Themed collection 2023 Chemical Science Covers

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.

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”.

A new phase of Ir₂Sm in the Laves phase family was synthesized. Alloying of Sm and Ir tunes the electronic properties of Ir and reduces the binding energy of oxygen intermediates, thereby accelerating the kinetics and enhancing the OER activity.

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.

Unprecedented bisbenzimidazole (Bbim)³⁻˙ radical-bridged dilanthanide complexes were isolated where the dysprosium congener features magnetic memory effect and the second highest coercive field for any organic radical-bridged dinuclear compound.

Chiral copper clusters displaying good luminescence and extended lifetimes were synthesised. Enantiomerically pure clusters capped using L- and D-isomers of the ligand displayed mirror image circular dichroism and circularly polarized luminescence.

UV irradiation induced conformational isomerisations of a 1,2-diketone in the crystal, causing multistep luminescence changes and eventual macroscopic melting.

Ultra-stable CsMnX₃ nanocrystals embedded glasses with bright and broad red photoluminescence (PL) emission at 649 nm were synthesized as an excellent red phosphor for white light-emitting diode (LED) devices with a high color rendering index (CRI).

Thiol-containing metabolites in all organisms are involved in the regulation of diverse biological processes. We have developed a new method comprising bicyclobutane for chemoselective capturing and mass spectrometric analysis of this compound class.

We report the first molecular probe for the selective detection of the most abundant cellular inositol pyrophosphate 5-PP-InsP₅, supported by computational chemistry, as well as an efficient new synthesis.

Peptide self-assembly into proteolytic self-processing amyloid structures associates with the major neurodegenerative disorder, Alzheimer's disease (AD). Active aggregates may be employed for cross-seeding of this important process.

We developed a volatile organic compound (VOC)-based probe cocktail for monitoring the dysregulation of tumour-associated enzymes via the detection of volatile tracers in animal breath, thereby allowing the discovery of a new tumour targeted therapy.

Atomically precise nanoclusters play an important role in nanoscaled catalysis, photonics, and quantum information science.

This theoretical study sheds light on the proteolysis mechanism of SARS-CoV-2 PL^pro and how the C270R mutation affects the proteolysis activity, paving the way for understanding the function of PL^pro and design of novel allosteric inhibitors.

Herein, we report the development of a MOF-semiconductor composite film active for water oxidation at a thermodynamic underpotential.

We revealed higher neurolysin activity in the blood samples of patients with colorectal tumors, indicating that single-molecule neurolysin activity is a promising candidate for a blood biomarker for colorectal cancer diagnosis.

The halogen bonding involving the Au(I) metal center was systematically studied using a series of nine co-crystals between NHC Au(I) aryl complexes and iodoperfluoroarenes through XRD and solid-state NMR techniques, as well as DFT calculations.

An asymmetric Strecker reaction of a chiral crystal of achiral imine was realized to give aminonitrile with >99% ee thanks to an amplification of ee. A retro-Strecker reaction proceeded with the stereoinversion of a chiral crystal of achiral imine.

In this study, engineered imine reductases (IREDs) of IRED M5, originally from Actinoalloteichus hymeniacidonis, were obtained through structure-guided semi-rational design.

A room temperature stable Y(II)bis(amide) has been prepared and fully characterized. The complex reacts with tert-butylisocyanide to make a rare example of a transition metal isocyanide, CN–Y(NHAr*)₂.

Silylboronate-mediated radical cross-coupling of aryl fluorides with arylalkanes is disclosed for the efficient defluoroalkylation enabling a mild construction of a new C–C bond by selectively coupling a C(sp²)–F and C(sp³)–H bond.

Base-mediated intermolecular macrocyclization and Rh- or Ni-catalyzed intramolecular double [2 + 2 + 2] cycloadditions allow enantio- and diastereoselective synthesis of planar chiral [2.2]triphenylenophanes.

Oxidized model membranes have differential effects on peptide fibril formation, driven by surface attraction, peptide charge and secondary structure stabilization.

SARS-CoV-2 spike proteins react with Au and Si, are electrically conductive as demonstrated by single-molecule scanning tunnelling break junction approaches, change structure at 1.5 × 10⁸ V m⁻¹ and denature at 3 × 10⁸ V m⁻¹.

Mechanically flexible single crystals of molecular materials offer potential for exciting new directions in advanced materials design. Unravelling the mechanisms of this fascinating bending phenomenon is needed and developed here.

Periodic density-functional theory (DFT) calculations and dissolution calorimetry measurements were used to predict the thermodynamic stability and the likelihood of interconversion between a series of halogen-bonded cocrystals.

Site energies and excitonic couplings in cyanobacterial photosystem I are calculated at the DFT/MRCI level of theory, including a fully atomistic model of the natural environment and considering the molecular dynamics of the system.

A new low, with a glow: novel NIR-emitting, deep-LUMO (−5.0 eV) nitro-aromatic terrylene diimides are reported.

Highly regioselective C–H alkylation of anisoles and 2-methyl substituted anisoles were achieved by a imidazolin-2-iminato Sc(III) alkyl complex, which afforded the alkylation products in moderate to high yields (56 examples, up to 99% yields).

A spectroscopic and computational study reveals that bulky electron-withdrawing imido substituents stabilize a rare S = 1 iron(IV)–bisimido complex with a pseudo doubly degenerate ground electronic structure, accounting for its facile HAT reactivity.

Computational volcano plots are used to predict selectivity in the context of (first-row) transition metal-catalyzed CO₂ reduction. The expected trends were tested experimentally and allowed for systematic improvement of the catalyst.

Through simple synthetic modifications, the indigo dye becomes an efficient red-light photoswitch – now also in the solid state.

The comprehensive picture of the fragmentation behaviour of H₂S has been provided by detecting the H, S(¹D) and S(¹S) atom products at wavelengths 155–120 nm.

The differing excited state energy landscapes of group 14 complexes can lead to Kasha and non-Kasha phosphorescence.

An easy-to-perform approach to assess and quantify steric properties of Lewis acids is reported. The novel LAB-Rep model (Lewis acid/base repulsion model) is introduced, which judges steric repulsion in Lewis acid/base pairs.