Non-targeted qualitative analysis has two aspects: instrumental, which involves collection of experimental data needed to solve a given problem, and mathematical, which involves analysis of these data to extract useful information and make reliable decisions. This review is devoted to the latter aspect, namely the general problems of chemometrics and machine learning, which are often incorrectly called artificial intelligence. Various problem formulations are considered, including discrimination and authentication; classification methods (binary, multi-class, or one-class); and types of made decisions (deterministic and probabilistic, soft and hard). Particular attention is given to analytical figures of merit such as sensitivity, specificity, and selectivity and how these characteristics are used for model optimization and validation. The concept of a cumulative analytical signal is also presented, and the prospects for its application in qualitative analysis are discussed. The bibliography includes 162 references.
Isoindolinones are privileged nitrogen-containing heterocycles widely found in bioactive molecules, natural products, and functional scaffolds. Compared with conventional approaches based on prefunctionalized substrates, transition-metalcatalyzed cascade C–H functionalization provides a more direct and step-economical strategy for isoindolinone construction. This review summarizes recent advances in isoindolinone synthesis through C(sp3)–H, C(sp2)–H and C(sp)–H activation, with emphasis on Pd-, Rh-, Ru-, Ir-, Co-, and Cu-catalyzed annulation systems. Key coupling partners, including alkenes, alkynes, diazo compounds, isocyanides, nitriles, CO surrogates, strained rings and multicomponent reagents, are discussed in relation to substrate scope, regioselectivity, stereoselectivity and product topology. Particular attention is given to mechanistic features such as cyclometalation, migratory insertion, β-hydride elimination, reductive elimination, carbonylation, radical relay, hydrogen atom transfer and cascade cyclization. Complementary photochemical, electrochemical, mechanochemical and metal-free strategies are also considered. By comparing metal-dependent reactivity and persistent limitations, this review highlights current challenges and future opportunities in directing-group economy, redox sustainability, substrate generality and asymmetric control. The bibliography includes 220 references.
This review summarizes the modern views on the mechanism, active site structure, and thermodynamics of the electrochemical oxygen reduction reaction catalyzed by heteroatom-doped carbon nanostructures for the subsequent rational design of catalytic sites and development of promising metal-free cathode materials for fuel cells for next-generation energy systems. The effect of both classic (B, N, S, P, O, Hal) and advanced "hybrid" (Si, Se) dopants in various states and in two- or threecomponent forms on the activity modulation of oxygen adsorption sites and on the reaction mechanism is considered. Particular attention is paid to the evolution of the views on the role of silicon, which switched from considering silicon to be inert due to its high oxophilicity to the discovery of unique catalytic properties of silicon in SiNx type catalytic sites. The conclusions made in the review open up new opportunities for the targeted design of hierarchical materials with adjustable properties via precise control of the composition and structure of heteroatom defects. The bibliography includes 252 references.
Improving hydrocarbon feedstock processing efficiency is an important objective for modern chemical science. To address this issue, technologies for catalytic conversion of light alkanes and alkenes should be developed. Metal-modified zeolites demonstrate the required catalytic performance for selective dehydrogenation, aromatization, and oxidation of light hydrocarbons. Understanding how metal-containing zeolites work on the molecular level can help in the successful design of industrial catalysts. This review summarizes the fundamental studies on the mechanisms of light alkane and alkene activation and transformation on zeolites modified with copper, zinc, silver, and indium. The available data on the structure and composition of active metal-containing sites, the nature of the key surface intermediates, and possible transformation pathways for C1 – C4 alkanes and C2 – C4 alkenes are systematized and critically analyzed. Conclusions regarding the basic principles and characteristics of metal-modified zeolite catalysis are provided. The bibliography includes 393 references.
Since its discovery in 1995, the Soai reaction remains the only experimental example of a chemical reaction capable of amplifying enantiomeric excess to a virtually enantiopure state. This review consolidates the results of three decades of research, including data from recent years that have broadened the understanding of the reaction mechanism. Competing catalytic models (dimeric, tetrameric, hemiacetal, and others) are critically reviewed; a broad spectrum of chiral triggers, ranging from circularly polarized light and chiral minerals to cryptochiral isotopomers, is systematized; and the phenomenon of absolute asymmetric synthesis is analyzed. The position of the Soai reaction among other chirality amplification mechanisms and its significance as a model for the origin of biological homochirality are discussed. The bibliography includes 159 references.
Quantifying fundamental concepts of chemical bonding, such as ionicity, covalency, effective atomic charges, and the decomposition of cohesive energy into chemically interpretable contributions, remains a persistent challenge in theoretical chemistry. This work reviews a recently developed first-principles methodology based on Wannier functions possessing atomic orbital symmetry, which provides a rigorous framework for numerically characterizing these bonding attributes across diverse systems. We survey the method′s theoretical foundations and application to a wide range of materials, highlighting key results that validate its reliability and universality. Examples demonstrate how the approach captures essential physics of chemical bonding, and bridges conceptual models with quantitative analysis. By synthesizing the accumulated evidence, this review underscores the method′s utility as a robust tool for bonding analysis and discusses its limitations and future prospects. The bibliography includes 19 references.
Cancer remains a leading cause of global mortality, highlighting the urgent need for safe and effective therapeutic strategies. Photothermal therapy (PTT) and photodynamic therapy (PDT) have emerged as promising approaches for tumour treatment. Quantum dots (QDs), semiconductor nanocrystals with unique quantum effects, offer significant potential in these therapies. Among them, metal sulfide quantum dots (MS QDs), with particle sizes ranging from 1 to 10 nm, stand out due to their excellent fluorescence, chemical stability, photophysical properties, and biocompatibility. These attributes make MS QDs particularly suitable for combined PTT/PDT in cancer therapy. This review systematically discusses the synthesis methods of MS QDs and highlights recent advancements in their application for PTT/PDT combination therapy. Finally, we provide perspectives on the future development of MS QDs in phototherapeutic applications. The bibliography includes 275 references.
Currently, the main type of electrochemical energy storage devices are lithium-ion batteries, the global production of which amounts to billions of units per year. Further progress in electrochemical energy storage systems may follow two general trends: improvement of existing lithium-ion batteries and design of alternative types of energy storage devices (so-called post-lithium-ion batteries). The former trend is limited by the fact that characteristics of lithium-ion batteries are approaching the theoretical limit. The latter one is concerned with sodium-ion batteries, lithium–air batteries and primary power sources, lithium–sulfur batteries, and redox flow systems. The present review analyzes state-of-the-art in the development of virtually all types of electrochemical energy storage devices, which makes it possible to compare their characteristics and determine the most appropriate applications for each type of device. The bibliography includes 316 references.
The development of effective encapsulation methods for hydrophobic compounds is a relevant interdisciplinary challenge, particularly for medicine and biotechnology where high therapeutic potential of compounds often cannot be implemented due to solubility and delivery issues. This review provides a systematic analysis of one-step ultrasonic synthesis of emulsion capsules composed of polymers. According to this approach, ultrasonic cavitation not only facilitates the formation of stable emulsions, but also initiates a cascade of physicochemical transformations of biopolymers (proteins, polysaccharides, and glycoproteins), resulting in the formation of robust shells at an interface. This review presents the first comparison and classification of shell formation mechanisms depending on the polymer type, clarifies the role of generated radicals, and highlights the synergistic effects observed in hybrid systems. Special emphasis is placed on the practical potential of this technique for the design of drug delivery systems, contrast agents, and smart materials with controlled release functionality. The bibliography includes 93 references.
This review is devoted to an important part of the chemistry of nanomaterials synthesized by laser deposition methods. The structural and composition features of these nanomaterials formed the key trend of research in this field: catalytic and sensing properties. This is not the only application where these materials show promise, but it is undoubtedly the most important one. Until very recently, research in this area was the preserve of specialists in laser physics, electronic and semiconductor technology, and nonlinear optics. The goal of this review is to partially fill the information gap and discuss the role of chemical factors that enable the preparation of nanomaterials with high catalytic and sensing properties. This will enable interested researchers to optimize the laser synthesis processes by deliberately selecting the composition of the starting materials and precursors relying on the information on possible phase compositions and crystallographic characteristics. The discussion of the chemical aspects of laser synthesis is preceded by a brief description of the fundamentals of pulsed laser deposition (PLD) method and laser-induced chemical liquid-phase deposition (LCLD) of metals from solutions. The description is focused on the formation of the phase structure of nanoparticles and nanofilms, which determines their sensing and catalytic properties. The prospects of using laser deposition processes for the design of nanomaterials for hydrogen energy, medicine, organic and inorganic catalysis, and ecology are also analyzed. The bibliography includes 219 references.
The proportion of waste electrical and electronic equipment is increasing year by year. This phenomenon is driven by the economic development and growing consumption. Acrylonitrile–butadiene–styrene copolymers represent a substantial constituent of electronic and household appliance waste. Butadienenitrile rubber and polyacrylonitrile are also classified as high-tonnage products. The waste from these polymers share the presence of a nitrile moiety in the macromolecules and the impossibility of selective solvolysis/hydrolysis to obtain monomers, as in the case of polyethylene terephthalate, polyamides, and polyimides. The chemical recycling of acrylonitrile copolymers is frequently rendered more complex by the presence of brominated flame retardants and synergists and therefore the elevated levels of nitrogen and bromine compounds present in the products. The review methodically analyzes the chemical recycling of polyacrylonitrile and its copolymers, including hydrolysis, hydrothermal recycling, gasification, and pyrolysis. The primary focus of this study is on brominated waste, which poses significant challenges in terms of reuse without undergoing chemical recycling. In contrast to previous review publications, the present study provides comprehensive analysis of the hydrocarbon composition of polymer conversion products and the content of nitrogen- and bromine-containing organic compounds. The potential for the further refining of pyrolysis products to yield not only fuels but also high value-added products, such as monomers, is considered separately. The potential of methods for preliminary preparation of polymer waste for recycling including hydrolysis and hydrothermal treatment, which have not received sufficient attention previously, is demonstrated. The bibliography includes 182 references.
The review addresses simple and efficient approaches to the rational synthesis of conjugates of oligonucleotides with functional molecules (FMs), including active low-molecular-weight compounds and macromolecules of various natures. These compounds can possess high reactivity, catalytic activity, or affinity for nucleic acid (NA) targets (e.g., intercalators, ligands exhibiting NA affinity); they can provide visualization (reporter groups, fluorophores), intracellular transport, desired cellular distribution, and related functions. The principles of "oligonucleotide construction set" are formulated as an algorithm taking account of specific features of conjugate formation depending on the structure of both the nucleic acid component and the FM component in terms of the pre-synthetic (direct) and postsynthetic (indirect) strategies. Unlike the existing reviews, which are most often devoted to one or a few conjugation techniques or conjugates of a particular type, the present review demonstrates the whole diversity of interactions between oligonucleotides and various compounds. The review covers both classic and modern methods that employ a minimal optimal set of efficient reactions and reagents that make it possible to preserve the functional properties of both components (NA and FM) and achieve the desired action of the conjugate on biological targets. The bibliography includes 420 references.
The review describes the phenomenon of phytomining, that is, accumulation of metals, including noble and rare-earth elements, by plants. Kinetic modelling is used to explore the process dynamics, which has a two-compartment nature. In terms the widely accepted concept of the plant origin of coal, the role of metal phytomining in the formation of coal deposits is analyzed, demonstrating the effect of accumulation of toxic metals in plants near coal mining areas and in industrial waste dumps. The metal contents of natural coals and ash and slag waste of coal-fired power plants in Russia are analyzed. The challenges of metal extraction by the conversion of technogenic mineral deposits are discussed. Data on the nature and kinetics of phytomining and on the geochemical and technological consequences of this global natural phenomenon are summarized and analyzed for the first time. The bibliography includes 107 references.
The review addresses potential applications of layered LiNixCoyMnzO2 (x + y + z = 1) oxides in the form of non-agglomerated large-crystalline (single-crystal) particles as cathode materials for lithium-ion batteries (LIBs). A unique feature of this review is integration of fundamental aspects into a unified material design strategy. Correlations between the thermodynamics of crystal facet surface energy, the chemical potentials of lithium and oxygen, and crystal growth kinetics were established for the first time. This enables targeted control of particle morphology depending on the surface composition and synthesis conditions. The chemistry and thermodynamic conditions of defect formation are described in detail, and existing gaps in their crystallographic description are highlighted. In comparison with other studies, the patterns of mechanical degradation of single crystals during long-term cycling were identified, which made it possible to formulate strategies for effective control of the defect structure to fabricate cathodes with high specific capacity and extended cycle life. Methods for investigating the mechanical properties of particles and methodological limitations of these methods are analyzed for the first time. The bibliography includes 308 references.
Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical technique for substance identification and analyte determination in ultralow concentrations in complex media. Recent progress in SERS-based biosensors has paved the way to reproducible, sensitive, rapid and easy-to-use point-of-care (PoC) systems that are promising for the implementation in diagnostics. This review summarizes different approaches in biosensor construction, analytical signal generation, as well as the first attempts of their use for the real clinical samples. The review focuses on the pathogen detection in the biological liquids in trace amounts. Available clinical diagnostics failed to meet criteria for accurate PoC diagnostics, such as time of analysis < 20 min, limits of detection of 100 – 1000 genomes mL1-1 and specificity of detection. Several SERS-biosensors met these criteria achieving multiple pathogens in the sample. Another significant ability of the SERS-based biosensors and test systems is rapid determination of drug-resistance at low pathogen titers. Several excellent examples and future prospects are discussed in the review. This critical analysis demonstrates that the successful integration of SERS into diagnostic platforms depends on the combination of three main elements: 1) a reproducible SERS substrate with a high enhancement coefficient, 2) a recognition element that ensures specificity of detection, and 3) additional approaches for concentrating the analyte and amplifying the analytical signal. The bibliography includes 300 references.
In view of the growing demand for highly functional hybrid polymers for electronics, medicine and smart materials, the relevance of studies of thermoplastic polyurethane-urea siloxanes has substantially increased; however, systematic data in this field are virtually absent. For the first time in the past 10 years, this review presents a comprehensive analysis of the advances in the field of linear segmented thermoplastic polyurethane-, polyurea-, and polyurethane-urea-siloxanes (TPU-Si). The key relationships between the synthesis methods, structure, and properties of materials, including problems of hydrolytic stability and microphase separation, are analyzed. A unique feature of the paper is in the original overview tables that compare more than 400 compounds and their physicochemical characteristics, which forms the basis for targeted design of materials. The review integrates chemical synthesis, computer simulation, and applied aspects, offering researchers and engineers an effective tool for the development of new polymers for robotics, biomedicine, and additive technologies. The bibliography includes 224 references.
Nowadays, it′s impossible to imagine the metallurgical industry without hydrometallurgical processes. This is due to the need to process ores with lower metal content and stricter environmental standards. Therefore, the search for new technological approaches to metal extraction has become increasingly important. The trend in the development of hydrometallurgical processes is changing. Previously, the primary focus was on finding new sorbents, extractants, flotation reagents, ionic liquids, etc., to improve extraction efficiency. However, as technological saturation reached, the most effective and stable reagents were identified, and the research shifted toward combining the best materials with methods of physical impact. At that time, significant attention was paid to photocatalytic reactions that could be applied to hydrometallurgical technologies. This opened a new era in separating metals from solid and liquid sources of natural and artificial origin. Photocatalytic approaches were also widely used to address environmental challenges related to the degradation of additional reagents used in hydrometallurgical processes. These reagents include flotation reagents, extractants, and leaching solution components such as cyanide and thiosulfate ions, and are highly toxic pollutants of soil, air, and groundwater. In this review, we examine the use of photocatalytic reactions in hydrometallurgy and discuss key trends in the development of this industry from 2015 to 2026. The review covers different metals that can be most efficiently recovered using photocatalytic reactions. In addition, the challenges are considered related to degradation of additional hydrometallurgical reagents. The use of the photocatalytic approach enables to degrade flotation reagents such as xanthate, octadecylamine, and morpholine; extractants such as tributyl phosphate; and components of leaching solutions such as cyanide and thiosulfate ions. This review helps to assess which of the stateof-the-art hydrometallurgical technologies can be changed or significantly improved using a photocatalytic approach. The bibliography includes 179 references.
NMR spectroscopy of paramagnetic metal complexes was long considered a challenging area of research due to signal broadening and difficulties in spectral interpretation. However, modern theoretical and experimental developments have transformed this physicochemical method into an indispensable tool, particularly for the design of functional molecular materials. This review offers the first comprehensive view of paramagnetic NMR spectroscopy, combining a detailed analysis of the physical foundations and experimental techniques with a summary of modern theories and approaches. Particular attention is given to the method′s potential for establishing the structure, electronic structure, and magnetic properties of complexes, determining the parameters of magnetic interactions critical for the creation of single-molecule magnets, spin switches, and other precursors to future functional materials. The synergistic effect of combining NMR spectroscopy with magnetometry and EPR is emphasized, allowing one to overcome the problem of overparameterization and obtain reliable data on the electronic structure of the complex. The bibliography includes 157 references.
Despite the substantial progress in the understanding of bactericidal mechanisms and the development of novel antimicrobial strategies, infections remain a major threat for the humankind. It is symptomatic that antibiotic-resistant bacterial infections are now the third most common cause of death, being inferior only to stroke and coronary heart disease. Another increasingly serious threat is posed by fungal infections, especially for hospitalized patients with immunodeficiency or those who recover from COVID-19. The main feature of this review is that it provides a unified systematic view on the control of pathogenic microorganisms. The review begins with a historical account and setting of relevant tasks for innovative medical materials and proceeds with a profound analysis of fundamental mechanisms and advanced solutions. The analysis focuses on the key strategies for controlling bacterial and fungal infections, which are considered in detail in relation to metallic and polymeric biomaterials, inorganic nanoparticles and heterogeneous platforms based on them for local therapy. Particular attention is paid to factors that regulate the release of ions and therapeutic agents, generation of reactive oxygen species, and synergistic effects involved in these processes. The review also addresses the antibacterial mechanisms of action of nanoparticles and metal-containing complexes, nanoparticle toxicity and ways to minimize it, and bacterial defence mechanisms against ions and nanoparticles. The achievements of modern chemistry related to surface functionalization and immobilization of therapeutic agents aimed at developing highly effective antimicrobial surfaces are demonstrated. Critical analysis of drawbacks of the existing models for in vitro and in vivo assays of the antibacterial activity of biomaterials is given. The bibliography includes 361 references.
This review summarizes the latest advances in the chemistry of β,γ-ethylenic ketones, which have emerged over the last decade as valuable synthetic building blocks to create molecules of high complexity and diversity. This family of multifunctional γ-aryl-β,γ-ethylenic ketones has now become accessible owing to the discovery and systematic development of a new general C(sp3) – C(sp2) bond-forming reaction, namely superbase-mediated C-vinylation of ketones with alkynes. In the context of the Favorsky reaction (the addition of acetylenic carbanions to the carbonyl group of ketones), this discovery represents a chemical paradox in the form of temperaturecontrolled inversion of electrophilicity and nucleophilicity of acetylenes and ketones. Various transformations of β,γ-ethylenic ketones: nucleophilic addition reactions, inverse-electron-demand Diels–Alder reactions, reactions involving a carbonyl group followed by transformations of functionalized adducts, etc. are discussed. The review also highlights the cascade reactions, in which the in situ formed β,γ-ethylenic ketones, are key intermediates in the synthesis of various highly functionalized carbo- and heterocyclic systems. The bibliography includes 102 references.
