Themed collection #MyFirstChemSci 2024

This perspective summarizes the mechanism and factors affecting magnesiothermic reduction reaction to make porous silicon for energy storage and fuel generation applications.

Over the years, spectroscopic, electrochemical and structural studies of [FeFe] hydrogenases have provided ‘pieces’ of information to complete the ‘puzzle’ of their catalytic cycle. However, there are still missing pieces that we need to fill in.

A deep understanding of electrode–electrolyte interfaces requires the development of modelling protocols spanning from the local microscale to system-level macroscopic sizes which can be validated by comparison with high-quality experimental results.

The comparison of homologous hydrogenases, in which the same inorganic active site is surrounded by a variable protein matrix, has demonstrated that residues that are remote from the active site may have a great influence on catalytic properties.

This article provides an in-depth analysis of the reaction chemistry of boryl compounds, including transition metal boryl complexes and diborane(4) compounds, from a structure and bonding perspective.

We review the current capabilities of local electron correlation methods up to the gold standard CCSD(T) level, which are now capable of routinely reaching large systems of practical interest in p- and d-block, as well as surface and biochemistry.

The formation of reactive oxygen species (ROS) in the brain can cause neuropathologic degradation associated with Alzheimer's Disease (AD). We report on a cocktail of two chelators that target Cu and Zn and effectively inhibit ROS formation.

The aqu BGC from Austroacremonium gemini encodes a versatile polyketide synthase capable of synthesising heteromeric depsides with diverse alkyl side chains.

Photo-cycloadduct diazetidines exhibit high energy storage densities exceeding 0.3 MJ kg⁻¹, offering long-term energy storage for up to 23 years and rapid solvent-assisted energy release.

Using interface-sensitive techniques, we investigated the photoresponsive release of the chemotherapeutic drug doxorubicin from micellar nanocarriers of arylazopyrazole photosurfactants at the air–water interface as well as bulk aqueous solution.

A generalizable machine learning technique (VBO) for efficient exploration of MOF design space was developed and demonstrated by optimizing MOFs for NH₃ storage.

We introduce a bioinspired antioxidative mechanism to adaptively control the photoluminescence and prevent photobleaching of molecular phosphors.

The first asymmetric total synthesis of naturally occurring atropodiastereomers of Amaryllidaceae alkaloids, such as narcipavlines A (1a) and B (1b) and narcikachnines A (2a) and B (2b), sharing a cis-dihydrobenzofuran structure is reported.

Spiropyran/merocyanine molecular switches can generate metastable proton gradients of four pH units, enabling efficient photoenergy harvesting and conversion.

Magnesium ions drive the selection of natural phosphatidic acids.

A Pd/C-catalyzed regiodivergent hydrocarboxylation of terminal alkynes to cinnamic and acrylic acids as well as hydroxy/alkoxy carbonylation of internal alkynes to α,β-unsaturated acids/esters have been devised using oxalic acid as a CO source.

Triarylboron compounds have been established as promising candidates in optoelectronic applications.

A new series of phenacylselenoesters that generate hydrogen selenide in the presence of esterase and a biological thiol under ambient conditions is reported.

Combined experimental and quantum-chemical studies were used to characterise the philicity/fugality features of tertiary phosphines and Michael acceptors in phospha-Michael reactions, which are key steps in phosphine-catalysed organic reactions.

Diene- and ene-like reactivity in transition metal coordinated arenes can be expected when there is a notable degree of aromaticity loss at the complexed arene.

This study demonstrates that water-soluble perylene-derivative dimers can efficiently induce either singlet fission or charge separation upon photoactivation.

Herein, we report the first visible-light-induced strategy for the rapid synthesis of densely functionalized α- and γ-phosphorylated β-sulfonyl enamines in a regio- and stereoselective manner from N-sulfonyl allenamides and H-phosphine oxides.

Computational and experimental investigation of metal oxo cluster surface chemistry via ligand exchange reactions with phosphinic and phosphonic acid ligands.

A PEC system utilizing BiFeO₃ nanoparticulate films, exhibiting tunable photocurrent reversal controlled by electrolyte composition is reported. The system's behavior, predicted by the Nernst equation, provides valuable insights for PEC-catalysis.

Ultrafast vibrational spectroscopy reveals that centrosymmetric dihydropyrrylopyrrole-based triads can follow three distinct photo-induced symmetry-breaking charge-transfer pathways, depending on the substituents and solvent.

Porous interlayers in 2D metal-halide perovskites enable new modes of reactivity. These include permanent intercalation of redox-active molecules as well as post-synthetic halide-to-halide and halide-to-pseudohalide exchange.

The direct conversion of esters to imines or enamines is achieved using zirconocene hydride (ZrH) catalysis. This transformation occurs through an amine-interrupted reduction, bypassing traditional pathways leading to alcohol products.

Design and single-molecule level scrutiny of a novel NIR absorbing and emitting terrylenediimide-based chromophore, TDI-TPA₄, is reported. The energy gap law and dielectric dependence of TDI-TPA₄ are validated at single-molecule and ensemble domains.

Copper nanoparticles with robust structural integrity and strong optical properties have been developed and projected as an affordable alternative to conventional plasmonic nanomaterials for high-temperature photothermal applications.

Reversibly photo-switchable acylhydrazone-based synthetic ion transporters with OFF–ON transport activity are reported. The involvement of H-bond forming and lone pair donating groups facilitate its function as a cation–anion symporting carrier.

Molecular solar thermal energy storage route using teralylenes with pyridine protonatable moieties for on-demand energy release achieved upon protonation with catalytic amounts of acid.

This study explores intricate pathway complexity in peptide self-assembly, revealing chiroptical switching phenomenon influenced by temperature, denaturation, and cosolvent content, offering new insights into switchable piezoresponsive behavior.

The first structurally and physically characterized complexes bearing the dianion radical of an s-tetrazine are presented and highlight the extraordinary ability of tetrazines to store more than one electron within their six-membered ring.

The first example of CO₂-adsorption actuated spin transition tuning in a 2D Hofmann-type framework is demonstrated, where effective spin-state stabilisation is disseminated as the CO₂ occupation rate in the framework based on gating temperature.

Symmetry-breaking approach exceeds the sensitivity of the vibrational Stark effect. Nitrile groups report on microscopic electric fields without interference from hydrogen-bonding interactions.

A three-dimensional MOF featuring an anthracene dimer ligand analogous to 4,4′-bipyridine undergoes selective dimensional reduction into a two-dimensional framework that can be mechanically exfoliated.

Naphthalenyl- and anthracenylpyridine cyclometalating ligands bind to Pt in different ways, which can be used to tune their emissive properties.

Mitochondrial-targeted protein degradation (mitoTPD) is explored using small-molecule degraders that leverage a mitochondria-localized protease. This approach restored mitochondrial morphology and shows potential for drug discovery.

Population-weighted principal moments of inertia and exit vectors analyses of shapeshifting bullvalenes reveals the diversity in their 3D structures.

A novel and highly diastereoselective NBS-mediated cyclization of N-alkoxy α,β-unsaturated silyl imino ethers to furnish nearly three dozen α-bromo N-alkoxy β-lactams with dual functional handles is described.

Bench-stable trityl isocyanide enables the photoredox catalytic cyanation of carboxylic acids, alcohols and alkyl halides.

Energy transfer barriers through affordable calculations. Density functional theory is shown to be a reliable tool to compute barriers between relatively large systems through the application of the classical formulation of the Marcus theory.

The report discloses the strategic deployment of lynchpins in crosslinking peptides and installing borono-heterocycles in peptide frameworks, which can be leveraged for multitasking prospects in biochemical applications.

The Ground State Stability (GSS) rule predicts the ground state of indenofluorene-type systems: a triplet is favored if the open-shell (OS) form has double or more the number of π-sextets as the closed-shell form; otherwise, an OS singlet is favored.

Demonstration of a switchable electrocatalysis mechanism modulated by hydrogen bonding interactions in ligand geometries.

We report the first systematic study of substituent effects on the electronic structure of pentalenides, giving insight into charge distribution, aromaticity and polarisation effects.

Inspired by the Burgess reagent, we report a mild and practical synthesis of primary sulfonamides from electron-rich aromatic compounds by using in situ formed N-sulfonylamine as the electrophile.

We develop reagents to optically control microtubule dynamics, with (1) lensless microscopy to track their bioactivity; (2) photo-SAR to find GFP-compatible reagents; & (3) fluorophore antennas to drive single-photon isomerisation even ≥600 nm.

Supramolecular catalysts based on a zinc-porphyrin molecular recognition site and a catalytically active iridium site enabled the selective ortho-C–H borylation of benzamides under a regime in which the C–H activation step is not rate-determining.

Group 6 metal/Al(C₆F₅)₃ donor–acceptor systems for N₂ activation surprisingly diverge from their B(C₆F₅)₃ analogues, providing access to M{NN(Al(C₆F₅)₃)}₂ adducts. Implications for the N₂ ligand are explored spectroscopically and computationally.

Naturally occurring and readily available α-hydroxy carboxylic acids (AHAs) are utilized as platforms for visible light-mediated oxidative CO₂-extrusion furnishing α-hydroxy radicals proved to be versatile C1 to Cn hydroxyalkylating agents.

Development of substrate-selective nanozyme requires careful attention. We show that proteins with dimensions larger than the pore aperture of MOF-808, installed with a bis-(μ-oxo) dicopper active site in its adamantane pore, can compromise the substrate selectivity of oxidase nanozyme.

Carbon–carbon (C–C) bond formation is a cornerstone of synthetic chemistry, relying on routes such as transition-metal mediated cross-coupling for the introduction of new carbon-based functionality.

A triboelectric generator harvesting electrical energy from oscillatory mechanical motion. Each grey circle represents a metal–organic framework or counter material used in our study to construct the triboelectric series.

Superior supramolecular packing and thereby efficient electron transport in economically viable n-type organic semiconductor materials suitable for solution-processed OFET devices yield high electron mobility and ambient stability.

Bacterial DNA-damage repair activates the SOS response, which promotes hypermutation and antibiotic resistance. SAR investigation identified OXF-077, a small molecule DNA-repair and SOS-response inhibitor that suppresses resistance evolution.

Herein, we report a peptide cyclisation strategy via intramolecular interception of cysteine desulfurisation. This method enables the cyclisation of unprotected peptides in aqueous solution via the installation of a hydrocarbon linkage.

Automated flow peptide synthesis (AFPS) gives access to peptides and proteins with post-translational modifications (PTMs) and enables investigation of PTM-mediated regulation, and was used to study the PTM-dependence of the MYC:Bin1 interaction.

A post-synthetic modification strategy was developed to graft metal chelating thiols to polydopamine inside Fe-BTC. X-ray absorption spectroscopy revealed interesting redox properties of the composite that help extract and reduce Pt(IV) from liquid.

We present the synthesis of oligomeric molecules by linking metal–organic polyhedra (MOPs) through the preparation of a 1-connected (1-c) MOP and its reaction with 1-c, 4-c, or 24-c molecules to yield dimeric, tetrameric, or satellite structures.

We devised an innovative probe platform using two highly environment-sensitive ¹⁹F-labeled nucleoside probes to elucidate the structure and ligand binding of the HIV-1 LTR G-rich region by fluorescence and ¹⁹F NMR techniques.

Carborane fused boron doped polycyclic aromatic hydrocarbons were accessed by dehydrobrominative and dehydrogenative borylation.

Solid-solution RuSn alloy NPs were successfully synthesised for the first time and exhibited enhanced HER catalytic activity compared with Ru NPs and commercial Pt NPs under alkaline conditions, providing new insights for the design of catalysts.

Synthesis of room temperature ferroelectric 2D Bi₂O₂S ultra-thin nanosheets through a mild chemistry route.

Efficiently merging low-cost high-throughput screening and characterisation, automated data analysis, computational modelling, and cagey – a custom database analysis tool, enhances large-scale data curation and accelerates discovery of organic cages.

A hydrophobic metal–organic framework displays some of the largest selectivities known for adsorption of the fluorinated greenhouse gases CF₄ and CHF₃ over N₂.

Integration of laser capture microdissection and top-down mass spectrometry aids protein identification in spatially-resolved native ambient mass spectrometry.

High spin monomeric complexes [Mn^II(OTeF₅)₄]²⁻ and [Mn^III(OTeF₅)₅]²⁻ represent novel homoleptic coordination environments at Mn(II) and Mn(III) centers with monodentate O-donor ligands.

FRET nanoparticles assembled with small-molecule ionic isolation lattices (SMILES) provide control of both emission wavelength and lifetime. This allows simple design of dye based nanoparticles for fluorescence lifetime microscopy.

Recent bioengineering of CYP450_OleT shows that peroxide-based CYP450_OleT can be converted to a reductase-based self-sufficient enzyme, which is capable of showing efficient hydroxylation and decarboxylation activity for a wide range of substrates.