Themed collection #MyFirstChemSci 2023
Recent developments for intermolecular enantioselective amination of non-acidic C(sp3)–H bonds
Recently, the field of intermolecular enantioselective amination of non-acidic C(sp3)–H bonds has witnessed rapid advances, which are discussed in this perspective
Advancing cell surface modification in mammalian cells with synthetic molecules
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.
Hydrogen spillover and substrate–support hydrogen bonding mediate hydrogenation of phenol catalyzed by palladium on reducible metal oxides
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.
Regioselective ortho halogenation of N-aryl amides and ureas via oxidative halodeboronation: harnessing boron reactivity for efficient C–halogen bond installation
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.
Merging electrocatalytic alcohol oxidation with C–N bond formation by electrifying metal–ligand cooperative catalysts
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).
Improving the potential of paraCEST through magnetic-coupling induced line sharpening
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.
Synthesis of substituted benzylboronates by light promoted homologation of boronic acids with N-sulfonylhydrazones
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 donor-stabilized tetra-coordinated germanium(IV) di-cations and their Lewis acidic properties
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.
Net-clipping as a top-down approach for the prediction of topologies of MOFs built from reduced-symmetry linkers
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.
Conformational control enables boroxine-to-boronate cage metamorphosis
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.
Engineering TADF, mechanochromism, and second harmonic up-conversion properties in regioisomeric substitution space
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.
Revisiting organic charge-transfer cocrystals for wide-range tunable, ambient phosphorescence
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.
Controllable synthesis of a Na-enriched Na4V2(PO4)3 cathode for high-energy sodium-ion batteries: a redox-potential-matched chemical sodiation approach
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.
Skeletal rearrangement through photocatalytic denitrogenation: access to C-3 aminoquinolin-2(1H)-ones
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 deliver genotoxic formaldehyde to human cells
N-Acyloxymethyl-phthalimides are esterase-sensitive chemical tools that enable controllable delivery of formaldehyde to human cells.
Trifluoromethylarylation of alkenes using anilines
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: a chirality-aware deep learning model for predicting the outcomes of the hydrolase-catalyzed kinetic resolution
EnzyKR is designed to guide the identification of hydrolase scaffolds for resolving a racemic substrate mixture for stereoselective synthesis.
Transient co-assemblies of micron-scale colloids regulated by ATP-fueled reaction networks
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.
New insights into H2 activation by intramolecular frustrated Lewis pairs based on aminoboranes: the local electrophilicity index of boron as a suitable indicator to tune the reversibility of the process
The condensed-to-boron electrophilicity index (ωB) is a tunable property to rationally perform modifications for reaching reversibility in H2 activation by intramolecular aminoborane frustrated Lewis pairs.
Directing group assisted para-selective C–H alkynylation of unbiased arenes enabled by rhodium catalysis
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.
Resolving a guanine-quadruplex structure in the SARS-CoV-2 genome through circular dichroism and multiscale molecular modeling
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.
Electron count and ligand composition influence the optical and chiroptical signatures of far-red and NIR-emissive DNA-stabilized silver nanoclusters
AgN-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.
NMR exchange dynamics studies of metal-capped cyclodextrins reveal multiple populations of host–guest complexes in solution
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.
Generative organic electronic molecular design informed by quantum chemistry
Reinforcement learning methods, coupled with quantum chemistry, discover a diverse set of organic singlet fission and triplet–triplet annihilation candidates.
Photocyclization by a triplet–triplet annihilation upconversion pair in water – avoiding UV-light and oxygen removal
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 CAAC-ruthenium olefin metathesis catalysts modularly derived from a large-scale produced ibuprofen intermediate
A tunable family of ibuprofen intermediate-derived CAAC-base complexes for different applications, dependent from the size of the N-aryl substituent.
Hybrid bronzes: mixed-valence organic–inorganic metal oxides as a tunable material platform
Hybrid bronzes are air/water-stable mixed-valence organic–inorganic metal oxides displaying tunable optoelectronic properties and high conductivity relevant for energy-related applications.
“Freedom of design” in chemical compound space: towards rational in silico design of molecules with targeted quantum-mechanical properties
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.
Microscopic insight into the shaping of MOFs and its impact on CO2 capture performance
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.
Benchmarking the placement of hydrosulfide in the Hofmeister series using a bambusuril-based ChemFET sensor
Bambusuril-containing ChemFET sensor membranes show excellent selectivity for HS− and inform on its placement in the Hofmeister series.
Dimeric tetrabromo-p-quinodimethanes: synthesis and structural/electronic properties
High bromine containing dimers of tetrabromoanthra-p-quinodimethane as appealing building-blocks for organic synthesis. Thorough study of their isomerism and optoelectronic properties.
Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines
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.
A macrocyclic quinol-containing ligand enables high catalase activity even with a redox-inactive metal at the expense of the ability to mimic superoxide dismutase
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.
A unified strategy for the synthesis of aldohexoses by boronate assisted assembly of CH2X2 derived C1-building blocks
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.
Interrogating bioinspired ESIPT/PCET-based Ir(III)-complexes as organelle-targeted phototherapeutics: a redox-catalysis under hypoxia to evoke synergistic ferroptosis/apoptosis
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.
Kinetics of ligand exchange in solution: a quantitative mass spectrometry approach
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.
Stabilisation of the RirA [4Fe–4S] cluster results in loss of iron-sensing function
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.
A natural polyphenol activates and enhances GPX4 to mitigate amyloid-β induced ferroptosis in Alzheimer's disease
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.
Dynamic-dependent selectivity in a bisphosphine iron spin crossover C–H insertion/π-coordination reaction
Organometallic reaction selectivity is governed by dynamic motion rather than transition states or spin crossover.
Improving the molecular spin qubit performance in zirconium MOF composites by mechanochemical dilution and fullerene encapsulation
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.
Studying manganese carbonyl photochemistry in a permanently porous metal–organic 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.
Suitability of a diamine functionalized metal–organic framework for direct air capture
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.
Photoinduced iron-catalyzed C–H alkylation of polyolefins
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 glue for amplification and temporal regulation of biocatalytic reaction networks
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.
Boroles from alumoles: accessing boroles with alkyl-substituted backbones via transtrielation
The synthesis of monomeric 2,3,4,5-tetraalkyl-substituted boroles via metallacycle transfer from an alumole is reported.
Role of mutations in a chemoenzymatic enantiodivergent C(sp3)–H insertion: exploring the mechanism and origin of stereoselectivity
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.
Push-pull photochromic dyes for semi-transparent solar cells with light-adjustable optical properties and high color-rendering index
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.
A visible-light-driven molecular motor based on barbituric acid
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.
Tidying up the conformational ensemble of a disordered peptide by computational prediction of spectroscopic fingerprints
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 expansion with NUDELs – poised DNA-encoded libraries
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.
2,5-disubstituted bicyclo[2.1.1]hexanes as rigidified cyclopentane variants
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.
Continuous flow synthesis of pyridinium salts accelerated by multi-objective Bayesian optimization with active learning
Human-in-the-loop experimentation enables interactive machine learning for continuous flow chemistry reaction planning and optimization.
Programmed guest confinement via hierarchical cage to cage transformations
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.
Ultrabright two-photon excitable red-emissive fluorogenic probes for fast and wash-free bioorthogonal labelling in live cells
Our best fluorogenic probe enables live-cell imaging with high-contrast and no need for washing steps.
Terminal methylene phosphonium ions: precursors for transient monosubstituted phosphinocarbenes
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.
A highly enantioselective intramolecular 1,3-dipolar cycloaddition yields novel pseudo-natural product inhibitors of the Hedgehog signalling pathway
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.
Photochemical reactions of a diamidocarbene: cyclopropanation of bromonaphthalene, addition to pyridine, and activation of sp3 C–H bonds
Unprecedented photochemical reactions for the diamidocarbene 1 including the double cyclopropanation of 1-bromonaphthalene, the double addition to pyridine, and the activation of sp3 C–H bonds of alkanes are reported.
Establishing PQ-ERA photoclick reactions with unprecedented efficiency by engineering of the nature of the phenanthraquinone triplet state
Thiophene substitution at the 3-position of PQ enhances its reactivity in PQ-ERA photoclick reactions, resulting in increased efficiency, yields, rate constants, and oxygen tolerance, offering prospects for efficient photoclick transformations.
First principles reaction discovery: from the Schrodinger equation to experimental prediction for methane pyrolysis
The methane pyrolysis reaction network is constructed from first principles in the ab initio nanoreactor, going from reaction discovery through ab initio molecular dynamics to chemical kinetic modeling and comparison to experiments.
CrystalClear: an open, modular protocol for predicting molecular crystal growth from solution
We present a new protocol for the prediction of free energies that determine the growth rates of sites in molecular crystals for subsequent use in Monte Carlo simulations using tools such as CrystalGrower.
Development of a nitrogen-bound hydrophobic auxiliary: application to solid/hydrophobic-tag relay synthesis of calpinactam
Development of a new hydrophobic auxiliary, TCbz group at the N-terminus of peptides is disclosed. This auxiliary enabled C-terminal modification in LPPS and a de novo solid/hydrophobic-tag relay synthesis (STRS) of calpinactam.
Replacing the BO in BODIPY: unlocking the path to SBDIPY and BIDIPY chromophores
Synthesis, characterisation, and investigation of the luminescence features of a new class of chromophores: SBDIPY and BIDIPY.
Structural and dimensional control of porphyrin capsules using Group 15 tris(3-pyridyl) linkers
Changing the bridgehead atom of E(3-Py)3 (E = P, Sb, Bi) ligands can modulate the size and shape of supramolecular capsules, while coordination to the appropriate metalloporphyrin allows formation of discrete molecular capsules or extended structures.
Dynamic covalent self-assembly and self-sorting processes in the formation of imine-based macrocycles and macrobicyclic cages
The self-assembly of imine-based dynamic covalent architectures involves component selection and self-correction processes to generate homo-self-sorted outputs, even in dynamic constitutional networks of high complexity.
Palladium mono-N-protected amino acid complexes: experimental validation of the ligand cooperation model in C–H activation
Palladium complexes with mono-N-protected amino acid ligands (MPAA) have been prepared as models to experimentally study the C–H activation of arenes. Their reactivity shows the validity of the chelating model with the assistance of the acyl group.
Sodium mediated deprotonative borylation of arenes using sterically demanding B(CH2SiMe3)3: unlocking polybasic behaviour and competing lateral borane sodiation
Mechanistic studies on sodium-mediated borylation of arenes, uncover a unique polybasic behaviour for the formal borylation of two equivalents of the relevant arene as well as the competing formation of a borata-alkene complexes.
Unprecedented perspectives on the application of CinNapht fluorophores provided by a “late-stage” functionalization strategy
A simple and easy-to-implement process based on a nucleophilic aromatic substitution reaction with a wide variety of nucleophiles on a fluorinated CinNapht offers unprecedented perspectives.
Distal meta-C–H functionalization of α-substituted cinnamates
Distal meta-selective C–H olefination, allylation, acetoxylation and cyanation of α-substituted cinnamates have been reported. New coupling partners such as quinones, maleimides and sulfolene were utilized for the first time in meta-C–H activation.
Probing juxtaposed G-quadruplex and hairpin motifs using a responsive nucleoside probe: a unique scaffold for chemotherapy
We report the use of a new dual-app nucleoside probe composed of environment-sensitive fluorescent and 19F NMR labels in dissecting the structural polymorphism of G-quadruplexes formed by the EGFR gene, which is implicated in many cancers.
Two-photon isomerization properties of donor–acceptor Stenhouse adducts
Photo-switching of Stenhouse donor–acceptor adducts by a non-linear optical input.
About this collection
This themed collection highlights and celebrates articles shared by our authors using the #MyFirstChemSci hashtag on social media in 2023. This collection covers a diverse range of research from authors publishing in Chemical Science for the first time, from researchers with their first ever ChemSci publication to those with their first corresponding-author ChemSci publication.
If you are publishing in Chemical Science for the first time, please do share your work on social media using #MyFirstChemSci or get in touch with us via email (email@example.com) and we will be delighted to highlight your publication!