluoroisopropanol is a unique solvent that promotes it.

EnzyKR is designed to guide the identification of hydrolase scaffolds for resolving a racemic substrate mixture for stereoselective synthesis.

An ATP-fueled DNA based enzymatic reaction network regulates transient co-assemblies of micron-scale colloids. The system produces minimal waste, shows ATP-dependent behavior, and can be reactivated for up to three consecutive cycles.

The condensed-to-boron electrophilicity index (ω_B) is a tunable property to rationally perform modifications for reaching reversibility in H₂ activation by intramolecular aminoborane frustrated Lewis pairs.

Three polyamorphs of hydrochlorothiazide with distinct physicochemical properties were discovered. MD simulations show different dihedral angle distributions in polyamorphs I and II. Polyamorphs I and III were converted into polyamorph II.

A first work on rhodium-catalyzed para-selective C–H alkynylation has been reported and its mechanistic insights were gleaned from experimental and computational studies.

Parallel or hybrid? A combination of multiscale molecular modeling and circular dichroism is used to predict a G-quadruplex structure at atomistic resolution in the SARS-CoV-2 genome.

Ag_N-DNAs emitters at the far red/NIR spectral border have either 6 or 8 valence electrons and at least three distinct ligand compositions. Stokes shift magnitude and CD signatures are correlated with ligand composition.

Utilizing lanthanide-modified cyclodextrins and implementing the ¹⁹F-paraGEST method, up to three different co-existing populations of Ln-β-CD-guest complexes were experimentally identified, despite having similar thermodynamic and kinetic properties.

Reinforcement learning methods, coupled with quantum chemistry, discover a diverse set of organic singlet fission and triplet–triplet annihilation candidates.

A commercially available upconversion pair is applied to promote a photocyclization for the synthesis of bioisosteres using green light irradiation. The reaction concept is enabled to run in water without oxygen removal by a micellar medium.

A tunable family of ibuprofen intermediate-derived CAAC-base complexes for different applications, dependent from the size of the N-aryl substituent.

Hybrid bronzes are air/water-stable mixed-valence organic–inorganic metal oxides displaying tunable optoelectronic properties and high conductivity relevant for energy-related applications.

This work demonstrates that “freedom of design” is a fundamental and emergent property of chemical compound space. Such intrinsic flexibility enables rational design of distinct molecules sharing an array of targeted quantum-mechanical properties.

The traditional synthesis method produces microcrystalline powdered MOFs, which prevents direct implementation in real-world applications which demand strict control of shape, morphology and physical properties.

Bambusuril-containing ChemFET sensor membranes show excellent selectivity for HS⁻ and inform on its placement in the Hofmeister series.

High bromine containing dimers of tetrabromoanthra-p-quinodimethane as appealing building-blocks for organic synthesis. Thorough study of their isomerism and optoelectronic properties.

Aromatic acyl O-hydroxylamines, synthesised in one straightforward step, undergo rearrangement under simple conditions to give ortho-aminated arenes. For benzoic acid-derived substrates, this leads directly to unprotected anthranilic acids.

Manganese, iron, and zinc complexes with the macrocyclic quinol-containing ligand H₄qp4 are highly active and durable catalysts for the dismutation of hydrogen peroxide but do not efficiently dismutate superoxide.

The synthesis of aldohexoses from CH₂X₂ derived C₁-building blocks relies on Matteson homologation and strategically applied, boron mediated olefinations. A 25 min video tutorial is available via QR-code or this link: https://youtu.be/vXy5oVavJUU.

We investigated organelle-targeted bioinspired ESIPT/PCET-based Ir(iii)-complexes as promising (photo)chemotherapeutic lead compounds which actively operational in redox-catalysis under hypoxia to evoke synergistic ferroptosis/apoptosis.

Delayed reactant labelling can provide thermodynamic parameters (ΔG, ΔH, and ΔS) of solution equilibria using ESI-MS monitoring. As a proof of concept, we investigated the equilibria of pyridine ligands with macrocyclic porphyrin cage complexes.

The regulator RirA senses Fe through its [4Fe–4S] cluster, which may have only three Cys ligands from the protein. Addition of a likely fourth Asp ligand stabilised the cluster, rendering it unable to sense Fe and locked into its DNA-binding state.

Tannic acid (TA) mitigates ferroptosis induced by amyloid β-Fe in Alzheimer's disease (AD) through a multipronged activity. TA activates and enhances the GPX4 levels to counteract the complex interaction between AD and ferroptosis.

Organometallic reaction selectivity is governed by dynamic motion rather than transition states or spin crossover.

Mechanochemical encapsulation of C₆₀ fullerene leads to a change in selectivity in the topology outcome and a significant increase in coherence among spin-active centers embedded in a moderately porous zirconium PCN-223 porphyrinic framework.

Photo-liberation of CO from a Mn(diimine)(CO)₃Br moiety anchored within a permanently porous MOF support is studied. The crystallinity and structural flexibility of the MOF allows crystallographic snapshots of the photolysis products to be obtained.

A comprehensive examination of mmen-Mg₂(dobpdc) as a direct air capture adsorbent to determine its practical feasibility and performance for potential industrialization in mitigating climate change by reducing atmospheric CO₂ levels.

A method for chemically introducing diverse polar groups into polyolefins via photoinduced iron-catalyzed C–H bond alkylation is reported. Diverse functional groups and polyolefins could be tolerated, and the multiply functionalized polymer could be synthesized through a module-assembled process.

A transient vesicular assembly enables gluing of enzymes, with augmented catalysis. Efficient temporal control of the enzyme activities is achieved even in complex reaction networks.

The synthesis of monomeric 2,3,4,5-tetraalkyl-substituted boroles via metallacycle transfer from an alumole is reported.

A molecular level understanding into the role of mutations in a cytochrome P450 catalyzed enantiodivergent carbene insertion reaction is provided through the use of computational tools.

Using push–pull photochromic dyes with carbazole units, we have fabricated translucent photovoltaic devices that vary their transparency with light intensity and maintain a high colour rendering index.

Yeehaw! The rotation of a visible-light-driven molecular motor based on barbituric acid is tamed by a hydrogen bonding “lasso” mechanism between its serendipitously-formed tertiary hydroxy stereocentre and its lower half carbonyl groups.

Pairing experiments with simulations, we predict spectroscopic fingerprints, enhancing understanding of disordered peptides' conformational ensembles. This helps rationalize elusive structure-spectra relationships for these peptides and proteins.

Fragment growing using poised DNA-encoded libraries, which allow the coupling of a targeted active fragment, allows the optimisation of fragment hits to potent compounds in a single operation, illustrated by the discovery of a 51 nM BRD4 ligand.

Identification of rigid counterparts for common flexible scaffolds is crucial to the advancement of medicinal chemistry. Herein, synthesis of new bicyclo[2.1.1]hexanes to act as rigidified cyclopentanes is described.

Human-in-the-loop experimentation enables interactive machine learning for continuous flow chemistry reaction planning and optimization.

A novel methodology based on the use of phenanthrenequinone is applied to selectively change the subcomponent of TPMA-based cages, thus controlling inclusion ratio of competing guests differing in size or chirality.

Our best fluorogenic probe enables live-cell imaging with high-contrast and no need for washing steps.

Diprotic terminal methylene phosphonium ions were prepared using bulky N-heterocyclic imine substituents. Deprotonation yields transient monosubstituted phosphinocarbenes, which insert into the CC bond of a phenyl ring via a Buchner ring expansion.

Synthesis of pyrrolo[3,2-c]quinoline pseudo-natural products by means of a highly enantioselective intramolecular 1,3-dipolar cycloaddition yielded a novel Hedgehog signalling inhibitor chemotype that targets the Smoothened protein.