In this Minireview we present and discussed a series of examples from various areas in which reactive intermediates have been detected during mechanochemical reactions. Understanding the factors behind the formation and stabilization of these intermediates could enhance mechanochemical methods and chemical reaction development.

This review shows how to design feedback-controlled reaction networks in different molecular systems that have a range of non-linear functions. These networks are a useful set of tools for creating chemical systems and materials that are interactive and have homeostasis-like animate features. These discoveries pave the way for the development of forthcoming next-generation systems and materials.

This Minireview sums up cutting-edge concepts regarding the formation of protein-based supramolecular structures, compartmentalization, and self-assembly monitoring; it compares the routes of their modifications and applications in multifunctional biomaterial design. We summarize the current knowledge about machine learning/artificial intelligence applications for protein structure prediction/obtainment and link it to biomaterial performance.

This review explores recent developments in light-driven radiochemistry, focusing on key isotopes (fluorine-18, carbon-11, zirconium-89) in positron emission tomography (PET). These technologies have been used to radiolabel small molecules, peptides and larger biomolecules such as monoclonal antibodies.

This Review aims to provide an overview on the recent photochemical strategies for the construction and/or functionalization of bicycloalkanes, cubanes, and some of their heterocyclic structural analogues. The synthetic methods have been organized according to the molecular target, and with a particular emphasis on the type of photochemical mechanisms involved. Future perspectives and open synthetic challenges within the field are presented.

Nanographenes (NGs) produced by top-down methods carry multiple functional groups. We utilized this aspect for the reproduction of purple light by adding red- and blue-light emitting fluorophores. Based on our results, NGs can be utilized as carriers of fluorophores capable of generating intermediate colors of light.

Upon membrane fusion and lipid mixing, the embedded functional dyes undergo cycloaddition to form the covalently bound product, resulting in the emission of FRET signal, which remains even after liposome destruction.

We synthesized a kind of supramolecular cationic polymer bearing cucurbit[7]uril (CB[7]) for the delivery of the plasmid encoding destabilized Cas9 (dsCas9) and single-guide RNA. The dynamic host-guest complexation between CB[7] moieties and trimethoprim, a stabilizer for dsCas9, can be competitively decomplexed by elevated polyamines in the tumor cells to activate Cas9-based genome editing in vivo, thereby ensuring the highly specific therapeutic genome editing for cancer gene therapy.

The small-molecule brachyury downmodulator DHC-156 was developed through the optimization of afatinib, an FDA-approved inhibitor. A series of structure–activity relationships, guided by biochemical assays and crystallography, lead to the discovery of DHC-156, which was shown to spare all wild-type kinases and downmodulates brachyury in a post-translational manner.

PTFBK has been employed as a multifunctional additive to target and modulate bulk perovskite defects and carrier dynamics of PSCs, endowing the decrease of Young′s modulus and residual stress in the perovskite layer. Moreover, benefit to the dominant crystal orientation and the suppression of non-radiative recombination, excellent stable inverted device with PCE of 24.99% was achieved.

The synthesis of ammonia over a Cs-promoted Fe catalyst via the novel approach of mechanocatalysis is carefully studied by ex situ characterizations of the catalyst. Physicochemical changes are related to the different stages of ammonia formation. Optimizations based on these results resulted in the intrinsically complicated low-temperature ammonia synthesis being one of the longest stable mechanocatalytic gas-phase reactions to date.

A new porphyrin conjugated polymer cathode, COP500-CuT₂TP is achieved under electrochemical polymerization. Self-exfoliation of polymer cathode promotes charge storage, leading to a specific capacity of 420 mAh g⁻¹ and 900 Wh Kg⁻¹. Excellent cycling stability up to 8000 cycles at 5 A g⁻¹ is achieved. Mechanistic insights by combining experimental and computational investigations supports the charge storage performance.

A weak *NH₂OH binding affinity and a favorable reaction pathway (*NHO pathway) jointly enable single-atom catalysts (SACs) with superior hydroxylamine (NH₂OH) selectivity. Then, an activity volcano plot of G_ad(*NHO) is established to predict Mn SACs as optimal electrocatalysts that exhibit pH-dependent activity. Furthermore, Mn−Co geminal-atom catalysts are predicted to optimize G_ad(*NHO) and are experimentally proven to enhance NH₂OH formation.

A new N−N coupling approach to the practical synthesis of hydrazides is disclosed by employing an S_N2 strategy at electrophilic amides with nucleophilic amines. The reaction exhibits mild conditions, broad substrate scope, excellent functional group tolerance, easy scalability, and is applicable to the late-stage modification of various approved drug molecules, thus enabling complex hydrazide scaffold synthesis.

In this report, we established a method that replicates a hydrophobic environment akin to that of the endoplasmic reticulum, leading to effective suppression in dead-end products and acceleration of reaction rates through high thiolate concentrations for the oxidative folding of cysteine-rich peptides and microproteins.

Endo/lysosomal cathepsin B activity differentiates among cell types and serves as a stimulus to trigger cell-specific endosomal escape. By designing nanocarriers armed with cathepsin B-activatable endosomal escape function, endosomal escape can be controlled to only occur in targeted cancer cells with upregulated endo/lysosomal cathepsin B activity. This innovative approach offers a new means to achieve targeted intracellular protein delivery.

With interlayer gap of 0.342 nm, graphite armor serves as a natural molecule sieve screening out bulky adversative molecules like O₂ or CO but allowing H₂ to diffuse along both the out-of-plane and in-plane direction. This creates perfect chance for fabricating robust HOR electrocatalysts.

The flexible Zn-ion electrochromic battery (ZIEB) with multiple color conversion, satisfactory capacity and superior cycle stability was assembled for real-time energy monitoring through visual color conversion.

Leveraging plasmonically-driven feature enrichment and machine learning-directed data augmentation to create a 3-dimensional (3D) nanoparticle structural space for bidirectional predictions of silver nanocube's purity, size, and shape (corner radius) in as-synthesized nanoparticle mixtures using extinction spectra and vice versa.

The Rh-catalyzed hydroamination of bis(allenes) with diamines was found to be an efficient strategy to access chiral crown ethers starting from achiral substrates. This new strategy is characterized by high chemo-, enantio-and diastereoselectivity with a wide range of substrates and with good functional group tolerance to access a wide range of chiral macrocycles in high yields under mild conditions.

Binding of precursor molecules to the side of a fibrous assembly of self-replicating macrocycles can improve the fidelity of replication and yield a novel error-correction mechanism, provided that the fibers bind selectively to precursors that match the building-block composition of the replicator.

In this work, a general post-synthetic strategy for constructing bifunctional catalysts, Rh-COF, which connect photosensitive covalent organic frameworks and transition-metal catalytic groups through covalent bonding, was developed. Fascinatingly, such complexes enable efficient photothermal conversion properties, which can improve the photothermal catalytic performances in C−H activation to obtain excellent yield, substrate suitability and recyclability.

Oxygen-activated boron nitride fibers (BNH) have been successfully synthesized and applied for the selective photocatalytic coupling of methanol to ethylene glycol (EG) reaction. The OB₃ unit in the BNH plays an important role in the selective dehydrogenation and C−C coupling of methanol molecules, leading to excellent activity and selectivity of BNH for EG production.

This work provides a foundational understanding of an electrochemical strategy for doping and structurally modulating electrically conductive metal-organic frameworks. Additionally, various applications of these MOFs have been developed based on their distinct electrochemical behaviors.

By elaborate thiophene π-bridge manipulation, BT-NS in which benzo[c]thiophene serves as π-bridge is constructed. An integration of experimental and theoretical studies disclosed BT-NS is advantageous for NIR-II FLI/PAI/PTI trimodal imaging-guided PDT/PTT treatment of tumors, displaying outstanding therapeutic efficacy and excellent biocompatibility.

A high-density Sn single atom catalyst is presented and ATR-FTIR is used to reveal the pH-dependent adsorption strength of *CO₂⁻, a key intermediate in acidic electrolyte on its surface. It is shown that the increase of electrolyte pH results in a redshift of the peak position of the *CO₂⁻ intermediate, i.e., the adsorption strength of the *CO₂⁻ intermediate increases, which in turn affects the performance of CO₂RR to direct HCOOH in acidic electrolyte.

A computational study demonstrates that Flavin-N5OOH species can function as both powerful nucleophiles and bases in the superfamily of flavoenzymes, which can mediate many kinds of challenging non-redox reactions, such as the cleavage of C−X (X=N, O, S, Cl) bonds. The findings revive oxygen activation chemistry by flavoenzymes and are expected to spur the discovery of many other Flavin-N5OOH-dependent enzymes.

An enzyme-cleavable solubilizing tag was described for the chemical synthesis of mirror-image proteins. Solubilizing tags were easily installed on the side chain groups of ^DLys/^DSer/^DThr and the N-terminal α-amino group of D-peptides via an L-Lys linker. Solubilizing tags were impervious to various commonly used reagents in D-protein synthesis. After protein assembly, multiple solubilizing tags can be removed under denaturing conditions.

Proton-Coupled electron transfer (PCET)-type reactivity of the dinuclear Au^II hydroxide complex Au^II₂(L)₂(OH)₂ (L=N,N′-bis (2,6-dimethyl) phenylformamidinate) towards weak X−H bonds is reported. For C(sp³)−H oxidation Au−Au σ-bond polarization leads to an adjustment of oxidation levels for both Au centers prior to the PCET event. The oxidation event for C(sp³)−H bonds is therefore described as a valence tautomerism induced PCET, where a basic reduced Au−OH unit serves as proton acceptor and the second more oxidized Au center as an electron acceptor.

Liquid structuring usually relies on the interfacial jamming of nanoparticle surfactants. Here we show that not only droplets in non-equilibrium shapes but also printed liquid patterns with useful geometries can be created from a highly interfacial active molecular Gemini surfactant that generates elastic, “solid-like” monolayers at the oil/water interface. The surfactant can also be used to produce ultra-stable emulsions with potent lubricity.

A highly reversible aqueous Zn battery was built by taking advantages of the biomass-derived cellulose nanocrystals (CNCs) electrolyte additive with unique physical and chemical characteristics simultaneously. The CNCs additive not only serves as fast ion carriers for enhancing Zn²⁺ transport kinetics but regulates the coordination environment and interface chemistry to form dynamic and self-repairing protective interphase, resulting in building ultra-stable Zn anodes under extreme conditions.

A smart DNA hydrogel that responds to the inflammatory environment by releasing multivalent functional units including photodynamic units, immune-activating units, and exosome killing units is constructed. The functional units have excellent tumor cell killing and immune activation efficacy, and the functional units can also synergistically modulate the immune microenvironment for efficient combination therapy.

A polyacrylonitrile-based zinc ion conductor (CPANZ) with a localized conjugated structure is induced and achieved at low temperature by Lewis acidic Zn(OTf)₂. The CPANZ layer effectively accelerates the Zn²⁺ migration but restricts the H⁺ migration. Encouragingly, the chemical corrosion, hydrogen evolution reaction and other side reactions are significantly mitigated at the CPANZ@Zn anode and homogeneous Zn deposition/dissolution is guaranteed.

Amine-releasable mediator methylammonium pyridine-2-carboxylic (MAPyA) is demonstrated to in situ repair the imperfections in perovskite film. The specific mechanism is that MAPyA-released methylamine gifts a crystal reconstruction environment by inducing liquid intermediate phase, thus reconvert the microcrystals and residual PbI₂ to perfect perovskites in situ. The optimized device exhibits efficiency of 24.06 % and excellent photostability.

A novel proximity-enhanced functional imaging (PEFI) analysis was developed for accurately visualizing tumors at cellular, tissue, and animal levels by enhancing metabolic differences. The strategy will potentially aid tumor identification, analysis, and surgical guidance.

THz spectroscopy is used to show that fluorine atoms have a discernible preference for bonding with sp³-boron over sp²-boron in the fluorination reactions of boric acid. This result helps resolve the F/OH substitution structural ambiguity. A reaction pathway for fluorination via the hydrothermal and room-temperature evaporation reactions is presented which gives insights into previously obscured aspects of the borate-fluorination process.

Synergistic Lewis and Brønsted acid sites in solid-acid electrocatalysts could achieve low potential and high formate selectivity toward glycerol valorization, because the Lewis centers promote OH* formation and the Brønsted centers enhance selective oxidation of glycerol to formate. This study demonstrates the vital roles of solid-acid sites in improving the activity and product selectivity for electrocatalytic biomass upcycling.

A multidisciplinary pipeline consisting of medicinal chemistry, molecular phenotyping, chemoproteomics, RNA-sequencing, short hairpin RNAs (shRNAs)-mediated gene silencing and in vivo studies led to a novel series of compounds suppressing pathogenic fibroblast activation via Hypoxia up-regulated protein 1 (HYOU1) inhibition. The first reported HYOU1 inhibitors are presented as a promising therapeutic approach in fibroblast-related diseases.

Polydopamine (PDA) containing pyrrole nitrogen atoms not only promotes charge separation but also serves as a ⋅O₂⁻ adsorption reduction active site for efficient H₂O₂ production. In the absence of sacrificial reagents, the H₂O₂ yield of CN-PDA was 742.8 μM h⁻¹, 47 times higher than CN.

A transition from electrochemically inactive Cl-terminated Ti₃C₂ to fast, pseudocapacitive behavior is reported for N,O-terminated Ti₃C₂ MXene, attributed to the presence of confined water between the MXene layers. This study evidences the crucial role surface terminations and confined water in charge storage and reaction kinetics in MXene materials.

In this work, the novel metallic heterostructure Co₃Mo₃N/Co₄N/Co was prepared and exhibited excellent water splitting performance. This metallic heterostructure enhances the electron transport efficiency and accelerates the reaction rate of water molecules on its surface by optimizing the electronic structure of the heterointerface.

Copper nitrenoids are key intermediates in copper-catalyzed direct C−H amination reactions but are difficult to study due to their high reactivity. This research shows that absorption to an antenna ligand can promote the denitrogenation of copper azide complexes in the gas phase and also channel the internal energy to promote the C−H amination reaction, which opens a new way to study the reactivity of highly reactive species under well-defined conditions.

Crystallization control of perovskite thin films is the key in commerciallization of perovskite solar cells. However, the fast crystallization of the thin film including nucleation, growth and Oswald ripening, is still a mystery though some efforts made. According to the theories of nucleation and Oswald ripening, we modified the perovskite surface energy and improved the grain solubility, and quantified the nucleation and ripening rate in experiments.

Three new non-fully conjugated dimerized giant acceptors with different alkyl-linked sites are developed. Among them, wing-sited 2Y-wing has fine-tuned packing and better miscibility with donor, allowing to 19.13 % efficiency (which is the highest value among the devices with giant acceptors) and highly stable organic solar cells.

This study describes an amplifiable RNA circuit based on the system of catalytic hairpin assembly with combination of controllable CRISPR-Cas9 function, which can directly build regulatory connections between originally independent endogenous genes in mammalian cells. With this design, artificial signaling pathways can be introduced into mammalian cells to control cellular responses and phenotypes through differentiated RNA expression.

The dynamic light-triggered depolymerisation of chiral molecular motor-based supramolecular polymers has been observed in real time with High-Speed Atomic Force Microscopy (HS-AFM). These results show the depolymerisation selectively from the polymer ends through a cooperative process.

Triazatruxene (TAT)-based PPNs were synthesized to investigate how the existence of a hexyl functional group would affect charge transfer. The hexyl group on the TAT unit ensured the transfer of photoexcited electrons from a donor unit to an acceptor unit, resulting in improved photocatalytic activity and hydrogen production.

A new plasticized polymer electrolyte integrated with fluoroethylene carbonate (FEC) additive was reported to address the interface instability issue existing in sodium metal batteries. Impressively, dome-like Na⁰ nucleation/growth with thin, amorphous, and fluoride-rich SEIs was identified, enabling excellent long-term cycling stability in Na//Na₃V₂(PO₄)₃ pouch cells (93.1 % capacity retention after 250 cycles at C/3) at room temperature.

An oxygen-containing-species coordination strategy to boost CO₂ electroreduction in the presence of O₂ was proposed. In the presence of O₂, one of the Co sites in the NiPc-Salen(Co)₂-COF that coordinated with the intermediate of *OOH from the oxygen reduction reaction could decrease the energy barrier for the activation of CO₂ molecules and stabilize the key intermediate *COOH of the CO₂RR over the adjacent Co center and thus boost the CO₂RR performance.

A Zn-porphyrin-based metallacage exhibited strong host-guest interactions with fullerene derivatives. The complexes could be dissembled by the further addition of 4,4′-bipyridine to form a more stable coordinated complex. This tunable host-guest complexation was further employed to generate different types of reactive oxygen species, enabling the highly efficient and selective photocatalytic oxidation of benzyl alcohols.

A novel method to site-specifically crosslink DNA duplex upon visible light irradiation. Ru complex on the third strand catalyzed [2+2] photocycloaddition of stilbene moieties via triplet-triplet energy transfer. Site specificity is realized owing to steep distance dependence of the energy transfer. This method will be useful in construction of complex photoresponsive DNA circuits, nanodevices and biological tools.

Implementing cationic customization and halogen engineering not only enable a dramatic enhancement of Curie temperature (ΔT_C=114.4 K), but also realize the first integration of notable ferroelectricity and long afterglow emission in (4-methylpiperidium)CdCl₃ with one-dimensional hybrid perovskite architecture.

The enantioselective reduction of 1,3-dipolar nitrones to hydroxylamines was achieved by Rh(III)-catalyzed asymmetric hydrogenation and transfer hydrogenation. A wide range of chiral N,N-disubstituted hydroxylamines were synthesized with up to 99 % yield and >99 % ee. Mechanistic investigations and DFT calculations were conducted to elucidate the origin of reactivity and enantioselectivity.

Bacteria spend years in a dormant, inactive state, yet revive in some nutrient environments. Iron nutritional immunity strategy was proposed to target iron nutrients. We developed a nanoplatform that can deceive bacteria to uptake “fake iron” and concurrently extract iron ions from the surrounding bacteria milieu, starving pathogens to death.

Rapid functional group transformation of carboxylic acids into a new ketone under mild conditions using the reagent 4-nitrophenyl-2H-azirine. The newly formed ketone was captured by our chemical probe methodology for quantification with enhanced mass spectrometric sensitivity. This bifunctional methodology is a new chemical biology tool for biomarker discovery and metabolomics.

Kinetic tests combined with temporal analysis of products revealed the fundamentals relevant for regulating the efficiency of the oxidative coupling of CH₄ to C₂H₆ over Gd-based catalysts. When Gd₂O₃ is modified with Na, Sr or Ba, the use of N₂O instead of O₂ significantly improves the selectivity even at 650 °C. The promoters affect the binding strength of monoatomic oxygen species derived from N₂O and thus control the methane oxidation to carbon oxides.

Utilizing readily available and cost-effective aryl halides, amines, and butadienes as starting materials, in conjunction with rac-BINAP and a Pd catalyst, we can efficiently synthesize highly valuable complex allylamines through a rapid one-step process enabled by photocatalysis.

An aromatic helical foldamer linked to a peptide rod, which is incapable of self-complexation or polymerization, has been shown to preferentially assemble through inter-strand hydrogen-bonding interactions into a [c2]daisy chain that undergoes fast contraction/stretching muscle-like motion without dissociation. The introduction of multiple recognition sites confers the system with contraction and stretching motion actuated by chemical stimuli.

A strategy to mimic the conventional N-terminal sortase substrate at protein C-termini is reported, enabling C- to C-terminal ligation. Installing this mimetic at the C-terminus of a protein with an internal sortase recognition motif enables sortase-catalyzed inversion of the C-terminal portion of the protein.

An abasic site within a DNA duplex reduces hydrolysis of a colocalised DNA-thioester. This forms the basis for an architecture for DNA-templated synthesis which protects DNA-tagged building blocks until a DNA strand exchange reaction removes the protective site and colocalizes a second reactive group.

Direct amination of benzylic C−H bonds generates important stereocenters. Our approach, in which the chirality of a bimetallic rhodium complex is located on its associated cations, achieves this on tertiary amide-containing substrates to give amination of arylbutyric and arylvaleric acid-derived amides. We believe that the amide most likely interacts directly with the chiral cation to provide a highly organised transition state for C−H amination.

Undesired reaction pathways of open-shell graphene fragments can be synthetically useful! To demonstrate their transformative potential, we employed oxidative dimerization of phenalenyl to peropyrene—the well-known π-radical “decomposition” process—to build up strain and access negatively curved and configurationally stable chiral polycyclic aromatic hydrocarbon.

The synthesis of a Ru(0)(BINAP)(PPh₃) complex (BINAP:2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) is reported. It behaves as a “masked” 16-electron Ru(0) complex: while being quite stable, it is capable to substitute PPh₃ with alkenes/dienes, and activate C−H, N−H or inert N−Et bonds. This compound gives novel insight into Ru(0) stabilization approaches while maintaining a high specific reactivity potentially useful for catalytic applications.

The high potential energy of aryne intermediates can induce reactions that proceed through unorthodox mechanisms. Herein we report the aryne-promoted formation of various helical dibenzochalcophenes from phosphine chalcogenides. Based on DFT computations we propose a mechanism to account for the final C−C bond formation that involves a rare, concerted ligand-coupling event within a hypervalent σ-phosphorane.

A data-driven approach is employed to achieve the controlled synthesis of four types of CsPbBr₃ crystals and successfully control the orientation of quasi-spherical CsPbBr₃ structures. Synthesis parameters are optimized using high-throughput characterization combined with machine learning. Furthermore, the synthetic mechanism is determined. Oriented quasi-spherical CsPbBr₃, screened by using the data-driven approach, exhibit significantly improved optical properties.

Addition of CO to a tetrametallic magnesium hydride cluster results in both carbon-carbon bond formation and deoxygenation to generate an acetaldehyde enolate [C₂OH₃]⁻ which remains coordinated to the cluster. DFT studies suggest that key steps in the mechanism involve nucleophilic attack of an oxymethylene on a formyl ligand to generate an unstable [C₂O₂H₃]³⁻ fragment, which undergoes subsequent deoxygenation.

In this study, we propose a new design strategy to stabilize triplet excitons for high-temperature phosphorescence by organic cocrystal engineering. The reported cocrystal has an ultralong emission lifetime of up to 2.16 s, which is the best performance in the case of organic cocrystals under ambient conditions so far.

Binding to a template bends a photonic wire consisting of 18 meso-meso linked porphyrins into a ring, allowing covalent cyclization by Glaser coupling, to yield a strained nanoring. The 18-legged template was synthesized efficiently via six-fold iridium-catalyzed C−H borylation. The nanoring was characterized by scanning tunneling microscopy (STM).

The synthesis of a three-dimensionally (3D) extended two-legged ladder compound was reported for the first time. The unique 3D extended lattice consists of one-dimensional (1D) mixed-valence halogen-bridged metal chains (⋅⋅⋅Pt−I−Pt−I⋅⋅⋅) and helically arranged macrocyclic units as the constituent legs and rungs. The out-of-phase mixed-valence Pt²⁺/Pt⁴⁺ arrangement arises from the weak interchain correlation among adjacent legs.

Controllable double difluoromethylene insertions into S−Cu bonds have been developed with TMSCF₂Br reagent, which provides a general synthetic protocol to contruct ArSCF₂CF₂Cu intermediates as well as the ArSCF₂CF₂Ar′ products.

The sequential defluorinative transformation of a difluoromethylene (CF₂) unit in perfluoroalkyl compounds has been achieved by a combination of photoredox catalysis and Lewis acid activation. A newly developed phenothiazine-based catalyst served as an efficient catalyst for defluoroaminoxylation. Spectroscopic measurements revealed the reaction mechanism. AlCl₃ facilitated further defluorinative transformation of the aminoxylated compounds.

For the first time, this work renews the halogen substitution strategy to obtain a series of high-T_c molecular AFEs, which opens up a new pathway to design high-T_c molecular AFEs and injects new vitalities in the halogen substitution strategy.

A series of ‘aniono’ helicates have been formed by the coordination of tetraphenylethene-decorated anion-binding ligand with phosphate ions. The triple helicates can be solution-processed with a polymethyl methacrylate matrix to generate functional thin films with multiple optical properties and used to recognize choline and its derivatives in water.

Cr_5.7Si_2.3P₈N₂₄, the first nitridic analog to amphibole minerals, was obtained at high-pressure high-temperature conditions. The structure was elucidated by microfocused synchrotron diffraction, atomic-resolution transmission electron microscopy, and magnetic measurements, which were able to prove the partial disorder of Si and Cr and the oxidation state +IV of chromium.