Themed collection 2023 Chemical Science Covers

Water oxidation liberating dioxygen under visible light irradiation poses a formidable challenge to natural and artificial photosystems. The quest for the “green shift” represents a major goal to enhance the overall photosynthetic performance by tailoring molecular architectures.

This perspective showcases how quantum chemical calculations drive predictive strategies to explore unknown reactions, catalysts, and synthetic routes toward complex molecules in synthetic methodology development.

Heterometallic cluster chemistry to control the function of titanium–organic frameworks.

By taking inspiration from the structures and reactivities of its past, organolanthanide chemistry has managed to reinvent itself for the challenges of today and the future.

Organo-functionalisation of polyoxometalates with peptide moieties is an effective approach to obtain diverse arrays of functional hybrid materials, where each component influences the resulting change, surface chemistry, polarity, and redox properties.

The combination of molecular imprinting approaches and nanomaterials has recently emerged in new approaches for the imprinting of nanomaterials. This review summarizes the latest studies and the potential implications and applications of this field.

This review provides a multidisciplinary overview of the challenges and opportunities for dynamic covalent chemistry-based macromolecules towards the design of new, sustainable, and recyclable materials for a circular economy.

A primer that covers the discovery and validation process for novel aptamers and highlights recent applications of aptamers in biosensing and cell separations.

We report a Cu^II peptide helicate that selectively binds DNA 3WJs in cells, damaging DNA replication foci by ROS production, thus demonstrating for the first time the selective cleavage of this noncanonical DNA structure with a chemical nuclease.

A novel supramolecular tryptophan hinge motif enables the self-assembly of nanotube monolayers by hierarchical non-covalent polymerisation of cyclic peptides in lateral contact.

1,2-Disubstituted bicyclo[2.1.1]hexanes have been synthesized, characterized, and biologically validated as saturated bioisosteres of the ortho-substituted benzene ring.

Excited state evolution of the rhodium(III) complex [Rh(III)(phen)₂(NH₃)₂]²⁺ (phen = 1,10-phenanthroline) has been investigated theoretically to gain a better understanding of light-driven activation of high-energy metal centered states.

A novel mixed-metal cobalt–iron polyoxometalate (POM) aids the understanding of the role of the inner, coordinatively saturated metal ions in Weakley archetype POMs on the catalytic OER activity.

We fabricated a range of N_y-MnO_x using compartmentalized microemulsion crystallization followed by post-calcination. These materials have the unique ability to generate sufficient ¹O₂ at room temperature without requiring an external field.

Sulfinamides can now be readily accessed from carboxylic acids and amines in a direct decarboxylative reaction enabled by the kinetically-driven reactivity of sulfinylamines and acridine photocatalysis.

Newly developed Δ²-learning models enable state-of-the-art accuracy in predicting the properties of chemical reactions.

First antimalarial autofluorescent artemisinin–coumarin hybrids are highly in vitro/in vivo active, able to overcome drug resistances and are suitable for investigating their mode of action in living P. falciparum parasites by fluorescence microscopy.

A novel H₂O₂ and NAD(P)H indicator for in vivo monitoring oxidative stress and antioxidant capacity in the model of acute myocardial infarction and trichloroethylene exposure has been reported.

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 covalent peptide ligand mimicking the binding motif in the E6AP protein selectively crosslinks to HPV16 E6 with quantitative conversion. This ‘reactide’ provides a starting point in the development of inhibitors against HPV-driven cancers.

Lappert's heavier tetrylenes E{N(SiMe₃)₂}₂ (E = Ge, Sn, Pb) have been efficiently prepared from GeCl₂·(1,4-dioxane), SnCl₂ or PbCl₂ and Li{N(SiMe₃)₂} via a completely solvent-free one-pot mechanochemical route followed by sublimation.

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

Exploring the impact of varied DNA-encoded chemical library (DEL) inputs on hit discovery rates in DEL screenings.

Doubly electrophilic pyrazabole derivatives (pyrazabole = [H₂B(μ-C₃N₂H₃)]₂) combined with one equiv. of base effect the ortho-borylation of N-alkyl anilines.

Bench-stable N-heterocyclic nitrenium ions were used for the efficient electrophilic amination of organometallic nucleophiles. The previously unexplored N-alkyl/aryl triazane intermediates were reduced to produce a diverse scope of primary amines.

A long range π-conjugation has been realized by the designed π–π interactions in phenanthrene/phenanthrene-based molecular crystals, forming the “transannular effect”, which can be amplified by high pressure and induce novel piezoluminescence.

A carbohydrate phosphorylase is utilised in the synthesis of unnatural Manβ1,4-GlcNAc and longer β-mannan like glycans, including formation of phosphorolysis-stable thioglycoside linkages via novel "reverse thiophosphorylase" enzymatic activity.

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.

A Ru-based artificial metalloenzyme (ArM) at just 1–5 mol% could catalyze olefin metathesis in blood to construct various molecular scaffolds. The cancer-targeting ArM at a low dosage could elicit tumor growth inhibition by in vivo drug synthesis.

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.

Secondary metabolites are important for the pathogenesis of the fungus Aspergillus fumigatus which causes lethal Aspergillosis. Expressing groups of A. fumigatus genes in the fungus Aspergillus nidulans reveals new A. fumigatus secondary metabolites.

We have developed cell-penetrating stapled peptides based on the amphipathic antimicrobial peptide magainin 2 for intracellular delivery of nucleic acids such as pDNA, mRNA, and siRNA.

Visible-light-induced [3+2] cycloadditions of donor/donor diazo precursors with alkenes to afford pyrazoles and (spiro)pyrazolines have been reported. Mechanistic and DFT studies suggested the non-covalent interactions promote the reaction.

The resonance between an electronic transition and an incident photon flux induces a pushing optical force. Instead, non-linear stimulated emission process induces a pulling force which direction is opposition to absorption processes.

The existence of two mesomerism structures could emit two phosphorescence bands simultaneously and well balance the distribution of excitons for multicomponent emissions.

Catalytic cracking could enable low temperature conversion of hard-to recycle polyolefin plastics. However, traditional cracking catalysts suffer from macro and microscopic mass transport limitations, which call for plastic pre-treatment.

The six-pots synthesis of latanoprost has been accomplished with excellent diastereo- and enantioselectivities through an organocatalyst-mediated Michael reaction, a substrate-controlled intramolecular Mukaiyama aldol reaction as key steps.

The active center of a paired Ir–O–Ir structure was generated via electronic perturbations of correlated Ir single atoms on Co₃O₄ nanosheets, and the O atom of which functioned as the main active site for the selective electrocatalysis of As(III).

Variation of three different stimuli: the type of guest molecules, temperature and light enables intentional manipulation of the mechanical, electronic and magnetic properties of a cyanido-bridged coordination polymer.

Polymer NHCs as a strong binding motif together with hydrophobicity control the accessibility of substrates at catalyst–electrolyte interface and enhance CO₂ electroreduction on metal catalysts.

Synthetic precision oligomers with complementary sticky ends and functional catalytic groups form dynamic constitutional libraries comprising cyclic di(oligomer)s which prove much more efficient for catalysis than other components of the library.

Cucurbit[7]uril complexes aggregate into well-defined trimers in dimethyl sulfoxide in the presence of a selection of cations, as long as the host cavity is filled with a guest that leaves one carbonylated portal available for cation binding.

Rational structure–mechanism-based strategies for identifying small molecules that are able to control multiple pathological targets in Alzheimer's disease are established, with an example of developing a promising multi-target-directed flavonoid.

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.

This work identifies a new mechanism for the origin of the superior ORR activity of ZrN in alkaline media, combining electrochemical surface state analysis, density functional theory, and pH-dependent microkinetic modeling.

In three Zn porphyrin–Re complex dyads, we explored room-temperature phosphorescence and photocatalytic CO₂ reduction. The dyad with a 5-position linkage to the bipyridine ligand showed notable activity due to dual triethanolamine coordination to Zn and Re ions.

Identification of azaserine biosynthetic gene cluster and in vitro reconstitution of O-(2-hydrazineylideneacetyl)serine synthesis showed that the diazo group of azaserine is synthesized by the stepwise oxidation of a hydrazinoacetic acid moiety.

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.

The progress of graphene-zipping reactions in graphene-based materials is successfully visualized using advanced temperature-programmed desorption (TPD) up to 2073 K.

The emergence of molecular oxygen (O₂) in the Earth's primitive atmosphere is an issue of major interest.

A solid-supported palladium complex successfully captured β-ketoamide-tagged peptides as palladium enolates and released them in high yield upon acid treatment.

We found that a cationic hetero tetranuclear complex including a calcium and three cobalts exhibited high catalytic activity toward alternating copolymerization of propylene oxide (PO) and carbon dioxide (CO₂).

We developed ²¹¹At-radiolabeled 2,6-diisopropylphenyl azide (ADIPA) for targeted α-particle therapy. In the experiment using a mouse model, low-dose (70 kBq) administration of ADIPA effectively suppressed tumor growth without causing adverse effects.

The total synthesis of the naturally occurring N–N atropo-diastereomers dixiamycin A (1a) and dixiamycin B (1b) using a key Cu(I)-catalyzed aerobic oxidation of xiamycin A methyl ester (2b) was developed.

Modified 8–17 DNAzymes that can induce target gene silencing in cells were developed based on the X-ray crystal structure of 8–17 DNAzyme and the modifications used in designing antisense oligonucleotides.

We report the first example of a synthetic thiol-based compound that promotes oxidative protein folding upon 1-equivalent loading to the disulfide bonds in the client protein to afford the native form in over 70% yield.

Reaction of a terphenyl bis(anilide) ligand with trivalent halide precursors of Ce and early actinides yield both neutral and “-ate” complexes. These molecules afford comparative insight into f-block metal–arene bonding.

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.

The transformation of inorganic gels into MOFs is developed as a general strategy to construct complex porous MOF architectures at nano, micro, and millimeter length scales.

The transfer of stereo-electronic information from achiral building blocks and templates to chiral cyclophanes is rationalized and exploited to produce self-assembled macrocyclic species carrying up to 16 stereogenic elements.

We report the development of a potent and selective de novo cyclic peptide ligand for epigenetic methyllysine reader domain. The cyclic peptide binds at the aromatic cage of PHD-finger and modulates the JmjC lysine demethylase activity of KDM7.

A conductive MOF, named Bi-based catecholate BiHHTP, exhibited excellent catalytic performance towards CO₂ electroreduction.

Very high photoluminescence intensity of a Eu(III) complex is achieved using a host–guest system. The intensity is 400 times larger than that of the Eu(III) complex itself.

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.

In a density of states format of the frequency-extended surface-enhanced Raman spectrum, potential-induced variations of the lifetime of hydrogen bonds and their dynamic behavior were observed at aqueous solution/Au interfaces.

The properties of metal clusters are highly dependent on their molecular surface structure.

First ever catalyst-free electro-photochemical generation of carbene radical anion from aryl diazoester with direct application into synthesis of interesting N-heterocycles with broad substrate scope and excellent diastereo-selectivity.

Schematic of fluoro-electrochemical microscopy. (a) Cartoon E. huxleyi is green under normal light, but (b) emits red fluorescence under UV. (c) Placed near an oxidizing electrode, its fluorescence fades and ultimately (d) “switches off”.