Strychnine is a notorious neurotoxic plant alkaloid that has been studied for centuries. A recent report from the O'Connor group has successfully elucidated the biosynthesis of strychnine for the first time using modern transcriptomics and protein expression methods, laying a foundation for future studies to engineer production or modifications of this important natural product.

Bimetallic catalysis has emerged as an important strategy for developing new reactions in stereodivergent synthesis. This strategy is also a simple and powerful approach for synthesizing all the possible stereoisomers of products bearing two stereocenters from the same set of starting materials. This Minireview summarizes recent progress and briefly gives perspectives for the future advancement of this field.

The role of coordination metal complexes as precursors for the generation of heterogeneous catalysts for the oxidation of fine chemicals is reviewed. Specific attention is paid to describing the phenomena leading to the genesis of the active sites, the clear characterization of the surface species, and their catalytic performance.

This Review provides summary and critical evaluation, including the challenges and pitfalls, of antibiotic-derived positron emission tomographic radiopharmaceutical development efforts aimed at infection imaging either considered for radiotracer development for infection imaging or radio-antibiotic PET imaging supplementing other tools for pharmacologic drug characterization.

This Review provides an overview of electrocatalysts designed for the direct splitting of seawater. The mechanism of seawater splitting is introduced before the primary principles for designing catalysts (noble metal, noble metal free, and metal-free) for seawater splitting are analyzed in terms of both the hydrogen and oxygen evolution reactions. The future development of electrocatalysts for clean hydrogen generation is also discussed.

A porous hydrogen-bonded framework (HOF) was constructed from a 18-crown-6-ether (18C6) derivative. Although a 18C6 macrocycle is flexible and has many possible conformations, directional intermolecular hydrogen bonds of 4,4′-dicarboxy-o-terphenyl modules in the periphery of the 18C6 allowed to form a rigid HOF with 1D channels with a bottleneck composed of 18C6 rings. The wet HOF shows proton conductivity (1.12×10⁻⁷ S cm⁻¹) through a Grotthuss mechanism (E_a=0.27 eV) under 98 %RH.

Systems with weak dipolar interactions have the potential to be used for molecular quantum computing. Orientation selective pulsed EPR was used to model the conformational flexibility of a molecular multi-qubit model system. Spectrally addressable centres allowed for the individual manipulation of each spin qubit, while differing relaxation dynamics resulted in a proposed handle for the implementation of quantum algorithms.

Two chiral-at-cage carbazole-modified carboranes emit circularly polarized luminescence (CPL) and aggregation-induced electrochemiluminescence (AIECL). The |g_PL| factors of (R/S)-Cb1 and (R/S)-Cb2 enantiomers in films reached 7.38×10⁻³. Significant solvation effect was observed in the fluorescence and CPL of Cb1, while Cb2 showed remarkable AIECL effect with excellent ECL stability and dopamine detection ability.

Boosted electron interaction of metal nano-alloy with Se-doped MXene and optimized distribution of Pd−Sn sites on PdSn_0.5/Se−Ti₃C₂ can modulate the d band center, decrease adsorption energies of CO* at Pd site and enhance OH* generation at Sn site, thus removing CO poisonous intermediates, and thereby significantly enhancing methanol oxidation reaction (MOR) efficiency and durability of the anodic catalyst for a direct methanol fuel cell (DMFC).

CMS membranes derived from polyimide precursors show dual model morphologies comprising a disordered continuous phase and distributed molecular sieving Langmuir domains. Our study showed that during physical aging, pore structure changes in the two different “C” phase and “L” domains both occur, which affects the gas separation performance of CMS membranes.

Here we report experimental and computational studies that quantify the measured effect of variations in metal-ligand covalency on the reactivity of phosphinodiboranate complexes with trivalent uranium and similarly sized lanthanides.

In situ inhibitor synthesis and screening (ISISS) links high-throughput bioorthogonal synthesis with screening tor target binding by fluorescence, as exemplified by the efficient identification of in vivo orally active inhibitors of PHD2, a target for anemia treatment.

Xenon tetrafluoride and WOF₄ react in CFCl₃ solvent to form the first transition-metal coordination complex of Xe^IV, F₃XeF_b- - -WOF₄. The complex was structurally characterized by Raman spectroscopy and single-crystal X-ray diffraction. Quantum-chemical analyses, such as MEPS, show the W- - -F_b bond is primarily an electrostatic, σ-hole bond with a smaller degree of covalent character.

Complex kinetic behavior was observed in a two-component system containing a viologen-based guest and oxatub[4]arene through the involvement of the three conformers of the host. In addition, an unprecedented threading mechanism involving the tilted conformation of the guests was revealed to be responsible for the very fast kinetics and for the threading of guests with very large stoppers.

An efficient and general micro-gas blasting (MGB) synthesis is developed to access versatile high-areal density noble metal single-atoms/metal oxide nanosheets, including Pt₁/CeO₂, Ir₁/CoO_x, Pd₁/CeO₂, etc. The as-prepared Pt₁/CeO₂−S catalysts are revealed to possess superior reactivity and tolerance than routinely structured alternatives by using water-gas shift (WGS) as a model reaction.

An advanced electrocatalyst has been developed by decorating single-Ni atoms on hollow S/N-doped football-like carbon spheres (Ni SAs@S/N-FCS) for the oxygen evolution reaction. Thanks to the abundantly surface-exposed single-Ni atoms, hollow S/N-codoped carbon matrix, as well as their strong synergistic interactions, the resultant Ni SAs@S/N-FCS electrocatalyst exhibits outstanding activity and stability for alkaline oxygen evolution reaction.

Prebiotically plausible isoxazole nucleosides are shown to be excellent candidates for proto-nucleosides and proto-RNAs. The proto-nucleoside forms 2 instructive H-bonds with guanosine and can directly rearrange in RNA to give cytidine. The stereochemical outcome of the reaction is controlled by already present canonical seed-nucleosides.

A non-enzymatically and orthogonally controlled catalytic DNA (CCD) circuit was prepared for on-site and efficient in vivo microRNA (miRNA) imaging without off-site signal leakage. The CCD circuit integrates the cell-specific endogenous stimulation of the auxiliary catalytic hairpin assembly (CHA) with the orthogonal activation of the main entropy-driven DNA reaction (EDR) for sensitive target detection.

An anthracene-based molecular crystal with a unique “slipped herringbone” packing motif has been developed by delicate crystal engineering through terminal tert-butylation. Appropriate exciton-exciton coupling/electron-phonon coupling originating from the unique crystal packing induces a remarkably strong solid-state emission (photoluminescence quantum efficiency, Φ_F=74.9 %) and efficacious charge transport (carrier mobility, μ=5.0 cm² V⁻¹ s⁻¹).

Affinity Bioorthogonal Chemistry tags (ABC-tags) based on 2-pyridyltetrazines serve a dual role by enabling protein purification through metal chelation and still maintaining their rapid kinetics in bioorthogonal reactions. ABC-tagging is successful for proteins tagged at the C- or N-terminus or at internal positions, is successful in complex mixtures including cell lysate, and can be carried out on-resin to generate multidomain proteins.

A novel 3D semiconducting coordination polymer Fe₅(C₆O₆)₃ is reported with high conductivity, broad electronic transitions and interesting thermoelectric/magnetic properties. The unique structure and properties of this material illustrate that controlling the oxidation states of redox-active components in conducting metal-organic materials can be a “pre-synthetic” strategy to carefully tune material topologies, properties, and functionalities.

A new 3D Hofmann-type metal–organic framework (MOF) {Fe(bpt)[Pt(CN)₄]} ⋅ 0.5anth (1, bpt=2,5-bis(4-pyridyl)thiophen; anth=anthracene) is prepared. It displays thermo- and photo-switchable magnetic and dielectric properties accompanied by structural phase transitions between different space groups.

A hybrid separation technique, referred to as Dual-Gradient Unified Chromatography (DGUC), enabling simultaneous multicomponent analysis of both small and large molecules across a wide polarity range is introduced. DGUC lays the foundation for the next generation of hybrid chromatographic techniques with the deployment of universal elution profiles obtained via multi-eluent blending beyond traditional separation modes.

A two-stage mechanism is discovered in the metal-dependent phase separation pathways of ssDNA to form all-DNA coacervates. Distinct ion-specific pathways allow the generation of new coacervate structures by mixing multiple coacervate systems, leading to pathway-controlled coacervate-protocell communication and information exchange.

The estimation of Michaelis–Menten kinetic parameters is highly sensitive to small experimental errors, even though the quantification of such parameters is critical. Monte Carlo simulations show that the kinetic efficiency, which governs limit of detection of assays that require low background, is the most precise kinetic parameter.

A metal-free allylic C−H amination protocol allows simple vinylsilanes and vinylboronates to be selectively functionalized without competitive consumption of the reactive vinylmetalloid core structure, preserving its reactivity for future transformations such as cross-coupling or addition reactions. The silicon/boron group directs the regioselectivity of amination to the distal side of the C=C bond, allowing access to a complementary substitution pattern.

As triggered by the target, an artificial enzyme was site-specifically formed at the tip of filamentous M13 phage, generating a novel catalytic nanomaterial for miRNA analysis. miRNAs in human plasma samples, tumor cells, and tissues were detected with high sensitivity comparable to qRT-PCR, showing a great possibility of clinical applications.

Selective electrocatalytic oxidation of alcohols to aldehydes has significant challenges, for example, it cannot realize the preparation of aldehydes selectively in alkaline aqueous solutions. By tuning the local microenvironment over the electrocatalyst, and thus selectively salting-out the aldehyde at the gas|electrolyte interface, the electrocatalytic synthesis of aldehydes was achieved in an efficient and green way.

A novel cascade cyclopolymerization is developed to synthesize polyacetylenes containing fused bicyclic rings via sequential cascade ring-closing metathesis. The regioselectivity is controlled by altering the structure of the catalyst, affording polymers containing fused bicyclo[4,3,0] or [4,4,0] rings. The resulting polymers show narrow band gaps due to the planarization of the conjugated segment resulting from the fused bicyclic structure.

Functionalization of white phosphorus (P₄) with N-hydroxyphthalimide esters to synthesize dialkylphosphines and trialkylphosphines under transition-metal- and photocatalyst-free conditions is presented. The oxidation products can be isolated in high yield via the air oxidation of alkylated phosphines.

Chiral Ag₂Se:Nd/Yd/Er NPs by introducing RuCl[(p-cymene(BINAP)]Cl as ligands were synthesized. Nd³⁺, Yb³⁺ and Er³⁺ as sensitizers case a fluorescence red-shift to 1550 nm with an intensity increased by 145.7-fold compared with Ag₂Se:Nd/Yd/Er NPs. The fluorescence imaging efficiency of R-Ag₂Se:Nd/Yd/Er NPs was 2-fold higher than that of S-Ag₂Se:Nd/Yd/Er NPs.

An oncolytic virus-mimicking strategy is proposed to enhance T cell-mediated tumor immunotherapy by synthesizing an ion-enhanced nanoplatform PolyIC@ZIF-8. This nanoplatform not only mimics an oncolytic virus-like function by inducing cell apoptosis to recruit T cells in a tumor antigen-dependent manner but also releases Zn²⁺ to enhance T cell recruitment and activation in a tumor antigen-independent manner.

A pair of chiral Cu^I-based CMA enantiomers, (R,R)-PSIPr*-Cu-DMAC and (S,S)-PSIPr*-Cu-DMAC, have been constructed to exhibit aggregation-dependent circularly polarized luminescence with large luminescence dissymmetry factor of up to +0.027. Inspiring aggregation-dependent TADF properties strongly associated with ligand-ligand rotation of enantiomer molecules were also demonstrated.

Half-sandwich rare-earth catalysts serve as a unique platform for the regio- and diastereoselective formal [2+2] cycloaddition of a wide range of allenes with amino-functionalized alkenes via allene C(sp²)−H activation, affording a new family of cyclobutane and cyclobutene derivatives which were difficult to access previously.

Although aryl thioamides are often used to assess the pharmacological effects of H₂S, their reactivity is extremely sluggish and their release of H₂S is highly inefficient. Herein, we report that H₂S liberation from this donor class can be augmented with intramolecular nucleophilic assistance. We envision this new chemistry serving as a general design strategy for accessing efficient donors that selectively respond to various biological stimuli.

A dimer single-molecule junction with positively charged units is constructed through host–guest interaction using graphene-based static molecular junctions. A transition mechanism from temperature-independent coherent tunneling to temperature-dependent incoherent transport is observed, which is caused by thermally-induced specific molecular vibration modes. The introduction of positive charge can improve the incoherent transport process.

The hydroxypolyfluoroalkylation of alkenes is reported, wherein the intrinsic aldehyde/ketone-gem-diol equilibrium and photocatalytic phosphine-mediated deoxygenation play key roles. A range of electron-deficient alkenes are compatible in this transformation, thus leading to structurally varied bis(trifluoromethyl)carbinols in moderate to excellent yields.

Microbial degradation of poly(ethylene terephthalate) (PET) with Ideonella sakaiensis releases the greenhouse gas carbon dioxide. Here, a fermentative metabolic pathway in Ideonella sakaiensis was uncovered facilitating PET degradation while producing valuable feedstock chemicals or electricity in a microbial fuel cell with Geobacter sulfurreducens. This ‘plastic fermentation’ process provides opportunities for future bioenergy technologies while combating plastic pollution.

The construction of axially chiral acyclic aryl-alkene skeletons via classic Suzuki–Miyaura reaction has been challenging compared to the biaryls. Rational optimization established an enabling 3,3′-triphenylsilyl-substituted phosphite ligand for asymmetric coupling of hindered aryl halides and vinyl boronates under mild conditions, affording the acyclic aryl-alkenes in good yield, atroposelectivity and E/Z selectivity.

This study employs electrochemical DNA-based sensors to investigate the hydrolytic activity of a previously unknown nuclease, cyclophilin B. The protein is secreted by pancreatic cancer cells and could be a biomarker for early-stage cancer diagnoses. However, the demonstrated nuclease activity will limit bioassay development based on natural nucleic acid aptamers. Instead, we propose DNA stereoisomers (l-DNA) to overcome this challenge.

An in situ photoreduction strategy is taken to synthesize diatomic Pd−Cu catalysts on 2D phosphorene. Owing to the strength of the unique synergistic effect of PdCuP₄ coordination, the adsorption of NO₃⁻, the transfer of intermediates, and the formation of N≡N bond are all enhanced, leading to a high NO₃⁻ removal rate and N₂ selectivity.

A unique structural motif for leader binding and interdomain interactions was identified in the crystal structure of the kinase domain of class III lanthipeptide synthetase CurKC responsible for the biosynthesis of curvopeptin. This motif consists of two N-terminal antiparallel β-sheets, a central α-helix, and three C-terminal antiparallel β-sheets.

The first antibiotics with low nanomolar activity against the multidrug-resistant Mycobacterium abscessus are achieved by rational redesign of rifamycins. Structure-based modification on the rifamycin ansa-chain, together with microbiological, biochemical, biophysical and in vivo characterizations, provides novel candidates that are 300-fold more active than rifampicin, completely bypass the resistance, and possess promising pharmacokinetic profiles.

Four isostructural Ag₂₂ nanoclusters protected by a metallamacrocyclic monolayer were synthesized in high yields by in-situ ligand formation strategy. The high-electron-affinity triazine-based cyanurate ligands endow the clusters with unique core-shell interfacial bonding structure and donor-acceptor type electronic structure, resulting in the first mixed valence Ag^0/I nanocluster with thermally activated delayed fluorescence (TADF) characteristic.

HNO has broad chemical and biomedical properties and Cu cyclam is a useful platform to make excellent HNO sensors including imaging agents. A computational study reproduced their various experimental reactivities and revealed subtle and sometimes unexpected interwoven effects of steric and electronic factors, which offer the first mechanistic understanding of substituent effects for excellent HNO sensors to facilitate future development.

A far-red fluorescent probe with blinking and lasting emission is developed to meet the contradictory requirements of super-resolution imaging and single-molecule tracking. A microfluidic device is fabricated to trap red blood cells (RBCs) and to enable the manipulation of the microenvironment. The integration of the probe and device has uncovered nanoscale dynamics of living RBC membranes, providing a means to advance diagnostics to the molecular level.

The diazo group is highly reactive and provides biological activity to natural products. By genome mining of the diazo group-biosynthesizing enzymes, an avenalumic acid (AVA) biosynthetic gene cluster was identified in Streptomyces sp. RI-77. This pathway includes two enzymes, AvaA6 and AvaA7, catalyzing the diazotization of 3-aminoavenalumic acid using nitrous acid and substitution of the diazo group for hydride to synthesize AVA, respectively.

A continuous-flow biocatalytic system based on the co-compartmentalization of enzymes and cofactors within Pickering emulsion droplets has been developed. As exemplified by enzyme-catalyzed ketone enantioselective reduction and enantioselective transamination, this system features long-term operational stability, excellent catalytic efficiency and no need for exogenous cofactors.

A toolbox of living polymerization methods has been applied for the stereomodulation of poly(4-methyl-1-pentene) (PMP) to provide new fundamental forms in which thermal phase transitions, T_g and T_m, can be adjusted over a wide range. Also reported for the first time are the synthesis and properties of authenticated 1,2-regioregular atactic PMP, which serves to correct past errors and misinformation.

In contrast to the extensively investigated steady-state upconversion luminescence (UCL), systematic studies on temporal UCL are carried out, which have enabled wide modulation of the rise and decay dynamics of the UCL, and consequently a record adjustment of 20-fold lifetime, ≈70-fold red-to-green intensity ratio, as well as reversibly definable Er³⁺ emission color by simply tuning the pulse width of the excitation laser.

A novel photocatalyst based on Earth-abundant chromium is described. The catalyst enables a dearomative (3+2) cycloaddition between indoles and vinyldiazo reagents. Densely functionalized indoline compounds are readily accessed in high yields and exclusive regioselectivity.

A NIR light-driven photocatalyst for overall water splitting was constructed by site-selective photodeposition of platinum single atoms/clusters (Pt-SACs) on Ni-phytate (PA-Ni)-sensitized polymeric carbon nitride (PCN).

Carboxyl-rich benzodiimidazole oligomers (BDO-HC) are obtained through a side-group assisted self-assembly. The carboxyl-based strong built-in electric field promotes charge separation, and the nano-range crystals provide short channels for charge transfer. The photocatalyst is capable of efficient hydrogen and oxygen evolution.

A general and facile colloidal method to synthesize ultrathin nanowires at atmospheric pressure and low temperature (50 °C) is developed. The mechanism of nanocrystal growth along different dimensions is discussed. Fifteen kinds of RE-Mo-O (RE=Y, La-Nd, and Sm-Lu) ultrathin nanowires could be synthesized using this method. All of them exhibited polymer-like behavior.

The encounter of a donor/acceptor diazo derivative with a hydrocarbon inside the chiral binding pocket crafted by London dispersion about a heterobimetallic [BiRh] paddlewheel complex entails highly effective asymmetric C−H insertion; the resulting products formally correspond to the outcome of classical ester alkylation, allylation, benzylation, or aldol reactions.

Oxygen-dependent photo-reactivity for robust tumor therapy: A PDT-to-PACT evolving photo-reactivity with response to oxygen-consumption was found in cyclometalated gold(III)-alkyne complexes, leading to potent cytotoxicity towards cancer cells, strong anti-angiogenesis in zebrafish, and efficient suppression of mouse tumor xenografts.

Coordination cages containing porphyrin subunits are reduced up to fourteen times in the gas phase. While the presence or absence of Nickel(II) coordinated in the porphyrin binding site does not affect the rate of reduction, the reactivity of the reduced species toward molecular O₂ is significantly enhanced in the former case. Additionally, the presence of a C₆₀ fullerene guest within the nickelated cage reduces its reactivity.

An anchoring strategy was firstly proposed to generate solution processable TADF emitters from isotropic orientation to horizontal one by attaching bipolar 9,9′-spirobi[fluorene] subunits as anchoring groups onto TADF emitting core via flexible chains. With outstanding characteristics in pristine films, unprecedented EQE_maxs of 30.6 % and 25.6 % were achieved for solution processable non-doped OLEDs and TSF OLEDs, respectively.

Well-controlled phase junction nanocomposites are prepared by a novel surface ligand (decanethiol)-directed strategy. The conductivity is increased by modulation doping, and the phase boundary enhances phonon scattering, which helps to reduce lattice thermal conductivity. The combined effects yield a record-high zT=2.1 in metal sulfide thermoelectric materials.

Sactipeptides are a class of microbial peptides possessing thioether crosslinks. We demonstrate sactipeptide engineering without compromising their post-translational modification introduced by sactisynthases. A variety of natural and hybrid sactipeptide constructs were generated and analyzed for the presence of thioether crosslinks, demonstrating the possibility to design variants with novel functionalities.

The degree of ground state electronic interaction in the mixed-valence complex [{Cp*(dppe)RuC≡C}₂(μ-1,3-C₆H₄)]⁺ can be tuned through the introduction of an OMe substituent to the bridging ligand. These effects are sensitive to the position of the substituent, and follow the same patterns as those predicted by quantum circuit rules for weakly coupled molecules in molecular junctions.