The cytokinin receptor OHK4/OsHK4 regulates inflorescence architecture in rice via an IDEAL PLANT ARCHITECTURE1/WEALTHY FARMER'S PANICLE-mediated positive feedback circuit.

Inflorescence architecture is important for rice (Oryza sativa) grain yield. The phytohormone cytokinin (CK) has been shown to regulate rice inflorescence development; however, the underlying mechanism mediated by CK perception is still unclear. Employing a forward genetic approach, we isolated an inactive variant of the CK receptor OHK4/OsHK4 gene named panicle length1, which shows decreased panicle size due to reduced inflorescence meristem (IM) activity. A 2-amino acid deletion in the long α-helix stalk of the sensory module of OHK4 impairs the homodimerization and ligand-binding capacity of the receptor, even though the residues do not touch the ligand-binding domain or the dimerization interface. This deletion impairs CK signaling that occurs through the type-B response regulator OsRR21, which acts downstream of OHK4 in controlling inflorescence size. Meanwhile, we found that IDEAL PLANT ARCHITECTURE1(IPA1)/WEALTHY FARMER'S PANICLE (WFP), encoding a positive regulator of IM development, acts downstream of CK signaling and is directly activated by OsRR21. Additionally, we revealed that IPA1/WFP directly binds to the OHK4 promoter and upregulates its expression through interactions with 2 TCP transcription factors, forming a positive feedback circuit. Altogether, we identified the OHK4-OsRR21-IPA1 regulatory module, providing important insights into the role of CK signaling in regulating rice inflorescence architecture.

Canonical and Alternative Auxin Signaling Systems in Mono-, Di-, and Tetraploid Potatoes.

It has long been known that the phytohormone auxin plays a promoting role in tuber formation and stress tolerance in potatoes. Our study aimed to identify and characterize the complete sets of auxin-related genes that presumably constitute the entire auxin signaling system in potato (Solanum tuberosum L.). The corresponding genes were retrieved from sequenced genomes of the doubled monoploid S. tuberosum DM1-3-516-R44 (DM) of the Phureja group, the heterozygous diploid line RH89-039-16 (RH), and the autotetraploid cultivar Otava. Both canonical and noncanonical auxin signaling pathways were considered. Phylogenetic and domain analyses of deduced proteins were supplemented by expression profiling and 3D molecular modeling. The canonical and ABP1-mediated pathways of auxin signaling appeared to be well conserved. The total number of potato genes/proteins presumably involved in canonical auxin signaling is 46 and 108 in monoploid DM and tetraploid Otava, respectively. Among the studied potatoes, spectra of expressed genes obviously associated with auxin signaling were partly cultivar-specific and quite different from analogous spectrum in Arabidopsis. Most of the noncanonical pathways found in Arabidopsis appeared to have low probability in potato. This was equally true for all cultivars used irrespective of their ploidy. Thus, some important features of the (noncanonical) auxin signaling pathways may be variable and species-specific.

A Model of the Full-Length Cytokinin Receptor: New Insights and Prospects.

Cytokinins (CK) are one of the most important classes of phytohormones that regulate a wide range of processes in plants. A CK receptor, a sensor hybrid histidine kinase, was discovered more than 20 years ago, but the structural basis for its signaling is still a challenge for plant biologists. To date, only two fragments of the CK receptor structure, the sensory module and the receiver domain, were experimentally resolved. Some other regions were built up by molecular modeling based on structures of proteins homologous to CK receptors. However, in the long term, these data have proven insufficient for solving the structure of the full-sized CK receptor. The functional unit of CK receptor is the receptor dimer. In this article, a molecular structure of the dimeric form of the full-length CK receptor based on AlphaFold Multimer and ColabFold modeling is presented for the first time. Structural changes of the receptor upon interacting with phosphotransfer protein are visualized. According to mathematical simulation and available data, both types of dimeric receptor complexes with hormones, either half- or fully liganded, appear to be active in triggering signals. In addition, the prospects of using this and similar models to address remaining fundamental problems of CK signaling were outlined.

In Planta, In Vitro and In Silico Studies of Chiral N6-Benzyladenine Derivatives: Discovery of Receptor-Specific S-Enantiomers with Cytokinin or Anticytokinin Activities.

Cytokinins, classical phytohormones, affect all stages of plant ontogenesis, but their application in agriculture is limited because of the lack of appropriate ligands, including those specific for individual cytokinin receptors. In this work, a series of chiral N6-benzyladenine derivatives were studied as potential cytokinins or anticytokinins. All compounds contained a methyl group at the α-carbon atom of the benzyl moiety, making them R- or S-enantiomers. Four pairs of chiral nucleobases and corresponding ribonucleosides containing various substituents at the C2 position of adenine heterocycle were synthesized. A nucleophilic substitution reaction by secondary optically active amines was used. A strong influence of the chirality of studied compounds on their interaction with individual cytokinin receptors of Arabidopsis thaliana was uncovered in in vivo and in vitro assays. The AHK2 and CRE1/AHK4 receptors were shown to have low affinity for the studied S-nucleobases while the AHK3 receptor exhibited significant affinity for most of them. Thereby, three synthetic AHK3-specific cytokinins were discovered: N6-((S)-α-methylbenzyl)adenine (S-MBA), 2-fluoro,N6-((S)-α-methylbenzyl)adenine (S-FMBA) and 2-chloro,N6-((S)-α-methylbenzyl)adenine (S-CMBA). Interaction patterns between individual receptors and specific enantiomers were rationalized by structure analysis and molecular docking. Two other S-enantiomers (N6-((S)-α-methylbenzyl)adenosine, 2-amino,N6-((S)-α-methylbenzyl)adenosine) were found to exhibit receptor-specific and chirality-dependent anticytokinin properties.

Carbon Quantum Dots' Synthesis with a Strong Chemical Claw for Five Transition Metal Sensing in the Irving-Williams Series.

Carbon quantum dots (CQDs) are an excellent eco-friendly fluorescence material, ideal for various ecological testing systems. Herein, we establish uniform microwave synthesis of the group of carbon quantum dots with specific functionalization of ethylenediamine, diethylenetriamine, and three types of Trilon (A, B and C) with chelate claws -C-NH3. CQDs' properties were studied and applied in order to sense metal cations in an aquatic environment. The results provide the determination of the fluorescence quench in dots by pollutant salts, which dissociate into double-charged ions. In particular, the chemical interactions with CQDs' surface in the Irving-Williams series (IWs) via functionalization of the negatively charged surface were ascribed. CQD-En and CQD-Dien demonstrated linear fluorescence quenching in high metal cation concentrations. Further, the formation of claws from Trilon A, Trilon B, and C effectively caught the copper and nickel cations from the solution due to the complexation on CQDs' surface. Moreover, CQD-Trilon C presented chelating properties of the surface and detected five cations (Cu2+, Ni2+, Ca2+, Mg2+, Zn2+) from 0.5 mg/mL to 1 × 10-7 mg/mL in the Irving-William's series. Dependence was mathematically attributed as an equation (ML regression model) based on the constant of complex formation. The reliability of the data was 0.993 for the training database.

Cytokinin Perception in Ancient Plants beyond Angiospermae.

Cytokinins (CKs) control many plant developmental processes and responses to environmental cues. Although the CK signaling is well understood, we are only beginning to decipher its evolution. Here, we investigated the CK perception apparatus in early-divergent plant species such as bryophyte Physcomitrium patens, lycophyte Selaginella moellendorffii, and gymnosperm Picea abies. Of the eight CHASE-domain containing histidine kinases (CHKs) examined, two CHKs, PpCHK3 and PpCHK4, did not bind CKs. All other CHK receptors showed high-affinity CK binding (KD of nM range), with a strong preference for isopentenyladenine over other CK nucleobases in the moss and for trans-zeatin over cis-zeatin in the gymnosperm. The pH dependences of CK binding for these six CHKs showed a wide range, which may indicate different subcellular localization of these receptors at either the plasma- or endoplasmic reticulum membrane. Thus, the properties of the whole CK perception apparatuses in early-divergent lineages were demonstrated. Data show that during land plant evolution there was a diversification of the ligand specificity of various CHKs, in particular, the rise in preference for trans-zeatin over cis-zeatin, which indicates a steadily increasing specialization of receptors to various CKs. Finally, this distinct preference of individual receptors to different CK versions culminated in vascular plants, especially angiosperms.

Global View on the Cytokinin Regulatory System in Potato.

Cytokinins (CKs) were earlier shown to promote potato tuberization. Our study aimed to identify and characterize CK-related genes which constitute CK regulatory system in the core potato (Solanum tuberosum) genome. For that, CK-related genes were retrieved from the sequenced genome of the S. tuberosum doubled monoploid (DM) Phureja group, classified and compared with Arabidopsis orthologs. Analysis of selected gene expression was performed with a transcriptome database for the S. tuberosum heterozygous diploid line RH89-039-16. Genes responsible for CK signaling, biosynthesis, transport, and metabolism were categorized in an organ-specific fashion. According to this database, CK receptors StHK2/3 predominate in leaves and flowers, StHK4 in roots. Among phosphotransmitters, StHP1a expression largely predominates. Surprisingly, two pseudo-phosphotransmitters intended to suppress CK effects are hardly expressed in studied organs. Among B-type RR genes, StRR1b, StRR11, and StRR18a are actively expressed, with StRR1b expressing most uniformly in all organs and StRR11 exhibiting the highest expression in roots. By cluster analysis four types of prevailing CK-signaling chains were identified in (1) leaves and flowers, StHK2/3→S t H P1a→StRR1b/+; (2) shoot apical meristems, stolons, and mature tubers, StHK2/4→S t H P1a→StRR1b/+; (3) stems and young tubers, StHK2/4→S t H P1a→StRR1b/11/18a; and (4) roots and tuber sprouts, StHK4→S t H P1a→StRR11/18a. CK synthesis genes StIPT3/5 and StCYP735A are expressed mainly in roots followed by tuber sprouts, but rather weakly in stolons and tubers. By contrast, CK-activation genes StLOGs are active in stolons, and StLOG3b expression is even stolon-confined. Apparently, the main CK effects on tuber initiation are realized via activity of StLOG1/3a/3b/7c/8a genes in stolons. Current advances and future directions in potato research are discussed.

Ascorbic Acid-Assisted Polyol Synthesis of Iron and Fe/GO, Fe/h-BN Composites for Pb2+ Removal from Wastewaters.

Iron powders and Fe/graphene oxide and Fe/boron nitride composites were synthesized by means of a polyol synthesis method. The effect of NaOH/Fe and ascorbic acid/Fe ratios on the characteristics of synthesized products were evaluated. The samples were characterized by X-ray diffraction, scanning and transmission electron microscopy, low-temperature nitrogen adsorption and Raman-spectroscopy. Ascorbic acid-assisted polyol synthesis resulted in the 10-fold decrease of the iron particles' size and almost 2-fold increase of lead removal efficiency. The deposition of iron on the surface of graphene oxide lead to the formation of small 20-30 nm sized particles as well as bigger 200-300 nm sized particles, while the reduction in presence of boron nitride resulted in the 100-200 nm sized particles. The difference is attributed to the surface state of graphene oxide and boron nitride. Adsorption properties of the obtained materials were studied in the process of Pb2+ ion removal from wastewater.

Modeling of Protein⁻Protein Interactions in Cytokinin Signal Transduction.

The signaling of cytokinins (CKs), classical plant hormones, is based on the interaction of proteins that constitute the multistep phosphorelay system (MSP): catalytic receptors-sensor histidine kinases (HKs), phosphotransmitters (HPts), and transcription factors-response regulators (RRs). Any CK receptor was shown to interact in vivo with any of the studied HPts and vice versa. In addition, both of these proteins tend to form a homodimer or a heterodimeric complex with protein-paralog. Our study was aimed at explaining by molecular modeling the observed features of in planta protein-protein interactions, accompanying CK signaling. For this purpose, models of CK-signaling proteins' structure from Arabidopsis and potato were built. The modeled interaction interfaces were formed by rather conserved areas of protein surfaces, complementary in hydrophobicity and electrostatic potential. Hot spots amino acids, determining specificity and strength of the interaction, were identified. Virtual phosphorylation of conserved Asp or His residues affected this complementation, increasing (Asp-P in HK) or decreasing (His-P in HPt) the affinity of interacting proteins. The HK-HPt and HPt-HPt interfaces overlapped, sharing some of the hot spots. MSP proteins from Arabidopsis and potato exhibited similar properties. The structural features of the modeled protein complexes were consistent with the experimental data.

Auxins in potato: molecular aspects and emerging roles in tuber formation and stress resistance.

The study of the effects of auxins on potato tuberization corresponds to one of the oldest experimental systems in plant biology, which has remained relevant for over 70 years. However, only recently, in the postgenomic era, the role of auxin in tuber formation and other vital processes in potatoes has begun to emerge. This review describes the main results obtained over the entire period of auxin-potato research, including the effects of exogenous auxin; the content and dynamics of endogenous auxins; the effects of manipulating endogenous auxin content; the molecular mechanisms of auxin signaling, transport and inactivation; the role and position of auxin among other tuberigenic factors; the effects of auxin on tuber dormancy; the prospects for auxin use in potato biotechnology. Special attention is paid to recent insights into auxin function in potato tuberization and stress resistance. Taken together, the data discussed here leave no doubt on the important role of auxin in potato tuberization, particularly in the processes of tuber initiation, growth and sprouting. A new integrative model for the stage-dependent auxin action on tuberization is presented. In addition, auxin is shown to differentially affects the potato resistance to biotrophic and necrotrophic biopathogens. Thus, the modern auxin biology opens up new perspectives for further biotechnological improvement of potato crops.

Cytokinin perception in potato: new features of canonical players.

Potato is the most economically important non-cereal food crop. Tuber formation in potato is regulated by phytohormones, cytokinins (CKs) in particular. The present work studied CK signal perception in potato. The sequenced potato genome of doubled monoploid Phureja was used for bioinformatic analysis and as a tool for identification of putative CK receptors from autotetraploid potato cv. Désirée. All basic elements of multistep phosphorelay required for CK signal transduction were identified in the Phureja genome, including three genes orthologous to three CK receptor genes (AHK 2-4) of Arabidopsis. As distinct from Phureja, autotetraploid potato contains at least two allelic isoforms of each receptor type. Putative receptor genes from Désirée plants were cloned, sequenced and expressed, and the main characteristics of encoded proteins were determined, in particular their consensus motifs, modelled structure, ligand-binding properties, and ability to transmit CK signals. In all studied aspects the predicted sensor histidine kinases met the requirements for genuine CK receptors. Expression of potato CK receptors was found to be organ-specific and sensitive to growth conditions, particularly to sucrose content. Our results provide a solid basis for further in-depth study of CK signaling system and biotechnological improvement of potato.

Studies of cytokinin receptor-phosphotransmitter interaction provide evidences for the initiation of cytokinin signalling in the endoplasmic reticulum.

Cytokinin receptors were shown recently to be localised mainly to the endoplasmic reticulum (ER); however, the activity of ER-located receptors was not proven. We have therefore tested the functionality of ER-located Arabidopsis receptors. The first step of cytokinin signal transduction is the transfer of a phosphoryl group from the activated receptor to a phosphotransfer protein. To determine the subcellular localisation of receptor-phosphotransmitter interaction in planta, BiFC experiments were performed. Receptors ARABIDOPSIS HISTIDINE KINASE 2 (AHK2), AHK3 and AHK4 (CRE1) and phosphotransmitters ARABIDOPSIS HISTIDINE-CONTAINING PHOSPHOTRANSMITTER 1 (AHP1), AHP2 and AHP3 fused to split-eYFP were transiently expressed in Nicotiana benthamiana leaves. Receptor-phosphotransmitter pairs were shown to interact in every possible combination in a pattern reflecting the ER. Receptor dimers, an active form of the receptors, were also detected in the ER. According to BiFC and protease protection data, the catalytic part of AHK3 was located in the cytoplasm whereas the hormone binding module faced the ER lumen. This topology is consistent with receptor signalling from the ER membrane. Finally, the functionality of receptors in different membrane fractions was tested using an in vitro kinase assay visualising the phosphorylation of phosphotransfer proteins. The detected cytokinin-dependent phosphotransfer activity was confined mainly to the ER-enriched fraction. Collectively, our data demonstrate that ER-located cytokinin receptors are active in cytokinin signal transduction. Hence, intracellular cytokinins appear to play an essential role in cytokinin signalling. An updated model for the spatial organisation of cytokinin transport form activation, intracellular trafficking and signalling from the ER is proposed.

Controlling photophysics of styrylnaphthalimides through TICT, fluorescence and E,Z-photoisomerization interplay.

The photophysical properties of naphthalimide dyes NI1-3 with electron releasing 4-methoxy- (NI1), 3,4-dimethoxystyryl- (NI2) and dimethylaminostyryl (NI3) groups are examined in a variety of protic and aprotic solvents. All compounds demonstrate positive solvatochromism in the steady-state absorption and fluorescence spectra. The analysis of the dependence of the Stokes shift on the polarity of the solvent using the Lippert-Mataga equation allowed us to determine the change in the dipole moment upon excitation. The obtained data correspond to the formation of highly polar charge transfer states. Based on the transient absorption spectra and time-resolved fluorescence measurements, the presence of two different emissive states was definitely proved. The primarily formed planar Local Excited (LE) state dominates in non-polar solvents like cyclohexane and toluene where it relaxes mostly through fluorescence and E,Z-isomerisation pathways. In polar solvents, an alternative relaxation channel emerges that consists of twisting around single bond between styryl and naphthalimide fragments, which leads to the formation of a Twisted Intramolecular Charge Transfer (TICT) state. The factors affecting the fluorescence of TICT states are discussed. The observed spectral effects are rationalized using quantum-chemical calculations, X-ray data and NMR spectroscopy.

Cage-like copper(II) silsesquioxanes: transmetalation reactions and structural, quantum chemical, and catalytic studies.

The transmetalation of bimetallic copper-sodium silsesquioxane cages, namely, [(PhSiO1.5 )10 (CuO)2 (NaO0.5 )2 ] ("Cooling Tower"; 1), [(PhSiO1.5 )12 (CuO)4 (NaO0.5 )4 ] ("Globule"; 2), and [(PhSiO1.5 )6 (CuO)4 (NaO0.5 )4 (PhSiO1.5 )6 ] ("Sandwich"; 3), resulted in the generation of three types of hexanuclear cylinder-like copper silsesqui- oxanes, [(PhSiO1.5 )12 (CuO)6 (C4 H9 OH)2 (C2 H5 OH)6 ] (4), [(PhSiO1.5 )12 (CuO)6 (C4 H8 O2 )4 (PhCN)2 (MeOH)4 ] (5), and [(PhSiO1.5 )12 (CuO)6 (NaCl)(C4 H8 O2 )12 (H2 O)2 ] (6). The products show a prominent "solvating system-structure" dependency, as determined by X-ray diffraction. Topological analysis of cages 1-6 was also performed. In addition, DFT theory was used to examine the structures of the Cooling Tower and Cylinder compounds, as well as the spin density distributions. Compounds 1, 2, and 5 were applied as catalysts for the direct oxidation of alcohols and amines into the corresponding amides. Compound 6 is an excellent catalyst in the oxidation reactions of benzene and alcohols.

Dihydrogen bond intermediated alcoholysis of dimethylamine-borane in nonaqueous media.

Dimethylamine-borane (DMAB) acid/base properties, its dihydrogen-bonded (DHB) complexes and proton transfer reaction in nonaqueous media were investigated both experimentally (IR, UV/vis, NMR, and X-ray) and theoretically (DFT, NBO, QTAIM, and NCI). The effects of DMAB concentration, solvents polarity and temperature on the degree of DMAB self-association are shown and the enthalpy of association is determined experimentally for the first time (-ΔH°assoc = 1.5-2.3 kcal/mol). The first case of "improper" (blue-shifting) NH···F hydrogen bonds was observed in fluorobenzene and perfluorobenzene solutions. It was shown that hydrogen-bonded complexes are the intermediates of proton transfer from alcohols and phenols to DMAB. The reaction mechanism was examined computationally taking into account the coordinating properties of the reaction media. The values of the rate constants of proton transfer from HFIP to DMAB in acetone were determined experimentally [(7.9 ± 0.1) × 10(-4) to (1.6 ± 0.1) × 10(-3) mol(-1)·s(-1)] at 270-310 K. Computed activation barrier of this reaction ΔG(‡theor)298 K(acetone) = 23.8 kcal/mol is in good agreement with the experimental value of the activation free energy ΔG(‡exp)270 K = 21.1 kcal/mol.

Plant membrane assays with cytokinin receptors underpin the unique role of free cytokinin bases as biologically active ligands.

Cytokinin receptors play a key role in cytokinin-dependent processes regulating plant growth, development, and adaptation; therefore, the functional properties of these receptors are of great importance. Previously the properties of cytokinin receptors were investigated in heterologous assay systems using unicellular microorganisms, mainly bacteria, expressing receptor proteins. However, within microorganisms receptors reside in an alien environment that might distort the receptor properties. Therefore, a new assay system has been developed allowing studies of individual receptors within plant membranes (i.e. closer to their natural environment). The main ligand-binding characteristics of receptors from Arabidopsis [AHK2, AHK3, and AHK4] and maize (ZmHK1) were refined in this new system, and the properties of full-length Arabidopsis receptor AHK2 were characterized for the first time. Ligand specificity profiles of receptors towards cytokinin bases were comparable with the profiles retrieved in bacterial assay systems. In contrast, cytokinin-9-ribosides displayed a strongly reduced affinity for receptors in the plant assay system, indicating that ribosides as the common transport form of cytokinins have no or very weak cytokinin activity. This underpins the central role of free bases as the sole biologically active cytokinin compounds. According to molecular modelling and docking studies, N (9)-ribosylation alters the bonding pattern in cytokinin-receptor interaction and prevents ß6-ß7 loop movement important for tight hormone binding. A common feature of all receptors was a greatly reduced ligand binding at low (5.0-5.5) pH. The particularly high sensitivity of ZmHK1 to pH changes leads to the suggestion that some cytokinin receptors may play an additional role as pH sensors in the lumen of the endoplasmic reticulum.

Synthesis of gem-difluorinated nitroso compounds.

A method for the synthesis of gem-difluorinated nitroso compounds is described. The reaction involves interaction of organozinc reagents with (bromodifluoromethyl)trimethylsilane followed by nitrosation of difluorinated organozinc species with an n-butyl nitrite/chlorotrimethylsilane system.

Difluoromethylene phosphabetaine as an equivalent of difluoromethyl carbanion.

A method for nucleophilic difluoromethylation of reactive Michael acceptors, aldehydes, and azomethines is described. The reaction is performed using the readily available and air-stable reagent difluoromethylene phosphabetaine. The process involves interaction of an electrophilic substrate with in situ generated difluorinated phosphonium ylide followed by hydrolysis of the carbon-phosphorus bond under mild conditions.

Geminal silicon/zinc reagent as an equivalent of difluoromethylene bis-carbanion.

A new difluorinated reagent, [difluoro(trimethylsilyl)methyl]zinc bromide, bearing C-Zn and C-Si bonds is described. The reagent is conveniently prepared by cobalt-catalyzed halogen/zinc exchange. It can be coupled with two different C-electrophiles in a stepwise manner (with allylic halides for C-Zn bond and aldehydes for C-Si bond) affording products containing a difluoromethylene fragment.

Solvent-controlled synthesis of tetranuclear cage-like copper(II) silsesquioxanes. Remarkable features of the cage structures and their high catalytic activity in oxidation with peroxides.

Two principally different in their molecular architecture isomeric tetranuclear copper(ii) silsesquioxanes, "Globule"-like compound [(PhSiO1.5)12(CuO)4(NaO0.5)4] (1) and "Sandwich"-like derivative [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (2), were synthesized by the partial cleavage of polymeric copper(ii) silsesquioxane [(PhSiO1.5)2(CuO)]n by tetraphenylcyclotetrasiloxanolate. The route leading to the formation of either 1 or 2 entirely depends on the nature and composition of the solvent used for this reaction. Thus, the process in an ethanol-1-butanol solution gives compound 1. When a 1,4-dioxane-methanol mixture was used, compound 2 was prepared. The structures and unusual crystal packing of the cages were confirmed by the X-ray studies. It has been found that the reaction of benzene with H2O2 in acetonitrile solution at 50 °C catalyzed by 1 requires addition of trifluoroacetic acid (TFA) in low concentration and gives phenol with a turnover number (TON) of 250 after 3 h. The initial reaction rate W0 linearly depends on the concentration of catalyst 2. The oxidation of 1-phenylethanol to acetophenone with hydrogen peroxide catalyzed by complex 1 in the presence of TFA is not efficient. In contrast, 1 exhibited excellent activity in the oxidation with tert-butyl hydroperoxide (TBHP) in the absence of any acid (the yield of acetophenone was close to the quantitative, TON attained 475 after 2 h). A kinetic study of this reaction led to the conclusion that the process occurs with the participation of radicals tert-BuO˙ produced in the Cu-promoted decomposition of TBHP. The mode of dependence of W0 on the initial concentration of TBHP indicates the formation of an intermediate adduct between the catalyst 1 and TBHP (characterized by the equilibrium constant K1≈ 2 M(-1) for the conditions of conducted experiments) followed by subsequent decomposition of the adduct (k2≈ 0.2 s(-1)) to generate an intermediate species tert-BuO˙ which induces the alcohol oxidation.