This Minireview summarizes recent progress in the production of HCHO from CO₂, including chemical catalysis (hydrogenation using H₂ and hydroboration/hydrosilylation), photo/electrocatalysis, and biocatalysis (enzymatic reduction). From analysis of advantages and deficits of each methodology, we present viewpoints and potential strategies for optimizing the CO₂-to-HCHO conversion.

This Review analyzes recent advances regarding the preparation of complex and stereochemically defined fluoro-organic molecules by routes originating from purchasable or readily accessible alkenyl and allylic fluorides. The untapped potential of other, far less explored, commercially available organofluorine compounds as launching points for the development of stereoselective processes that may be valuable to drug discovery is underscored.

Efforts to deepen the understanding of sustainable development have resulted in the concept of green carbon science. In this Review, technological achievements in green carbon science are discussed, with a focus on pilot testing, industrial demonstrations, and commercial applications beyond the laboratory stage.

By introducing a modified cross-linking mass spectrometry (XL–MS) approach, termed COMPASS (COMPetitive Pairing StatisticS), we unravel conformational changes of the intrinsically disordered protein α-synuclein upon liquid-liquid phase separation (LLPS). The conformational ensemble of α-synuclein shifts from a “hairpin-like” structure towards more “elongated” conformational states in liquid droplets. During this early LLPS stage, α-synuclein remains monomeric and highly flexible.

We present a proximity-driven, lysine-specific acetylation approach to construct precisely acetylated histone proteins. The approach is facilitated by a click reagent equipped with an acetate group donor to acetylate a nearby lysine in a sequence-controlled manner.

After demonstrating the potential of Th-based nanoscale metal–organic framework (nMOF) as excellent radiosensitizer with Monte Carlo simulations, we designed Th-DBP nMOF with Th₆ secondary building units and DBP photosensitizers for efficient radiotherapy-radiodynamic therapy. Th-DBP greatly enhanced hydroxyl radical and ¹O₂ generation upon irradiation to kill cancer cells and regress colon and pancreatic cancers in mice models.

We leverage the photoexcitation of arene–pyridinium electron donor–acceptor (EDA) complexes to achieve C(sp²)−H pyridination. Black light irradiation of the simple combination of arene substrate, pyridine, acid (to generate a pyridinium acceptor in situ), and O₂ (terminal oxidant) affords N-arylpyridinium products. This transformation proceeds without an exogenous photocatalyst, complementing prior photochemical C(sp²)−H amination methods.

The chemical composition of frustrated Lewis pairs is mapped to their performance in catalytic direct hydrogenation of CO₂ to formate using linear scaling relationships. This map highlights the need for appropriately balancing the acidity and basicity of the components for enhanced activity, which led to the demonstration of hitherto unreported catalytic turnover for this transformation.

A catalytic system involving titanium used for the exhaustive reduction of carboxylic acid derivatives to the corresponding methyl- compounds is reported. The catalytic system also works with other types of oxo-chemicals such as alcohols, aldehydes, ketones, lactones, and carboxylates while the products might be promising for bio-applications. Preliminary mechanistic studies reveal that the in situ generated Ti^III−H species was key for this transformation.

Synthetic polymers consisting of L-proline monomer units exhibit temperature driven aggregation in water with unprecedented hysteresis. This protein-like behavior paves the way to new processes, driven by either temperature or ionic strength changes, such as simple “with memory” thermometer.

Piezoelectric ZnO core-triboelectric microporous organic polymer (MOP) shell nanoparticles showed enhanced small energy harvesting performance, compared with ZnO and MOP. The piezo-triboelectric nanogenerator (PTENG) with the optimized 7 wt % ZnO@MOP/polyvinylpyrrolidone (PVP) film showed excellent durability for 30 000 cycles with peak-to-peak voltages of up to 534 V and a maximum power density of 1.19 mW cm⁻².

The first nickel-hydride-catalyzed diastereo- and enantioselective hydroalkylation of cyclopropenes has been developed for rapid synthesis of chiral alkylcyclopropane motifs. The reaction is efficient and versatile, taking place under mild conditions, and having excellent functional group tolerance. Concise asymmetric synthesis of antidepressant drug, D-Milnacipran, was performed to demonstrate the synthetic usefulness.

Described herein are the first total syntheses of (±)-dracocephalone A (1) and (±)-dracocequinones A (4) and B (5). An initially-envisioned intramolecular isobenzofuran Diels–Alder strategy guided the evolution of a Lewis acid-promoted spirocyclization approach that allowed for access to the carbocyclic core of 1. Further advancement by a series of carefully choreographed oxidations and rearrangements allowed for conversion to 1, 4, and 5.

The molecular-scale structure of the interface between copper electrodes and bicarbonate electrolyte, a key system for electrochemical CO₂ reduction, is clarified by in situ scanning tunneling microscopy, revealing two highly complex coexisting adlayer structures above a critical potential. Ab initio calculations identify these as carbonate/water coadsorbate layers and indicate a strongly stabilizing effect of the adjacent liquid solution.

Boroaminomethylation of olefins with CO as −CH₂-source via the mechanism of a carbene insertion into the N−H bond was described. In the present of CuCl and Xantphos as the catalyst, a variety of γ-boryl amines were obtained with broad functional groups tolerance. The new aromatization and other transformations of the γ-boryl amines demonstrate their utility. Notably, ¹³C labeled product was produced with isotope-labeled ¹³CO.

An enantioselective [3+2] annulation of oxime ethers and alkynes has been developed via catalytic transient axial-to-central chirality transfer strategy. More importantly, this annulation represents a rare example of construction of all-carbon quaternary centers through tandem Pd^II-catalyzed atroposelective C−H activation/double carbopalladation process.

Saturated N-heterocycles are important motifs found in many biologically active molecules. In this work, difunctionalization of 4–7-membered enecarbamates is achieved using both Cu/Pd and Ni-catalysed arylboration to deliver synthetically versatile borylated saturated N-heterocycles in good selectivity. The products are synthetically useful, as demonstrated by manipulations of the boronic ester to access biologically active compounds.

The chemical synthesis of pyridine-containing macrocyclic peptide pyritide A2 is reported. Inspired by biosynthesis, which proceeds through cycloaddition of post-translationally modified peptides, the described approach features rapid synthesis of a trisubstituted pyridine directly from a simple amino acid precursor. This strategy proved general for the preparation of different pyridines associated with this class of natural products.

After many years of being invoked as an intermediate, the existence of PhI(OTf)₂ was recently disproven. Taking advantage of a nitro substituent that suppresses decomposition; an NO₂-PhI(OTf)₂ molecule has been synthesized and structurally characterized.

A water-stable and deep-red-emissive radical cation P^.+−DPA−Zn was developed for mitochondria-targeted delivery of zinc ions to promote degradation of mutp53 in cancer cells via proteasome-dependent pathway and facilitate abrogation of various mutp53-conferred gain of function phenotypes.

A novel strategy named “scrambling polymerizations” is realized to produce polyester with tunable topologies by one-pot-one-step ring-opening copolymerization of a substituted δ-lactone derived from CO₂ and 1,3-butadiene with ϵ-caprolactone mediated by sodium phenolate. The obtained transparent, non-cytotoxic and degradable network presents great resilience and excellent elastic recovery properties for application as a polyester elastomer.

An osmium nitride is shown to insert nitrogen into indenes to afford isoquinolines. A synthetic cycle to regenerate the starting nitride is presented alongside mechanistic studies of each step.

Durch die in situ Aktivierung des Hafnocens meso-I wird isotaktisches Polypropylen anstelle des ataktischen Polypropylens von meso-I und rac-I hergestellt. Mit unserem praktischem Isomerisierungs- und Polymerisationsprotokoll lassen sich Produktivitäten erzielen, die mit reinem rac-I vergleichbar sind, wenn es auf reines meso-I oder ein Gemisch aus beiden Isomeren angewendet wird.

Sauerstoff-K-Kantenspektroskopie des hydratisierten Protonenkomplexes in Lösung bietet stichhaltige Beweise eines ausgeprägten Einflusses auf die elektronsiche Struktur der Wassermoleküle, die an der Hydratation beteiligt sind, wobei eine Hierarchie der Kopplungsstärke zum Proton durch tiefgreifend starke Orbitalwechselwirkungen in den räumlich nächsten drei Wassermoleküle und Coulomb-Wechselwirkungen der positiven Protonenladung mit den Wassermolekülen der ersten Hydrathülle deutlich wird.

Aufklärung von Ionenadsorptionreaktionen. Die Kombination aus oberflächenempfindlicher v-SFG-Spektroskopie und Flussexperimenten ermöglicht es, das Zusammenspiel einer dominanten Fluorid- und einer schwachen Calciumadsorptionsreaktion an der Fluorit-Wasser-Grenzfläche aufzudecken. Dies wird durch die systematische Änderung der Konzentration im Volumen und die Unterdrückung der Fluoridauflösung ermöglicht.

Using a fragment-based screening strategy by NMR, we identified 311 small molecule binders of 25 SARS-CoV-2 proteins, thus expanding the previously unexplored chemical and target space. Further, using experimental and bioinformatic analysis we identify potential binding sites. This comprehensive data would greatly assist medicinal chemistry efforts even beyond COVID-19.

Two region-specific selenium-based non-fullerene acceptors flanking conjugated side chains are compared with their sulfur-based analogue. mPh4F-TS with selenium at the outer positions show the most rigid skeleton, red-shifted absorption and compact stacking. The PM6 : mPh4F-TS organic solar cells exhibit the lowest energetic disorders, the highest charge carrier mobility and the best photon response, affording a top-ranking efficiency of >18 %.

The well-defined architecture, identical density of active sites, and monolayer characteristic of bimetallic Ni, Co two-dimensional polymer model oxygen evolution reaction catalysts can decouple the intrinsic activity of active sites from other factors. The experimental and density functional theory simulation show that the relative position and local coordination environment have a significant effect on the cooperation between the metal centers.

Cryptophanes are molecular hosts of particular interest for the development of biosensors based on xenon magnetic resonance imaging as they bind xenon reversibly. To prepare such a biosensor, a reactive site on the cryptophane core, which is desirable for such applications but synthetically challenging, has now been introduced by replacing a crown methylene bridge by a nitrogen atom to form a cryptophazane.

The first atomically monodisperse thiolated Pd nanocluster is obtained. It has a +6 charged di-tetrahedron Pd₈ kernel and a +3 charged μ-6 interstitial B atom The as-obtained Pd nanoclusters show better catalytic activity compared to 1.4 nm Pd nanoparticles, Pd₂ complexes and the commercial Pt/C catalyst for the oxygen reduction reaction.

New fluorine/chlorine regio-regular hetero-trihalogenated terminal was firstly synthesized and systematically employed to enhance single-crystal packing, improve film morphology, and boost device performance of the hetero-halogenated SMAs. The PM6 : Y-FClF achieved a remarkable PCE of 17.65 %, which is far better than that of Y-Cl and Y-FCl and is the highest efficiency for the hetero-halogenated SMAs-based binary OSCs.

A novel strategy to modulate the charge distribution of active centers of organic catalysts by using unsaturated bonds (UBs) is reported. The UBs can produce para-activation, identifying the para C=N group as active centers. The effect of UBs decoration on adsorption property of the catalysts is disclosed.

The spectral tuning—from green to red—of luciferase-free luciferin's electrochemiluminescence (ECL) was demonstrated by means of electrolyte engineering. The color change does not require, as still debated, a keto/enol isomerization of the light emitter, and brings evidence of the electrostatic-assisted stabilization of the charge-transfer (CT) excited state by double layer electric fields. Visual mapping of ECL and fluorescence fronts enables the optical quantitation of superoxide and oxyluciferin diffusivities.

Helical sense induction in polymers is usually commanded by the chiral residue directly attached to the polymer backbone. In this work, it is demonstrated that either a P or M helical sense can be induced into a poly(phenylacetylene) by activation of a chiral overpass effect followed by selective manipulation of the conformational composition at a remote chiral center.

We report a method for direct enantioselective alkylation of 3-alkynoic acids and 2,3-alkendioic acids that form quaternary stereogenic centers, and application of this method to the total enantioselective synthesis of complex alkaloid (+)-goniomitine. Crystallographic studies highlighted cation-π interactions between lithium and alkyne groups in the chiral lithium aggregate intermediate.

The first metal-free access to poly(cyclopentene carbonate) and its chemical recycling to monomer were achieved by using a dinuclear bifunctional organoboron catalyst, enriching the portfolio of the circular plastic economy.

We reported the use of single-stranded DNA (oligo-adenine, oligo-A) to encode the wettability of gold seeds by homogeneous gold adatoms. This oligo-A-based surface chemistry engineering method will enable controllable diffusion of adsorbed atoms on the nanoscopic surface to develop single-nanoparticle plasmonic devices for extreme nanophotonics and polariton chemistry.

Densely functionalized chiral allyl species, with an alkenyl CF₃ group, were prepared with excellent selectivity by selenium-catalyzed sulfenofunctionalization of allylboronic acids. The method can be used to access chiral allyl SCF₃, SCF₂R, SCN and SAr compounds.

An ultra-low cost reaction exploration algorithm (Yet Another Reaction Program, v2.0) is used to predict reaction outcomes and characterize multiple unimolecular and bimolecular reaction networks. The diversity of these benchmarks illustrate that reaction exploration algorithms are approaching general-purpose capability.

Reductive nickel catalysis was leveraged to orchestrate the multicomponent union of glycosyl halides, organoiodides and isobutyl chloroformate to assemble C-acyl glycosides in high anomeric selectivities. Computational studies provided insights that rationalize the origin of the high chemoselectivity. The method is applicable to the synthesis of complex C-linked disaccharides and late-stage keto-glycosylation of peptides.

A universal and straightforward strategy is designed to efficiently self-assemble MOF nanoparticles into robust MOFtors based on the Pickering emulsion. Such MOFtors are capable of enhanced organic- or heavy-metal-ion-contaminants remediation without mechanical stirring.

A set of molecular sensors with ¹⁹F barcodes enables multiplex detection of different biomarkers associated with organ injury and cancer. The barcoding strategy takes the advantage of ¹⁹F's high magnetic resonance (MR) sensitivity, prompt signal response to environmental changes, negligible biological background, quantitative signal output and multiplex capacity.

TADF conjugated polymers with narrowband emissions are developed by attaching multiple resonance emitting moieties as pendant onto the polycarbazole backbone, and the resulting OLEDs achieve a maximum EQE of 17.5 % with FWHM of 34 nm.

We report a new class of trimethine skeleton NIR-II fluorophores (NIR-II Cy3s) with improved stability over traditional heptamethine NIR-II fluorophores and emission above 1000 nm. The NIR-II Cy3s can reversibly respond to HClO and reactive sulfur species (RSS) and can serve as an effective platform for the reversible monitoring of the HClO/RSS-mediated redox process in a pathophysiology environment. Finally, we applied NIR-II Cy3-988 to the reversible assessment of the redox environment and dynamic effect of drug treatment in an acute inflammation model and of redox potential changes during liver injury and repair.

Visible-light-triggered carbon−heteroatom cross-coupling reactions without exogenous photocatalysts were realized using a nickel catalyst that was activated through intraligand charge transfer. Ligand polymerization afforded a porous, recyclable organic polymer for heterogeneous nickel catalyzed cross-coupling reactions. The heterogeneous catalyst demonstrates stable performance in a packed-bed flow reactor during a week of continuous operation.

We developed a general strategy for constructing photoactivatable probes by introducing a universal tag SO on fluorescent molecules. This strategy is applicable to most of the commercial fluorophores with various skeletal structures. We successfully applied these photoactivatable probes for time-lapse super-resolution tracking in living cells and super-resolution imaging of microtubules in fixed neurons.

Although the self-assembly of L-phenylalanine (LPF) is insensitive to the pathway followed, the co-assembly of LPF with naphthylamine derivatives is pathway-dependent. The helical nanofibers of LPF transform into diverse kinetically trapped chiral structures with opposite chirality through a kinetic co-assembly pathway (pathway B), while only thermodynamically stable nonhelical structures are formed by the thermodynamic pathway (pathway A).

QM/MM modeling revealed that the C(sp³)−H β-hydroxylation of L-PAPA in the diiron hydroxylase CmlA transpires unprecedentedly through a traceless amine-assisted O₂ activation pathway. This novel O₂ activation mode modulated by the L-PAPA substrate, which is associated with the adapted coordination environment of the diiron cofactor upon O₂ binding, opens up more structural and mechanistic possibilities in O₂ activation by non-heme diiron enzymes.

Coupling multiphase coacervate droplets to a chemical reaction cycle allows access to regimes inside the phase diagram not possible under thermodynamic control. Control over the stability, liquidity, and localization of the multiphases makes it a great synthetic platform to study the organization of membraneless organelles.

A bottleable, halogen-free, neutral, single-site Lewis superacid, tris(ortho-carboranyl)borane (BoCb₃) is synthesized in one pot from commercially available materials and its properties investigated. The electron withdrawing effect of ortho-carborane along with its lack of pi-delocalization of the LUMO induces the unusually high Lewis acidity. Catalytic C−F bond functionalizations indicate that BoCb₃ is a promising Lewis acid catalyst.

Ynamide coupling reagents combine the advantages of conventional active esters and coupling reagents, while overcoming their disadvantages, and exhibit superiority in addressing the notorious racemization/epimerization issue. The applicability of ynamide coupling reagents has been successfully expanded to peptide fragment condensation, head-to-tail cyclization, and solid-phase peptide synthesis on the basis of a systematic mechanistic study.

Biocatalytic cascades can be used for the efficient, asymmetric synthesis of bioactive compounds. A substrate multiplexed screening (SUMS) based directed evolution approach was implemented to improve the substrate scope overlap between a transaldolase and a decarboxylase. The matched substrate scope of the enzymes was leveraged to produce a variety of enantiomerically pure 1,2-amino alcohols in a one-pot cascade from aldehydes or styrene oxides.

Nickel-catalyzed asymmetric cyclization of fluoroalkyl-substituted 1,6-enynes with boronic acids is achieved triggered by C(sp³)−F bond activation, which provides an expedient access to 4-fluorovinyl-substituted 2-pyrrolidones in good yields with remarkably high levels of chemo-, regio- and enantioselectivities (90–99 % ee). The utility of this strategy was demonstrated in the enantioselective synthesis of the antiepileptic drug Seletracetam.

Dual-site synergism of vacant and protonated pyridine N in polymeric C₃N₄ significantly polarized the inert CO₂ molecules and eliminates the formation energy barrier of key *COOH intermediates, inducing a state-of-the-art activity enhancement (183 times) in CO production. Our atomic-precision strategy offers a promising way to overcome the technical challenges in molecular activation and rate-limiting proton transfer during CO₂ photoreduction.

Smart adsorbents are fabricated by introducing Cu⁺ into azobenzene-decorated metal-organic frameworks, in which azobenzene acts as light-responsive motifs and Cu⁺ as π-complexing sites. Ultraviolet-/visible-light irradiation triggers the isomerization of azobenzene, causing the changes in electrostatic potential around Cu⁺. This exposure/shelter effect adjusts CO capture and release by shifting light.

Ultra-thin microporous polymer composite membranes with extraordinary perm-selectivity for organic solvent nanofiltration were fabricated by employing two novel 2,2′-biphenol (BIPOL) derivatives as IP monomers. The enhanced microporosity arises from the hyper-crosslinked network structure and monomer rigidity. Moreover, it can achieve precise separation of organic molecules with similar molecular weights on their charge and molecular size.

A pyridine-stabilized N-phosphinoamidinato N-heterocyclic carbene-diboravinyl cation was obtained through the displacement reaction of the bromide substituent on a diborene derivative using pyridine. This newly formed species was shown to be a boron analogue of the vinyl cation which could be used for the activation of small molecules.

Hydrophilicity-based triple-code site-directed mutagenesis (S-T-Q) was applied to the wild-type enzyme RgDAAO, leading to a mutant Zn7 with greater than 2000-fold improvement in specific activity toward the unnatural substrate D-glufosinate, which was converted into PPO, a precursor of an excellent herbicide, L-PPT. Computational analysis revealed that the higher activity was mainly caused by an extended reaction pocket with greater hydrophilicity.

The regio- and stereodivergent asymmetric α-allylation of aldimine esters with racemic allylic alcohols was enabled by cooperative catalysis. The Et₃B additive plays a significant role in ionizing allylic alcohols to form electrophilic metal-π-allyl species and simultaneously promotes the formation of nucleophilic Cu-ylides. Computational mechanistic studies revealed the role of the Et₃B additive and the origins of stereo- and regioselectivities.

A planet-satellite-type amphiphilic supramolecular megamer is presented. It exhibits an unprecedented hierarchical self-assembly process in aqueous solution. The self-assembled structures formed by the megamer evolve from vesicles to vesosomes and eventually to a peapod-like structure with micrometer-sized tubes as the pod and vesicles encapsulated inside it as the peas.

A novel enzymatic cascade catalysis consisting of formate oxidase (FOx) and horseradish peroxidase (HRP) has been created for the high-throughput RAFT synthesis of well-defined, ultrahigh molecular weight polymers, under benchtop conditions at volumes down to 50 μL.

A versatile method allows zeolite nanosheets (NSs) to be prepared from single-species amorphous aluminosilicate NSs (AAS-NSs). The AAS-NSs were prepared by the two-dimensional reactor in amphiphilic phases (TRAP) method. Using this approach four zeolite types were prepared from single-species AAS-NSs by the dry gel conversion (DGC) process with structure-directing agents (SDAs).