Valentine P. Ananikov

• Prof. Dr.
• Russian Academy of Sciences

Humins, a by‐product of biomass‐to‐furanics processing, are sustainable and underutilized carbonaceous feedstock. This study introduces liquid humins as precursors for synthesizing innovative carbon materials tailored for Pd/C catalysts. These materials mitigate the “dead” metal issue, where inaccessible Pd particles hinder catalytic efficiency. By...

Digitization of molecular complexity is of key importance in chemistry and life sciences to develop structure–activity relationships in chemical behavior and biological activity. The complexity of a given molecule compared to others is largely based on intuitive perception and lacks a standardized numerical measure. Quantifying molecular complexity...

The accumulation of large datasets by the scientific community has surpassed the capacity of traditional processing methods, underscoring the critical need for innovative and efficient algorithms capable of navigating through extensive existing experimental data. Addressing this challenge, our study introduces a machine learning (ML)-powered search...

High-temperature organic chemistry represents a transformative approach for accessing reaction pathways previously considered unattainable under conventional conditions. This study focuses on a high-temperature synthesis as a powerful method for performing solution-phase organic reactions at temperatures up to 500 °C. Using the isomerization of N-s...

A novel series of bio‐based cationic surfactants, synthesized from the platform chemical 5‐(hydroxymethyl)furfural (5‐HMF), fatty acids, and bio‐based amines, has been developed, offering a sustainable alternative to conventional surfactants. These compounds, referred to as surface‐active ionic liquids (SAILs), have critical micelle concentration (...

Isophthalonitrile derivatives (IPNs) have emerged as promising organic photocatalysts due to their efficiency and accessibility; however, their inherent lability under light‐induced conditions poses significant challenges in monitoring their transformation pathways. Understanding these pathways is crucial for optimizing photocatalytic processes and...

Catalytic cross-coupling reactions, such as the Mizoroki–Heck reaction, play a crucial role in synthetic chemistry but pose significant environmental and health risks due to the toxicity of reaction components and their mixtures. In this study, we conducted a comprehensive cytotoxicity assessment of individual substances and complex reaction mixtur...

Adapting biological systems for nanoparticle synthesis opens an orthogonal Green direction in nanoscience by reducing the reliance on harsh chemicals and energy-intensive procedures. This study addresses the challenge of efficient...

Palladium catalysts constitute a cornerstone of modern chemistry with upmost scientific and industrial impact. Bulk palladium metal itself is chemically inert, and a sequence of chemical transformations has to be utilized to convert the metal into a Pd precatalyst covered by ligands. However, the “cocktail” concept of catalysis discovered recently...

Biofilms are critical for understanding environmental processes, developing biotechnology applications, and progressing in medical treatments of various infections. Nowadays, a key limiting factor for biofilm analysis is the difficulty in obtaining large datasets with fully annotated images. This study introduces a versatile approach for creating s...

Ionic liquids (ILs) are structurally tunable salts with applications ranging from chemical synthesis to batteries, novel materials and medicine. Despite their potential, the toxicity of ILs poses significant environmental and biological challenges. This study introduces a comprehensive dataset of cytotoxicity of 1227 ILs, compiled from 151 research...

The transition toward renewable resources is pivotal for the sustainability of the chemical industry, making the exploration of biobased furanic platform chemicals derived from plant biomass of paramount importance. These compounds, promising alternatives to petroleum‐derived aromatics, face challenges in terms of stability under synthetic conditio...

N,N′‐Diarylimidazolium salts containing haloalkyl functional groups that are reactive with various nucleophiles are considered to be promising reagents for the preparation of functionalized N‐heterocyclic carbene (NHC) ligands, which are in demand in catalysis, materials science, and biomedical research. Recently, 4‐chloromethyl‐functionalized N,N′...

A key goal of organic chemistry is to develop new principles for the control of reactions, which can be used to create promising materials demanded in all fields of scientific research and industry. This review is an overview of the scientific advances, which have been made by the N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy...

Determining molecular structures is foundational in chemistry and biology. The notion of discerning molecular structures simply from the visual appearance of a material remained almost unthinkable until the advent of machine learning. This paper introduces a pioneering approach bridging the visual appearance of materials (both at the micro‐ and nan...

The current discussion surrounding the role of artificial intelligence (AI) in chemistry often centers on the provocative question of whether AI will supplant chemists in the laboratory. Such debates, while stimulating, tend to overshadow a more pressing and realistic consideration. At present, there is little evidence to suggest that AI will repla...

The transition to a sustainable future requires the use of waste‐free technologies for production. Potentially, additive technologies can be a promising approach for accessing circular economy due to the precise amount of feeding materials and the absence of molds. However, the initial feeding materials for additive approaches are often based on no...

Working with liquid/gas-phase systems in chemical laboratories is a fundamentally important but difficult operation, mainly due to the explosion risk associated with conventional laboratory equipment. Such systems, in the case of improper operation or destruction, may pose a significant threat to researchers. To address this challenge, our work exp...

Nickel and palladium NHC complexes with fluorine substituents have been synthesized. Their electronic parameters, including σ-donation and π-acceptance, were evaluated, considering the position and number of substituents.

A new approach for the preparation of a variety of 3-arylated 2-furoic acid derivatives has been developed. The approach involves selective Ru-catalyzed C3-H arylation of the furan moiety of readily available 2-furoyl-1-methylimidazole (using imidazole as a removable N-donor directing group), subsequent N-methylation, and nucleophilic substitution...

We propose a set of features for the ordered arrangement of palladium nanoparticles that are consistent with the intuitive understanding of researchers and allow quantification of the data in terms of easily interpretable physical parameters.

The beginning and ripening of digital chemistry is analyzed focusing on the role of artificial intelligence (AI) in an expected leap in chemical sciences to bring this area to the next evolutionary level. The analytic description selects and highlights the top 20 AI-based technologies and 7 broader themes that are reshaping the field. It underscore...

Mass spectrometry is a widely used method to study molecules and processes in medicine, life sciences, chemistry, catalysis, and industrial product quality control, among many other applications. One of the main features of some mass spectrometry techniques is the extensive level of characterization (especially when coupled with chromatography and...

The change in the composition of the electrolyte after life cycle testing (cycling) of lithium-ion batteries (LIBs) was studied. The cell with a nominal capacity of 22 A h was composed of a cathode based on nickel-rich layered lithium oxide LiNi0.6Mn0.2Co0.2O2 (NMC622) and an anode based on graphite. NMR and high-resolution mass spectrometry demons...

The formation of transient hybrid nanoscale metal species from homogeneous molecular precatalysts has been demonstrated by in situ NMR studies of catalytic reactions involving transition metals with N‐heterocyclic carbene ligands (M/NHC). These hybrid structures provide benefits of both molecular complexes and nanoparticles, enhancing the activity,...

Oxidative addition (OA) is a necessary step in mechanisms of widely used synthetic methodologies such as the Heck reaction, cross-coupling reactions, and the Buchwald–Hartwig amination. This study pioneers the exploration of OA of aryl halide to palladium nanoparticles (NPs), a process previously unaddressed in contrast to the activity of well-stud...

Polymer properties can be defned by functionalizing the monomer and tuned by modifying key properties, such as, molar mass and dispersity. Typically, these modification approaches require significant alterations to the synthesis process, or even re-optimization of the whole process. In this study, we demonstrate that deuteration, a mainly overlooke...

The beginning and ripening of digital chemistry is analyzed focusing on the role of artificial intelligence (AI) in an expected leap in chemical sciences to bring this area to the next evolutionary level. The analytic description selects and highlights the top 20 AI-based technologies and 7 broader themes that are reshaping the field. It underscore...

The formation of transient hybrid nanoscale metal species from homogeneous molecular precatalysts has been demonstrated by in situ NMR studies of catalytic reactions involving transition metals with N‐heterocyclic carbene ligands (M/NHC). These hybrid structures provide benefits of both molecular complexes and nanoparticles, enhancing the activity,...

This review explores the pivotal role of sulfur in advancing sustainable carbon‐carbon (C–C) coupling reactions. The unique electronic properties of sulfur, as a soft Lewis base with significant mesomeric effect make it an excellent candidate for initiating radical transformations, directing C–H‐activation, and facilitating cycloaddition and C–S bo...

This review explores the pivotal role of sulfur in advancing sustainable carbon‐carbon (C–C) coupling reactions. The unique electronic properties of sulfur, as a soft Lewis base with significant mesomeric effect make it an excellent candidate for initiating radical transformations, directing C–H‐activation, and facilitating cycloaddition and C–S bo...

The aim of the present study was to explore the transformations of heteroleptic and homoleptic Au(I) complexes in detail and to systematically map their chemical evolutionary pathways. The relationships between these Au(I) complexes and the formation of gold nanoparticles and between the leaching processes of Au species from nanoparticles by NHC ca...

In modern organic chemistry, harnessing the power of multicomponent radical reactions presents both significant challenges and extraordinary potential. This article delves into this scientific frontier by addressing the critical issue of controlling selectivity in such complex processes. We introduce a novel approach that revolves around the revers...

Aryl chlorides, due to their affordability and accessibility, are preferred reagents in Pd‐catalyzed arylation reactions. However, the reactivity of aryl chlorides is often lower than that of aryl bromides and iodides due to the significantly higher barriers of the oxidative addition stage. This research introduces a novel design for NHC ligands, w...

In the realm of modern organic chemistry, harnessing the power of multicomponent radical reactions presents both significant challenges and extraordinary potential. This article delves into this scientific frontier by addressing the critical issue of controlling selectivity in such complex processes. We introduce a novel approach that revolves arou...

Supercapacitors (SCs) have emerged as critical components in applications ranging from transport to wearable electronics due to their rapid charge‐discharge cycles, high power density, and reliability. This review offers an analysis of recent strides in supercapacitor research, emphasizing pivotal developments in sustainability, electrode materials...

Fine chemical synthesis is the key area of industry and academic research, with a strong focus on catalytic C–C bond formation targeted at drug design, biologically active compounds and new materials. Until recently, such catalytic technologies had been employed without a rigorous analysis of a plausible ecological impact, which is now a key questi...

Encapsulation of hygroscopic, toxic, flammable chemicals in 3D-printed capsules accelerated reaction optimization by a factor of 60 while improving the operator safety. The capsules were compatible with organic transformations and provided good yields.

Carbon−carbon and carbon−heteroatom bond formations via direct reductive elimination as one of the possible mechanisms of reductive elimination in Pd(II) complexes are the key stages of catalytic processes in fine organic synthesis. For the (R)2Pd(L)2, (X)2Pd(L)2 and (R)(X)Pd(L)2 complexes (where R = Me, Vin, Ph, or Eth; X = B, N, O, Si, P, S, Se,...

Constructing molecular complexity from simple precursors stands as a cornerstone in contemporary organic synthesis. Systems harnessing easily accessible starting materials, which offer control over stereochemistry and support a modular assembly approach, are particularly in demand. In this research, we utilized calcium carbide, presenting a sustain...

After the appearance of the green chemistry concept, which was introduced in the chemistry vocabulary in the early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form the basis for an ideal chemical process. This review analyzes the accumulated experience and achievement...

This review addresses the largely overlooked yet critical issue of “dead” metal in heterogeneous metal catalysts. “Dead” metal refers to the fraction of metal in a catalyst that remains inaccessible to reactants, significantly reducing the overall catalyst performance. As a representative example considered in detail here, this challenge is particu...

Metal‐catalyzed asymmetric alkylation of indoles with α‐diazoesters is well‐known, however, the underlying mechanisms of this reaction, particularly the origin of stereoselectivity, remain uncertain. For the Pd catalysis, we address this cutting‐edge challenge from two complementary viewpoints – i) the molecular level regarding a single catalytical...

Additive manufacturing technologies (or 3D printing) have emerged as potent tools in the creation of a diverse array of objects, promising a paradigm shift in production methodologies across industries. However, the benefits of these technologies can be diminished by the use of suboptimal parameters or inferior materials, leading to defects that si...

This study presents a novel ″3-in-1″ hybrid biocatalyst design that combines the individual efficiency of microorganisms while avoiding negative interactions between them. Yeast cells of Ogataea polymorpha VKM Y-2559, Blastobotrys adeninivorans VKM Y-2677, and Debaryomyces hansenii VKM Y-2482 were immobilized in an organosilicon material by using t...

Comprehensive Summary Calcium carbide is considered a possible key component in the sustainable carbon cycle, including convenient recycling of carbon wastes to industrial uptake. However, currently employed CaC 2 manufacturing process produces significant amounts of CO 2 . One of the main factors of its appearance is the formation of carbon oxide...

Additive manufacturing technologies (or 3D printing) have emerged as potent tools in the creation of a diverse array of objects, promising a paradigm shift in production methodologies across industries. However, the benefits of these technologies can be diminished by the use of suboptimal parameters or inferior materials, leading to defects that si...

Microbial interactions are one of the major topics of current research due to their great societal relevance. It is now established that biofilms—associations of microorganisms, exchanging various chemical compounds, including proteins and nucleic acids—are capable of promoting horizontal transfer of resistance genes. However, our understanding of...

Imidazolium salts have found ubiquitous applications as N-heterocyclic carbene precursors and metal nanoparticle stabilizers in catalysis and metallodrug research. Substituents directly attached to the imidazole ring can have a significant influence on the electronic, steric, and other properties of NHC-proligands as well as their metal complexes....

Visible light irradiation of an aqueous solution of sodium alginate and organometallic complex [(C5H5)Fe(toluene)]BF4 transforms it into a rigid hydrogel due to crosslinking of the carboxylate groups by the iron ions. Irradiation of the same iron complex together with K2S2O8 initiates the polymerization of acrylamide, which provides an efficient me...

Electron microscopy is a key characterization technique for nanoscale systems, and electron microscopy images are typically recorded and analyzed in terms of the morphology of the objects under study in static mode. The emerging current trend is to analyze the dynamic behavior at the nanoscale observed during electron microscopy measurements. In th...

In this work, using a combination of scanning and transmission electron microscopy (SEM and TEM), the transformations of palladium‐containing species in imidazolium ionic liquids in reaction mixtures of the Mizoroki‐Heck reaction and in related organic media are studied to understand a challenging question of the relative reactivity of organic hali...

Understanding the interface between soluble metal complexes and supported metal particles is important in order to reveal reaction mechanisms in a new generation of highly active homogeneous transition metal catalysts. In this study, we show that, in the case of palladium forming on a carbon (Pd/C) catalyst from a soluble Pd(0) complex Pd2dba3, the...

Cross-coupling reactions are among the most important transformations in modern organic synthesis1–3. Although the range of reported (het)aryl halides and nucleophile coupling partners is very large considering various protocols, the reaction conditions vary considerably between compound classes, necessitating renewed case-by-case optimization of t...

An efficient protocol for the C−N cross‐coupling of aryl chlorides with (hetero)aryl‐ and alkyl amines under nickel catalysis has been developed. The main advantage of the protocol is the use of a self‐activated Ni/NHC catalytic system generated in situ from readily available bench‐stable air‐tolerant precursors: NiCl2Py2, IPr ⋅ HCl, and sodium ter...

During previous stages of research, high biocidal activity toward microorganism archival strains has been used as the main indicator in the development of new antiseptic formulations. Although this factor remains one of the most important characteristics of biocide efficiency, the scale of antimicrobial resistance spread causes serious concern. The...

An approach to the spatially localized characterization of supported catalysts over a reaction course is proposed. It consists of a combination of scanning, transmission, and high-resolution scanning transmission electron microscopy to determine metal particles from arrays of surface nanoparticles to individual nanoparticles and individual atoms. T...

The discovery of high-performance thermoplastics for additive technologies has opened new areas of science and industry with the paramount application of fused filament fabrication 3D printing (FFF). Indeed, it is the emergence of new materials that the further development of FFF technology is associated with. Such materials must combine several hi...

Water‐soluble Pt complexes are the key components in medicinal chemistry and catalysis. The well‐known cisplatin family of anticancer drugs and industrial hydrosylilation catalysts are two leading examples. On the molecular level, the activity mechanisms of such complexes mostly involve changes in the Pt coordination sphere. Using ¹⁹⁵Pt NMR spectro...

Sustainable human development urgently calls for decreasing the cost of energy storage. Continuous massive consumption of dedicated carbon electrode materials with complex internal molecular architectures requires rethinking both the source of materials and the process of their production. Finding an efficient sustainable solution is focused on the...

Industrial activity results in ton-scale production of calcium carbide and generation of a significant amount of calcium carbide residue (CCR), which is often disposed of in the environment as waste. CCR is an active chemical, and rain washes away alkali from sludge, changing the pH of soils and water and damaging the environment. In this work, we...

Sugar production is accompanied by the formation of waste in the form of beet pulp. In this study, a procedure is described for turning sugar beet pulp waste into structured carbon materials for making electrodes in supercapacitors. The overall sustainable path is to produce sugar for human consumption and prepare high‐quality carbon material for e...

Pd/NHC complexes (NHCs - N-heterocyclic carbenes) with electron-withdrawing halogen groups were prepared by developing an optimized synthetic procedure to access imidazolium salts and the corresponding metal complexes. Structural X-ray analysis and computational studies have been carried out to evaluate the effect of halogen and CF3 substituents on...

Biomass-derived C6-furanic compounds have become the cornerstone of sustainable technologies. The key feature of this field of chemistry is the involvement of the natural process only in the first step, i.e., the production of biomass by photosynthesis. Biomass-to-HMF (5-hydroxymethylfurfural) conversion and further transformations are carried out...

In a previous development stage, mostly individual antibacterial activity was a target in the optimization of biologically active compounds and antiseptic agents. Although this targeting is still valuable, a new trend has appeared since the discovery of superhigh resistance of bacterial cells upon their aggregation into groups. Indeed, it is now we...

Straightforward access to bidentate phosphorus ligands and bis(phosphineoxide)ethanes is described based on atom-economic addition reaction. A practical approach was developed to incorporate ² H and ¹³ C labels using easily available reagents.

For the first time, the transformation of biobased 5-HMF derivatives succeeded in a 2 × [4 + 2] cascade cycloaddition reaction, leading to a drastic (3-5-fold) increase in molecular complexity as a result of one synthetic step. A new approach to the use of plant biomass in organic synthesis using a cascade Diels-Alder reaction of 5-HMF dimer deriva...

A simple approach aligned with dynamic catalysis principles was successfully applied in a study of hydrosilylation reactions. The readily available Pt 2 dba 3 complex formed a “cocktail”-type system with comparable performance to known catalysts.

The mechanism of the formation of catalytic species in the practically important Mizoroki–Heck reaction, which is in demand in modern fine organic synthesis, has been studied. It has been shown that catalysts based on palladium complexes with N-heterocyclic carbene ligands are transformed into a “ligand-free” form under the conditions of the Mizoro...

Agriculture is the most massive material circulation activity of humans, with significant annual volumes of production as well as substantial amounts of waste. Transforming agricultural wastes into high‐value‐added products is the key to sustainable development with efficient usage of renewable resources. The present study demonstrates the fine‐tun...

Fossil resources are rapidly depleting, forcing researchers in various fields of chemistry and materials science to switch to the use of renewable sources and the development of corresponding technologies. In this regard, the field of sustainable materials science is experiencing an extraordinary surge of interest in recent times due to the signifi...