Nikolay Zelinsky was one of the leading chemists worldwide at the beginning of the 20^th century. He discovered four reactions that bear his name and his work formed the basis for the petrochemical industry in the Soviet Union. This Essay looks back at his achievements and sets the historical context.

CRISPR, a sensing and actuating machine, mediates biosensing toward point-of-care diagnosis and understanding cellular biology.

A-maze-ing recent results enabled the realization of complex reaction machineries of organic transformation promoted by graphene oxide.

Polyoxometalate chemistry has shown great application potential in the field of catalysis. This Minireview outlines and discusses the advantages, recent advances, challenges, strategies and future development of POM-based compounds as photo/electrocatalysts in hydrogen evolution reaction, oxygen evolution reaction, and CO₂ reduction reaction.

Center of attention: This Review gives an overview of methods to investigate HER-active atomic centers and discusses active sites with different coordination configurations. Active centers with one metal atom, two different metal atoms, as well as nonmetal atoms are analyzed at the atomic scale. Future research perspectives are also proposed. HER=hydrogen evolution reaction.

The first catalytic asymmetric synthesis of Remdesivir by the coupling of the P-racemic phosphoryl chloride with protected nucleoside GS441524 has been realized using a chiral bicyclic imidazole catalyst, which is crucial for the racemization process involving the phosphoryl chloride and subsequent stereodiscriminating step (96 % conv., 22:1 S_P:R_P). Furthermore, a 10 gram scale reaction was successfully realized, showing its potential for industrial application.

The first 8-connected network based on the I-WP minimal surface is formed by dynamic soft self-assembly of X-shaped polyphiles with oligo(para-phenylene-ethynylene) cores. This Im m cubic liquid-crystalline phase is one of a new kind of cubic phases combining a network structure of rod-bundles interconnected by polar spheres.

Highly active Ni₃C branched particles are demonstrated and their selective electrocatalytic conversion of methanol to formate is probed by using advanced in situ infrared spectroscopy combined with nuclear magnetic resonance spectroscopy.

The para-selective arylation of sulfonate, phosphonate, and phenol derivatives bearing 2,6-disubstitution patterns and a suitable meta-directing group is achieved by using Pd and norbornene cooperative catalysis. The present protocol enables the synthesis of hexa-substituted arenes by sequential regioselective C−H functionalization.

The tendency of biomolecular droplets to fuse is key to cellular functions and diseases. Using optical tweezers, fluorescence microscopy, and theoretical modeling, we have begun to unravel the molecular origin for disparate fusion speeds among different biomolecular droplets. Fusion speed is dictated by macromolecular packing density inside droplets, which can be reported by thioflavin T fluorescence.

The regioselectivity of the hydrocupration of α,β-unsaturated carbonyl compounds can be reversed in the presence of an appropriate ancillary chiral ligand. This ligand-controlled reversal of regiochemistry enables enantioselective and β-selective hydroamination of α,β-unsaturated carbonyl compounds, with 1,2-benzisoxazole as an electrophilic aminating reagent, thereby providing simple and efficient access to N-unprotected β-amino acid derivatives.

A low-symmetry organic molecular cage with distinctive geometry was successfully synthesized through the desymmetrized vertex design strategy.

The treatment of a trifluoroacetimidoyl chloride (TFAIC) with the carbenoid iodomethyllithium results in the chemoselective formation of a bis-trifluoromethyl-β-diketiminate. This sequential two-events strategy involves the homologation of the imine surrogate followed by the lithiation of the intermediate operated by the same carbenoid and attack of a second TFAIC unit.

A thin and well-intergrown zeolitic imidazolate framework (ZIF-95) membrane was developed for H₂ separation. A simple vapor-assisted in-plane epitaxial growth method generated a highly oriented ZIF-95 membrane. A notable reduction of intercrystalline defects and transport pathways was achieved compared to a randomly oriented ZIF-95 framework, resulting in a 4.6 times enhancement of H₂ permeance for the separation of H₂ (0.29 nm) from larger gas molecules.

The reversible migration of hydrogen atoms from methyl groups of the ubiquitous C₅Me₅ (Cp*) ligand to the Rh^I center in [(η⁵-C₅Me₅)Rh(PMe₃)₂] is demonstrated, revealing the potential role of Cp* as a proton shuttle by a route that was previously restricted to early transition metals. The incorporation of bulky and electrophilic gold fragments allows the isolation of key bimetallic species in support of the reversible C−H activation at Cp*.

A benzothiadiazole-based [12]cycloparaphenylene (TB[12]CPP) is obtained and characterized. TB[12]CPP exhibits a lime to orange emission with a quantum yield up to 98 %, ranking it as one of the brightest CPPs. As a supramolecular host, TB[12]CPP is bright as well, showing adaptable ring structure. A ternary assembly between TB[12]CPP, fullerene, and buckybowl is realized.

Three MOFs with high crystallinity were synthesized from the conjugated ligand tetrahydroxybenzoquinone (THBQ) and Fe, Co, Mn metal ions. Fe-THBQ has a negative Seebeck coefficient and the highest electrical conductivity in THBQ-based MOFs, which could be due to the Fe^II/Fe^III mixed valence. Strong absorptions in the visible light region provide the possibility of application in the light-harvesting devices.

The addition of N-heterocyclic carbenes on Ru/C induces a catalytic activity switch to favor hydrogen isotope exchange over reductive deuteration. This catalyst modification led to an increase in regio- and chemoselectivity in the context of the C−H deuteration of pharmaceutically relevant substructures, as well as to the discovery of a novel reactivity for such heterogeneous Ru catalysts, namely selective C-1 deuteration of aldehydes.

An enantiomerically pure additive can direct chiral symmetry breaking towards opposite outcomes, depending on the relative contributions of kinetic and thermodynamic processes. Kinetic growth inhibition directs symmetry breaking towards the enantiomer of the opposite configuration to the additive, whereas thermodynamic solid solution formation favors the same absolute configuration, thus offering a mechanism for the propagation of homochirality.

An automated electrochemistry screening platform based on a single-droplet microfluidic reactor enables multifunctional capabilities for investigation of electroorganic synthesis. Reaction condition screening of an electrochemical radical–radical cross-coupling reaction and measurements of kinetics for two mediated anodic oxidation reactions are realized with fast turnover time and minimal reagent consumption.

Caged crRNA was readily developed through a terminus modification with a photolabile linker and vitamin E for construction of a caged CRISPR/Cas9 system. The system was successfully used for photomodulation of VEGFA gene editing and control of EGFP gene silencing through the temporary inhibition of the interaction between the target DNA and Cas9/crRNA/tracrRNA complex.

Ionic-enforced covalency in M−B bonds of MBX₃⁻ species originates from strong electrostatic interaction between the metals and boranes. This interaction keeps the atoms within proximity of each other through strong coulombic forces but causes non-negligible degrees of electron sharing.

An organocatalytic enantioselective [2,3]-sigmatropic rearrangement is described. This reaction enables chiral cyclic sulfides bearing an α-quaternary chiral center to be prepared in high optical purity. The enantioselectivity is controlled by a cooperative organocatalyst pair consisting of a chiral amine and a chiral phosphoric acid (CPA). NIS=N-iodosuccinimide.

The Li-O₂ battery can be photoactivated, thus reducing the recharge potential to 2.7 V with a binder- and carbon-free TiO₂-based oxygen electrode, which also enhances the stability of the system. The electrode exhibits excellent stability with about 100 % coulombic efficiency during continuous cycling of up to 200 cycles. This work reveals a new strategy towards the development of highly efficient oxygen electrode materials for Li-O₂ batteries.

We describe the synthesis of compounds exhibiting gallium–phosphorus double bonds. The stability of these species is dependent on the saturation of the phosphanyl moiety, and the saturated variant behaves as a frustrated Lewis pair that is capable of activating H₂ and forms a 1:1 adduct with CO₂.

A solid-state PCN/LaOCl composite has been shown to feature fast inter-particle charge separation properties by a one-photon excitation pathway. It thus shows high photocatalytic activities toward overall water splitting to produce hydrogen and oxygen.

Chiral crystals of ϵ-Zn(OH)₂ were crystallized from supersaturated aqueous solutions in the presence of l- or d-arginine and chiral discrimination was observed during the crystallization. A new method for identifying chirality in crystals by using electron paramagnetic resonance (EPR) has also been developed.

Bis(perchlorocatecholato)germane is a hard and soft Lewis superacid with unlimited water stability. Its utility in catalysis as both a Lewis and Brønsted acid was demonstrated by application to a variety of catalytic transformations, such as hydrodefluorination, hydrosilylation, transfer hydrogenation, and carbonyl–olefin metathesis.

Electrophilic ketone activation: Triflic anhydride mediated activation of acetophenones leads to highly electrophilic intermediates undergoing various transformations with nucleophiles. The methodology gives access to α-arylated and α-oxyaminated acetophenones under metal-free conditions in moderate to excellent yields.

The conserved histidines (HisA₂, HisB₁ and HisB₂), influenced by adjacent residues (HisB₁+1, HisB₂+1 and waterkeeper residue), are responsible for the hydroxylase activity. Starting from a catechol oxidase (CO) a tyrosinase (TYR) with monophenolase activity well within the range of naturally occurring plant TYRs has been designed.

A π-spacer blocks electronic communication between two ionic rhodamine dyes in a dyad isolated in vacuo as it screens for the electric field that each dye senses from the other. Energy transfer based on the dipole–dipole interaction is thus less efficient than that for systems with alkyl spacers.

Heterogeneous couplings and energetics for singlet fission (SF) processes were developed in dendritic structures which mimic complicated SF dynamics in amorphous solids. SF in dendritic structures was thoroughly investigated by time-resolved spectroscopic techniques and quantum chemical calculations in respect of relative orientation/distance between chromophores and through-bond/-space interactions.

Nuclear magnetic resonance (NMR) spectroscopy was employed to monitor methyl relaxation in the side chains of the light-driven proton pump bacteriorhodopsin (bR) and its less active M145A mutant. The findings provide a detailed picture of equilibrium dynamics on different time scales for ground-state bR.

Curved platinum single crystals provide stepped surface arrays featuring terraces, steps, and kinks. Linking the structural elements of these surfaces to their chemical activity towards hydrogen dissociation provides new insights into the scalability of reactivity at low-coordinated sites, such as those featured on heterogeneous catalyst particles.

A non-annealed, ultrathin, amorphous metal oxyhydroxide was introduced to suppress interfacial charge recombination and reduce energy loss in electron-transport-layer (ETL)-free perovskite solar cells. The cells achieve a record efficiency of 21.1 %, outperforming their ETL-containing metal oxide counterparts (18.7 %).

The cation exchanged synthesis of diverse hollow metal-phytate (PA) polyhedral complexes is reported using hollow Co²⁺-PA micropolyhedra as templates in a liquid phase. The synthetic strategy enables facile addition of multiple functionalities within the metal-PA polyhedral networks with simultaneous control of their physicochemical features under mild conditions.

A pH-activatable fluorescent probe (pHocas-RIS) with moderate bone-binding affinity was synthesized by conjugating a BODIPY fluorophore to bisphosphonate-targeting risedronate ligands. The probe enabled the imaging of acidic osteocytic lacunae that contain bone resorbing osteocytes in deep bone tissues in living animals.

Rapid, reversible, and highly selective adsorption of ethene and propene was observed for trinuclear copper(I) complexes. In situ PXRD was used to directly observe the solid-state rearrangement of the trinuclear complexes into dinuclear alkene adducts.

To chemically modify proteins inside cells with an exogenously prepared, labeled backbone fragment we have explored the fastest splicing split intein. Excess intein reagent is removed to the nucleus to increase the signal-to-noise ratio in the cytoplasm. We report synthetic fluorophore attachment for super-resolution and single-molecule tracking studies.

Statistical rebinding and chelate binding reinforce each other and cooperatively increase the affinity for a multivalent target. The distance-defined display of two small clusters of a glycomimetic compound on a rigid PNA-DNA scaffold provided the first molecularly defined, nanomolar binder of the C-type lectin receptor langerin. The high-affinity binders are selectively internalized by langerin-expressing cells.

A novel class of tetradentate C^C^N^N ligand-containing gold(III) complexes with a preferential horizontal orientation has been obtained through a one-pot reaction. A high maximum external quantum efficiency of 20.6 % has been realized in the vacuum-deposited gold(III)-based OLEDs, with operational half-lifetimes of around 37 500 h at 100 cd m⁻².

A chlorine radical (^.Cl) nano-generator is constructed with a SiO₂-coated upconversion nanoparticle (UCNP) interior and decorated with Ag⁰/AgCl hetero-dots on the outside. Upon NIR light irradiation, the emission light of the UCNPs activates Ag⁰/AgCl to catalyze Cl⁻ production, generating ^.Cl. The resulting radicals have strong oxidizing capacity and nucleophilicity, leading to efficient tumor therapy without dependence on O₂ and H₂O₂.

A tumor microenvironment (TME) stimuli-responsive fluorescence imaging and trimodal synergistic cancer treatment nanoplatform is facilely constructed via assembling carbon dots and Cu²⁺. This could act as a potential strategy to achieve enhanced cancer therapeutic efficiency with minimized side effects.

Fluorination of semiconducting polymers resulted in highly bright polymer dots (QY=3.2 %) in the NIR-II region. By performing through-skull and through-scalp imaging of the mouse brain, the vascular morphology of transgenic brain tumors was quantitatively analyzed.

We describe a DNA-based nanodevice that acts as a sulfur switch and can be temporally controlled through redox cycles of a disulfide-linked allosteric modulator. The system has an unprecedented high tolerance to waste products and displays transient behavior for over 40 cycles without significant loss of efficiency. The approach is reversible and allows the transient loading and release of a ligand upon successive reduction and oxidation of the modulator.

The direct synthesis of unprotected secondary and tertiary alkylamines from alkenes is reported. Aminative difunctionalization was mediated by an iron catalyst to yield a family of ten hydroxylamine-derived aminating reagents. Several medicinally relevant amine groups, such as methylamine, morpholine and piperazine, were installed through the aminochlorination, -hydroxylation, -azidation and carboamination of alkenes.

Carbon dioxide was electroreduced to 1-butanol on oxide-derived copper. The reaction mechanism was determined to proceed through a combination of electrochemical and chemical steps, some of which require contrasting conditions. This example highlights limitations in one-pot synthesis and provides a case for utilizing independently optimized sequential reactors in a tandem system to build complex molecules from low molecular-weight feedstocks.

The impact of enzyme orientation on the performance of lipase-powered nanomotors was explored and analysed, indicating that hydrophobic interaction is the best strategy for immobilizing lipase to provide high-efficiency catalysis. This results in high-efficiency enhanced Brownian motion, which would be vital in promoting the future applications of enzyme-powered micro/nanomotors.

The oxidative addition of OH, NH, and weak CH bonds to a palladium(0) complex is facile, allows for additive-free catalysis, and suggests the non-innocence of water in palladium catalysis. The oxidative addition of protic solvents or adventitious water switches the chemoselectivity in catalysis with alkynes through activation of the terminal C−H bond.

PhotoAffinity Bit (PhABit) is a photoreactive fragment-screening platform to covalently capture fragment–protein interactions. Hits can be profiled and subsequently developed as reporters in a competitive displacement assay to identify novel hit matter. The PhABit platform is widely applicable to novel protein targets, identifying starting points in the development of therapeutics.

By growing amorphous multi-transition-metal (cobalt and iron) oxide on two-dimensional (2D) black phosphorus (BP), a bifunctional electrocatalyst (CoFeO@BP), which is able to efficiently catalyze both HER and OER was developed. The overpotentials for the hybrid CoFeO@BP catalyst to reach a current density of 10 mA cm⁻² in 1 m KOH are 88 and 266 mV for HER and OER, respectively.

A general method for the multiple site hydrogen isotope labelling of complex molecules using the commercially available and air-stable iridium precatalyst [Ir(COD)(OMe)]₂ is reported. This new synthetic method possesses multiple key features far beyond the state-of-the-art methods for tritium labelling, including a very broad substrate scope and an exceptional functional group tolerance facilitating the access to complex pharmaceuticals with high molar activities.

Reported is the first remote difunctionalization of unactivated alkenes with CO₂ by visible-light photoredox catalysis. Mechanistic studies indicate that a 1,5-hydrogen atom-transfer process is the rate-limiting step and reduction of radical intermediates generates the corresponding carbanions. Other electrophiles, including aldehydes, ketones, and benzylic bromides, are also applicable in this process, demonstrating a general strategy for redox-neutral remote difunctionalization of unactivated alkenes.

Scanning electrochemical microscopy was developed as a direct nanomachining technique on semiconductor wafers through a close-loop of current feedback to the positioning system. Arbitrary 3D microstructures were translated into a spatially distributed current and fabricated.

The catalytic reactivity and lability of atomically precise Au₂₅ nanoclusters was investigated by monitoring the movement of a free valence electron of the Au 6s orbital. Donation of an electron to a neutral Au₂₅⁰ nanocluster generates Au₂₅⁻ with undermined reactivity, whereas dislodgment of an electron generates Au₂₅⁺ with undermined stability. The correlation of the free valence electrons and catalytic properties of the Au₂₅ nanoclusters can be achieved at a single-electron level.

A spatio-temporal feedback on the intratumoral catalytic Fenton reaction is described. It bridges dual-modal MRI/NIR imaging, thereby conquering inherent unpredictable barriers in chemodynamic therapy. This approach paves a way to accurately evaluate ^.OH dose-dependent feedback.

The first antimony pyrophosphate, K₂Sb(P₂O₇)F, with an unprecedented Cairo pentagonal layered structure, not only exhibits a strong second-harmonic generation response (4.0×KH2PO4), but also displays the second largest birefringence (0.157@546 nm) among all phosphate optical materials.

A Pt^IV prodrug with axial oleate and cinnamate ligands was synthesized. It is active against HER2-positive breast cancer, which is an aggressive breast-cancer subtype that typically responds poorly to standard chemotherapy. Moreover, the new Pt^IV prodrug is capable of overcoming the resistance of cancer stem cells (CSCs), inducing death in both CSCs and differentiated cancer cells.

Heterochiral self-discrimination between two chiral decanuclear gold(I) enantiomers gives rise to self-assembled 2D nanostructures. The introduction of chiral anions has been shown to tune the morphology of these 2D NCs from rhombic NCs to bilayer strip and quasi-hexagonal nanosheets. The current finding provides an important alternative towards the easy fabrication of regular geometric 2D nanostructures based on polynuclear gold(I) complexes.

Pd-P nanostructures are efficient electrocatalysts for selective semihydrogenation (deuteration) of terminal and internal alkynes using H₂O (D₂O) as the H (D) source at a lower potential via an adsorbed atomic hydrogen (H*_ads) addition pathway. P-doping causes enhanced specific adsorption of alkynes and promoted intrinsic activity for producing H*_ads from water electrolysis.

A single catalytic platform is described for which control of 1,2 versus 1,4 selectivity for enone hydroboration can be controlled by light. This was used to obtain rare syn-aldol products on cyclic substrates. Experiments and DFT calculations demonstrate that two distinctive mechanisms are operative.

Gaining control over the orientational order of nanoparticles, and by extension the formation of plastic crystals over large areas, remains challenging. Molecular-level polymeric surface interactions are now employed to modulate the orientational order of Archimedean nanoparticles. Two orientationally distinct supercrystals are formed using a single nanoparticle shape, including plastic crystals and uniform metacrystals.

A DNA nanoconstruct, named DOCTR, selectively recognizes a mutant RNA sequence that is a marker for cancer. The nanodevice then cuts out a fragment (purple) and uses this fragment to activate the cleaving function, which damages another RNA essential for cancer cell survival.

Under blue LED irradiation, dicinnamyl ether derivatives undergo double cyclization to afford tricyclic lignans. Six natural products are synthesized from the corresponding monolignols in two or three steps.

The experimental electron density obtained from 20 K synchrotron X-ray diffraction data was used here to quantify the zero-field splitting parameter in a Co^II-based single-molecule magnet. The methodology uses the d-orbital populations to derive the ground-state wavefunction composition, which is shown to be strongly correlated to the zero-field splitting.

Total synthesis of the plicamine-type alkaloids zephycarinatines C and D has been achieved. The key feature of the synthesis is a stereoselective radical ipso-cyclization using visible-light-mediated photoredox catalysis. Biological evaluation of zephycarinatines and their derivatives revealed that a synthetic derivative displays moderate inhibitory activity against LPS-induced NO production.

Steam and dry reforming of methane catalyzed by gas-phase rhodium–vanadium–oxygen cluster anions at room temperature with high syngas selectivity has been identified under photo-irradiation conditions. The crucial step to govern syngas selectivity is the photo-excitation of reaction intermediates such as Rh₂VO₃CH₂⁻ to electronically excited states that selectively produce H₂ and CO.

The first example of tetracyanobuta-1,3-diene-based derivatives, showing unprecedented configurational stability and a peculiar light-triggered enantiomer conversion mechanism enabled by triplet-state photogeneration, is reported.

N-Heterocyclic carbene based molecular “ballbots” modify a gold surface with atomic accuracy. These molecular species not only form atomically precise surface defects, but can coordinatively operate to restructure the surface. The well-defined and step-wise operation mechanism provides a new approach to tailor both the local and long-range structure of gold surfaces.

SAPT calculations of chalcogen bonds show that neither the induction (orbital delocalization effects) nor the electrostatic term is causing the spatial orientation of strong chalcogen bonds in tellurium-containing aromatics. Instead, steric interactions (Pauli repulsion) are responsible for the orientation. These results underline the importance of often overlooked steric interactions in conformational control of σ hole interactions.