Ratcheting is the mechanism by which stochastic molecular dynamics, and other random exchange processes in chemistry, can be directionally biased and driven away from equilibrium. In this Review we discuss the recognition, invention and development of molecular ratchets and kinetic asymmetry, which underpins it. We explain the design principles for different types of ratchet and energy sources, and outline some current challenges and opportunities for the future.

Beyond engineering the catalyst, rational design of the local reaction environment near the catalyst surface, including local pH, the choice of the species of cations and anions as well as local reactant/intermediate concentrations, also acts as an effective approach for further improving the catalytic performance of CO₂ reduction to valuable multicarbon products.

Fluorinated ethers are synthesized with weak-solvation ability owing to the duple steric effect derived from the designed longer carbon chain and methine group. The electrolyte solvation structure rich in AGGs (97.96 %) renders modified interphase and remarkable CE of 99.71 % as well as high CE of 98.56 % even at −20 °C. It also renders stable performance of pouch Li-S battery.

This study presents a unique approach for the selective synthesis of stereodefined trisubstituted vinylsilanes via the anti-selective addition of a novel solid Me₃SiZnI to terminal alkynes. An equilibrium exists between the intermediate syn- and anti-adducts, where the anti-selectivity is determined by the larger barrier at the single electron reduction of alkyl halides and the thermodynamic stability of the Ni(III) adduct.

The strong electronic metal–support interactions between Cu and In₂Se₃ cause the charge rearrangement, which is conducive to *OOH intermediate generation. The introduction of Cu not only reduces the energy of the 2-electron oxygen reduction intermediate but also inhibits the 4-electron oxygen reduction reaction, which facilitates the efficient production of H₂O₂.

Charge transfer between donor Ir(III) and acceptor Pt(IV) introduces synergistic activity for these photodynamic and phototherapeutic centres, ¹O₂ and radical generation, higher Pt accumulation, and damages cell nuclei and releases chromosomes. X-ray fluorescence revealed a broad distribution in cells, with Ir localised in small compartments, some as a cleaved fragment.

A nano-immunomodulator consisting of glutathione activable resiquimod and π-extended NIR-absorbing system is engineered for spatiotemporally controlled photothermal immunotherapy. The synergistic immunity and photothermal effect lead to complete tumor ablation against both primary and distal tumors, presenting a generic strategy for engineering nano-immunomodulator to achieve a precise regulation of photothermal immunotherapy.

New Fabry-Perot optical cavities were developed that enable studying Vibrational Strong Coupling (VSC) by Nuclear Magnetic Resonance (NMR) spectroscopy. We demonstrate that the London dispersion-driven conformational equilibrium of a molecular balance is altered when the C−H stretching vibration is strongly coupled to the cavity. Unexpectedly, VSC does not substantially affect molecular electron density distributions which has profound implications for the possible mechanisms at play in polaritonic chemistry.

A universal and accessible acylation strategy for fabricating cloaked crRNA to realize photo-initiated one-pot CRISPR–Cas12a assays regardless of the crRNA sequences has been developed. This innovative acylation strategy can bring great advantages and convenience in photo-controlled CRISPR technologies, highlighting their potential in genomic editing, disease therapy, and cell imaging.

The electrocatalytic 2eORR activity of the graphdiyne catalyst toward H₂O₂ production is successfully adjusted by steering the sp-carbon content in graphdiyne from 20 at % to 50 at %.

Cyano and fluorine dual-polar-group decorated multipolar polymer framework namely CNF-COF has been explored as an efficient and stable ionic sieve via electronic modulation to composite with solid polymer electrolytes for long-life all-solid-state (ASS) Li batteries at high rate. The CNF-COF incorporation not only affords rapid selective Li ion conduction, but also enables the LiF-rich SEI formation for stable Li anodes. Thus, the newly-developed composite electrolytes with an ultralow CNF-COF content of 0.5 wt % endow an ASS Li metal battery with excellent cycling stability over 2000 cycles at 1 C and over 1000 cycles at 2 C.

Palmarumycins are a major type of fungal spirobisnaphthalenes that are biosynthesized by two distantly located biosynthetic gene clusters (BGCs) jointly. PalA, an unusual, multifunctional P450, catalyzes the dimerization of DHNs to form the unique spiroketal and 2,3-epoxy groups. PalB installs the 5-hydoxy group, while PalC functions as a 1-reductase/dehydrogenase and epoxide reductase. PalD catalyzes the 1-dehydrogenation to form 1-keto products.

Bioinspired artificial proton channels that can sieving protons out of ions or water molecules with perfectly selectivity are constructed. The channels use the interlayer spacings of covalent organic framework materials consisting of hydrophilic functional groups to sterically reject all atoms or molecules, while providing hydrogen bonding network for proton hopping.

A hypoxia-responsive azocalix[4]arene (Naph-SAC4A) has been developed that can achieve a biotin/(strept−)avidin-level binding affinity (up to 10¹³ M⁻¹ ) through its expanded hydrophobic surface. Naph-SAC4A demonstrated the sensitive recognition of rocuronium in serum and a hypoxia-responsive delivery of doxorubicin with minimum leakage at the cellular level.

The tandem catalyst of Mo-PCN-222(Co) exhibited excellent activity in the electrosynthesis of urea, in which the two types of active sites independently stabilized the key intermediates of *CONH₂ in urea formation via tandem catalysis.

Strong metal-support interactions between Au nanoparticles and BiVO₄ supports are achieved under reductive treatment for photoelectrochemical water splitting. The electron-rich Au^δ− could extract photogenerated holes and accelerate the charge separation. The encapsulation of VO_x on Au surface enhances the *OH adsorption and the *OOH generation to promote the oxygen evolution reaction kinetics.

A kind of redox molecular junction sp² carbon-conjugated metal-covalent organic framework with multiple active sites have been prepared and can be successfully applied for light-assisted CO₂ energy storage.

We combined orientation-selective PELDOR and ¹⁹F Mims ENDOR to characterize the structural ensemble of RNA duplexes and their internal motions. In a quantitative comparison to MD simulations of RNA with and without spin labels, we found that state-of-the-art force fields with explicit parameterization of the spin label can describe the conformational ensemble present in our experiments.

A noncoplanar polyaromatic amine, 4,4′,4′′,4′′′-methanetetrayltetrakis(benzene-1,2-diamine) (MTLB), was used as a molecular building block for fabricating thin-film composite membranes via interfacial polymerization. The resulting membrane exhibited a high salt/antibiotic selectivity and water permeance. The excellent antibiotic desalination performance can be maintained in industrial-scale spiral-wound module.

Trioxa[9]circulene and dimethoxydiepoxycyclononatrinaphthalene were synthesized through intramolecular oxidative coupling of dimethoxydioxa[8]helicene, resulting in the formation of a nine-membered ring. Dimethoxydioxa[8]helicene and dimethoxydiepoxycyclononatrinaphthalene exhibit absorption and luminescence dissymmetry factors on the order of 10⁻², and trioxa[9]circulene exhibits remarkable π–π interactions in the crystals.

Long isomeric fibonacenes—a phenacene, a helicene and a croissant-shaped isomer—are found to show strikingly different absorption and emission spectra, despite their equivalent Kekulé structures. Complementary computations based either on magnetic or electronic criteria for aromaticity indicate that in long helicenes, the Clar and Kekulé rules of preferred sextet localization do not hold.

We modify activation conditions to stabilize different Cu-oxo and Cu-hydroxyl dimers in the zeolite SSZ-13. Subsequently we combine theory and experiment to investigate how the Cu site structure impacts the conversion of methane to methanol. Our results indicate that site stoichiometry controls methanol production in a stepwise conversion process.

A magnetic zeolite with Fe₃O₄ colloidal nanoparticles nucleus and single-crystalline ZSM-5 zeolites shell have been fabricated by a stepwise crystallization strategy. The resulting Fe₃O₄@HZSM-5 catalyst shows a high catalytic activity, selectivity, and stability for the dehydration of ethonal in a magnetically stabilized bed (MSB) reactor.

The ether-based electrolyte functionalized with an electron-withdrawing group (chloro-substitution) enabled the formation of a dual halides-based solid-electrolyte interphase (SEI), thereby enhancing the cycling stability (6000 cycles), high voltage (4.3 V) performance, and wide temperature operation (−5 °C to 45 °C) of potassium ion batteries.

The light-triggered translocation of ClO₄⁻ anion from cationic to neutral-binding site along BPym-OH dye is visualized by emission. The combination of time-resolved fluorescence and molecular dynamic simulation allows its description in time and energy domains. This reaction generates dramatically red-shifted fluorescence extending to near-IR that appears at ~83 ps, resulting from electrochromic modulation of coupled proton-electron transfer.

The sulfonate-functionalized metal–organic framework ZU-609 realizes 1,3-butadiene purification from complex C4 mixtures via synergistic size-exclusion and thermodynamic mechanisms, and polymer-grade C₄H₆ (99.5 %) is obtained via a single adsorption-desorption cycle under ambient conditions.

Two different p-tert-butylthiacalix[4]arene protected silver nanoclusters (Ag54 and Ag33) with different stabilities were isolated from identical reactants under different temperatures. Upon stimulation with bpbenz (bpbenz=1,4-bis(pyrid-4-yl)benzene), the kinetically metastable Ag54 and the thermodynamically stable Ag33 can yield the same product of Ag31via the breakage-reorganization and ligand exchange transformation mechanism, respectively.

This work constructs a monolithic and amorphous electrode/electrolyte interphase at low temperature which is thin, stable, and contains more organic components, facilitating fast Na⁺ kinetics, enabling sodium-ion batteries to achieve long-term cycling performance and great rate capability at −30 °C.

We present the first solid solution series of the new class of nitridomagnesophosphates with excellent luminescence properties in the cyan spectral range, tunable by Ba/Sr ratio. Extensive investigations have made it possible to attribute the luminescence to the doping of one crystallographic site. DFT calculations were carried out to investigate the influence of Mg in the P/N network for the first time.

Ordered octahedral site vacancies and filling of trigonal bipyramidal interstitial sites by transition metals stabilizes a 2×2×1 P6₃/mmc superstructure of NiAs with kagome nets in Ni_0.7Pd_0.2Bi, Ni_0.6Pt_0.4Bi, and Mn_0.99Pd_0.01Bi. Further ordering of the interstitial sites via composition generates a net polarization in Ni_0.9Bi and Ni_0.79Pd_0.08Bi with polar Fmm2 symmetry. The control of polarity is reflected in electronic transport properties.

A pair of acid/base responsive cages that can be interconverted without affecting the coordination environment have been self-assembled from 1,5-enedione/pyrylium based ligands, leading to a three-state supramolecular switch that can be controlled through strong acid/bases. A guest-binding-induced strain-triggered cage-to-cage transformation was found, in addition to chemical stimuli (acid/base, NH₃) responsive cage transformations.

Palladium-organic cages with acrylamide side chains were incorporated in N-isopropylacrylamide-based nanogels by precipitation polymerization. Due to the presence of cage crosslinks, the resulting nanogels can be used as specific sorbents for chloride ions.

This work reports an electrocatalytic cascade method for synthesizing ketones using CO2 as a CO surrogate. By employing a synergistic combination of two earth-abundant metal catalysts, high yields are achieved in a simple setup, demonstrating the potential for sustainable and efficient carbonylation reactions.

A series of anhydride-based covalent organic frameworks (i.e., PI-DP-COF and PI-DT-COF) with specifically designed zigzag hopping sites and zincophilic anhydride groups that can serve as desired platforms to investigate the related Zn²⁺ hopping/transfer, dendrite-inhibition, and plating/stripping behaviours as well as the interfacial interaction.

Chiral ammonium-oxocarbenium dications are accumulated in superacid through a tandem diastereoselective proton-transfer/intramolecular cyclization. Their reactivity in the diastereoselective remote functionalization of non-activated alkene is explored.

Water, a poison in traditional olefin polymerization processes using Ziegler–Natta catalysts, enables coordination-insertion copolymerization of ethylene and diverse polar monomers to produce significantly high-molecular-weight linear polar polyolefins (219–549 kDa) using single-component and neutral nickel catalysts under mild conditions.

A light-triggered J-aggregates system is developed for a converting cancer therapy with enhanced therapeutic outcomes. The photodegradation of cyanine leads to the destruction of J-aggregation, facilitating the conversion from photodynamic/photothermal therapy to long-lasting chemodynamic therapy. This work presents a safe and effective strategy for prolonging the therapeutic efficacy of ROS-based therapy.

A fluorinated phosphate cross-linked gel polymer electrolyte (FP-GPE) has been designed and fabricated for high-voltage lithium metal batteries (LMBs). The FP-GPE-based batteries display excellent electrochemical performance and high safety simultaneously even at practical conditions. Moreover, the first reported solid-state 18650 cylindrical LMBs have been successfully fabricated and demonstrate exceptional safety under mechanical abuse.

A series of porous bismuth-based metal halide perovskites with tunable band gap compositions are prepared and explored as photocatalysts for solar-light-driven oxidative phenol C−C and C−O coupling reactions. The porous morphology, appropriate band-edge alignment and Lewis acid sites of CsBi₂Br₉ are found to play a crucial role in stabilizing the phenolic intermediates, thereby boosting the reaction kinetics.

Aided by the syntheses of potassium indyl reagents, access is possible for the first time to a complete series of metal-trielyl complexes featuring the same xanthene-derived NON-framework. Analysis of mercury compounds of the type (boryl)HgE(NON) (E=Al, Ga, In) by structural, spectroscopic and theoretical methods shows that the aluminyl metallo-ligand [(NON)Al]⁻ is the most potent σ-donor.

The work reports a pyridine-based covalent organic frameworks (COFs) functionalized with pyridyl-imine structures to boost photocatalytic hydrogen peroxide (H₂O₂) production. The unique pyridyl-imine structures can effectively suppress the two-step two-electron (2e⁻) oxygen reduction reaction (ORR) process on imine-nitrogen sites, facilitating a more efficient one-step 2e⁻ pathway for H₂O₂ production.

The aprotic acetone-mediated five-membered-ring intermediate as the active site for the epoxidation reaction over a Ti-Beta/H₂O₂ system is observed for the first time by using in situ and 2D MAS NMR spectroscopy and theoretical calculations. The critical role of this intermediate in cyclohexene epoxidation is revealed.

While descriptor-based analysis has effectively delineated activity trends, addressing selectivity trends has proven to be a challenging hurdle in the quest to develop innovative catalysts for electrosynthesis of hydrogen peroxide via 2e-ORR. This contribution validates the efficacy of a novel selectivity descriptor, ΔΔG, using an extensive library of binary alloys. We demonstrate ΔΔG as the ultimate selectivity descriptor for 2e-ORR.

A novel pathway involving the evolution of Cu−(CO)x moieties driven by the synergistic adsorption of CO and H was identified for dynamic Cu sintering in Cu−N−C catalysts under CO2 reduction conditions.

“Innovative low-temp synthesis of single-atom Fe−N−C catalysts prevents Fe nanoparticles sintering, ensuring dense Fe-N₄ site formation, and leads to improved ORR activity and fuel cell efficiency, with potential for diverse high-performance single-atom materials.”

Light touch: A photosensitive copolymer made from elemental sulfur and low-cost dienes such as cyclopentadiene could be rapidly modified with low-power lasers operating in the visible and infrared wavelengths. Erasable information coding and direct laser lithography were demonstrated.

The unlocked birdcage symbolizes the material opening its spin gates, with the liberated bird representing charges. By unlocking the spin gates, the movement of charges becomes smooth and unrestricted, corresponding to the enhanced dynamics and stability of transition metal oxides during energy storage processes.

Two photoswitches, i.e., 6-nitro-spiropyran and o-fluoroazobenzene are shown to operate in a wavelength-orthogonal manner both in solution and when integrated into a porous material scaffold. Selective isomerization of each photoswitch can be triggered by a specific wavelength of light giving rise to four independently accessible states of the porous material, thus providing a basis for the dynamic multifunctional materials.

Atomically dispersed Ti−CNO catalysts are synthesized for photothermal catalytic cycloaddition of styrene oxide and CO₂ to styrene carbonate, achieving an excellent catalytic performance (98.3 % in 6 h, 10 cycles). The addition of Ti single atoms creates abundant mesoporous structure, enhances photothermal effect and Lewis acidic/basic sites, which facilitate the activation of styrene oxide and CO₂ to form styrene oxide^.+ and CO₂^.−, respectively.

Syngas conversion reaction induces the in situ generation of copper grain boundaries which leads to the formation of long-chain hydrocarbons. The synergy of grain boundaries and their vicinal low-index facets leads to the CO insertion where non-dissociative adsorbed CO on low-index facets migrates to grain boundaries and inserts into the metal-alkyl bond for the chain growth.

Breaking the tetrapyrrolic π-skeleton and implementing N-confusion modification offer a distinctive ligand platform for metalla-carbaporphyrinoid species. Through d-π orbital interaction, the resultant open-ring Pd/Pt complexes demonstrate near-infrared-II absorption capability and high photothermal conversion efficiency.

Mammalian cytochrome P450 drug metabolizing enzymes rarely cleave C−C bonds. Here we report the mechanisms of two unusual CYP3A-mediated cleavages of non-polar, unstrained C(sp²)−C(sp³) bonds in the metabolism of tyrosine kinase inhibitor pexidartinib. One bond is cleaved by CYP3A-mediated ipso-addition of activated oxygen, and the other occurs by a pseudo-retro-aldol reaction after hydroxylation of a C(sp³) site.

Based on coordination-driven self-assembly, weak C−H⋅⋅⋅halogen interactions together with aromatic stacking interactions are strategically utilized to selectively realize the construction of one unlocked metallacycle and four doubly interlocked metalla-links.

Natural surface frustrated Lewis pairs (SFLPs) are found on the stable wurtzite crystal surfaces. All the surface atoms serving as Lewis acid/base sites contribute to the surface density of SFLPs reaching up to the highest value to date. The approaching orbital orientations of SFLPs are the origin of the outstanding performance for the activation of small molecules, thereby demonstrating great potential in heterogeneous catalysis.

After high-voltage CV scanning, the higher (de)intercalation voltage and lower diffusion activation energy for both Cl⁻ and K⁺ boost the comprehensive improvement of the discharge voltage, capacity, rate and cyclic performance. The comprehensive improvement of electrochemical performance utilizing anion-cation competition chemistry is universal for different types of PBAs.

A spin-crossover Fe(II) complex demonstrating high-performance pyroelectricity across a remarkably wide temperature range just above room temperature was reported. Detailed structural analyses revealed that pyroelectric response can be ascribed to a giant thermal expansion of polar axis accompanied by a gradual low-spin to high-spin transition of metal centers.

We couple boron-nitrogen (B−N) dative bonds and B−O covalent bonds to generate a new class of vitrimers, boron-nitrogen vitrimers (BNVs), to endow them with dynamic features at usage temperatures. Compared with boron-ester vitrimers (BEVs) without B−N dative bonds, the BNVs showcase enhanced mechanical performance.

Durch eine gold-katalysierte 7-endo-dig-Zyklisierung neuartiger Trien-In-Systeme wurden interessante Azuleno[b]thiophene und Azuleno[c]thiophene synthetisiert und charakterisiert. Es wurden UV/Vis-Spektren, CVs und DFT-Berechnungen durchgeführt.

Die Kristallstrukturen der Terpencyclasedomänen (TC) zweier pilzlicher Sesterterpensynthasen (NfSS und PbSS) wurden bestimmt. Die Modellierung carbokationischer Intermediate, ortsgerichtete Mutagenese und Isotopenmarkierung lieferte detaillierte Einblicke in ihre katalytischen Mechanismen. Strukturbasiertes Engineering von NfSS und PbSS führte zur Bildung von 20 Sesterterpenen, darunter 13 neue Verbindungen.

Chemoselective phosphonylation of unactivated C(sp³)−H bond distal to the amide group was achieved at room temperature under transition-metal-free, photocatalyzed conditions.

The first asymmetric hydroboration of cyclobutenes using Rh catalysis is reported, providing gem-difluorinated α-boryl cyclobutanes in excellent regio- and enantioselectivity. Upon in situ B,F-elimination (Pd is required for R=aryl), monofluorinated cyclobutenes are obtained through formal hydrodefluorination. Versatile downstream transformations make this method a platform for the diversified synthesis of chiral fluorinated cyclobutanes.

Silyl-heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. These are limited by the lack of catalytic methods for the preparation of diverse and functionalized silyl-heterocycles. Herein the borane-catalyzed intramolecular 1,1-carboboration of silyl-alkynes has been developed for the synthesis of 2,3-dihydrosilolyl and silylcyclobut-2-enyl boronic esters.

A robust palladium/nickel/chiral aldehyde synergistic relay system was developed for the enantioselective ring-opening functionalization of gem-difluorinated cyclopropanes with N-unprotected amino acid esters, enabling the efficient assembly of α-quaternary α-amino acid esters bearing a linear 2-fluoroallylic motif in a highly enantioselective manner.

Catalytic methods to access different regio- and enantiomers by switching the least reaction parameters are attractive yet challenging. Herein, a Co-catalyzed regiodivergent and enantioselective reductive hydroalkylation of 1,3-dienes with aldehydes have been achieved, allowing for regio-switchable 1,2-hydroalkylation and 4,3-hydroalkylation of 1,3-dienes to furnish different homoallylic alcohol architectures from identical starting materials.

Molecules that cannot self-assemble in either layers or cylinders often form complex in-between “bicontinuous” structures made up of interpenetrating networks. The most widespread is the achiral “gyroid” phase, containing two antichiral networks. Here it is shown that the introduction of an asymmetric unit into the rod-like molecular core can rewind the segments of one of the nets, “supertwisting” them in reverse and making the famous gyroid chiral.

A novel nickel-backboned polymer/carbon nanotube thermoelectric composite fiber is fabricated through a shear-induced orientation method. It shows simultaneous increases in electrical conductivity and Seebeck coefficient, with a power factor of 719.48 μW m⁻¹ K⁻² as high as 3.5 times of the bare carbon nanotube fiber, opening a new avenue for the development of metal-backboned polymers in power supply.

The high cleavage probability of the surface S−C bonds in gold and silver nanoclusters and the structure–activity relations of the generated radicals are revealed through experiments and DFT calculations. Based on this understanding, we design several alkyl thiolated gold nanoclusters and achieve a two-to-three-orders-of-magnitude enhancement of the photoinitiation activity.

We innovatively adopted an electrodeposition-annealing method, synthesizing transition metal oxides (TMOs) single-particle nanoelectrode with well-defined structure and composition. Not only did we accurately measure their electrocatalytic activity, but we also specially designed a structure with a conductive core wrapped in a semiconductor (SEMI) shell, to support the actual evaluation of perovskite-type SEMI catalysts for oxygen evolution reaction (OER).

An efficient and straightforward strategy has been developed to create intricate and dense micro-architected copper structures using an ion-exchangeable hydrogel. The resulting copper geometries showcase a minimum feature size of around 40 μm, coupled with a notable twin density, electrical conductivity, and hardness. This methodology presents an effective pathway for the fabrication of micro-architected 3D metal structures.

High purity Ti₃C₂T_x (T=−CF₃SO₃) nanosheets were directly obtained via an etching route using an organic Lewis acid solvent that was completely free of HF. The obtained Ti₃C₂T_x terminated with −CF₃SO₃ had large nanosheets with an average size of approximately 4 μm, the largest size reached 15 μm, and the CF₃SO₃⁻ surface chemistry could generally improve the stability of the suspension.

A large bowl-shaped nanocarbon molecule with 126 π electrons was synthesized, and a ball-in-bowl complex was obtained by capturing C₇₀ at the concave site. A method for elucidating the stoichiometries in solution-phase equilibria was devised by developing a procedure to estimate the Occam factors for Bayesian inference.

In dieser Studie konnten wir die chemischen Strukturen einer neu entdeckten Gruppe von bakteriellen schwefelhaltigen Aminolipiden (Cysteinolides) mittels analytischer Techniken, Isolierungs- und Abbauexperimente sowie ihrer Totalsynthese revidieren und ihre absolute Stereochemie bestimmen. Im Gegensatz zu früheren Strukturvorschlägen auf der Basis von Homotaurin, weisen Cysteinolide eine cysteinolsäurehaltige Kopfgruppe auf, die mit verschiedenen (α-Hydroxy-)Carbonsäuren acyliert ist.