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A new family of protic ammonium ionic liquids (ILs) with various inorganic anions was synthesized from bio-derived 5-HMF. Starting with cellulose biomass, a complete preservation of the C₆ unit was achieved throughout the synthetic sequence (no carbon loss). Evaluation of green metrics showed a significant advantage of the developed bio-derived pathway to access ILs from a natural renewable source, depending on feasible routes to 5-HMF manufacturing. The reduced number of synthetic steps and availability of the starting materials were the key advantages. Experimental physicochemical and biological studies, as well as computational modeling revealed a unique multifunctional intrinsic organization of these bio-derived ILs. The nature of interactions between the cations and anions of the novel ILs was mapped at the molecular level. The substituents in the cationic core and the nature of the original building blocks had a prominent impact on cytotoxicity of the novel ILs. The obtained results suggest possible sustainable applications of the least toxic ILs, while the regulation of biological activity of the ILs via the corresponding structural adjustments can find biological and medicinal applications. The 5-HMF-derived IL with a sulfate anion demonstrated potentially useful properties in dissolution of microcrystalline cellulose.

In this Essay, we present a critical analysis of two common practices in modern chemistry-that is, of using speculations about the "greenness" and "nontoxicity" of developed synthesis procedures and of a priori labelling various compounds derived from natural sources as being environmentally safe. We note that every organic molecule that contains functional groups should be biologically active. Thus, analysis of the particular greenness and the potential environmental impact of a given chemical process should account for the biological activity of all its components in a measureable (rather than empirical) way. We highlight the necessity of clarifying discussions on biological activity and toxicity and propose possible ways of introducing tox-Profiles as a reliable overview of the overall toxicity of chemical reactions.

We introduce new quantitative environmental metrics - "cytotoxicity potentials" - which can be used for the preliminary evaluation of the safety of chemical reactions from the viewpoint of the cytotoxicity of their components. We also elaborate the concept of bio-Profiles to be employed for fast estimation of the potential environmental dangers of chemical processes by (1) including the common cytotoxicity scale for all routes of synthesis of a particular product and (2) proposing a novel, more compact representation of the bio-Profiles themselves in the form of bio-Strips. These improvements allow direct comparisons of various synthetic routes for a particular target product, thus providing faster assessment of the reactions in question from the viewpoint of their "overall cytotoxicity". The advantages of these developments are illustrated by 36 routes of synthesizing 1,1'-biphenyl and 72 routes of synthesizing 4-methoxy-1,1'-biphenyl. The effect of incomplete conversion on bio-Strips and their metrics is also discussed. In addition, we address the impact of the selection of a particular cell line on the evaluation of the reaction safety by comparing the results obtained in three cell lines of various origins.

The CSDB Linear notation for carbohydrate sequences utilized in the Carbohydrate Structure Database (CSDB) has been improved to meet modern requirements in glycoinformatics. The new features include: the possibility to combine repeating and nonrepeating moieties in one structure; support of carbon-carbon bonds; and usage of SMILES encodings for unambiguous chemical description of glycan structures, including aglycons and atypical components. The new capabilities of CSDB Linear, together with the older ones, allow efficient detection of errors in CSDB and, at the same time, ensure the absence of informatic problems common for human-readable notations. The CSDB Linear implementation provides translation to other carbohydrate notations and multiple procedures for content error checking.

Until recently, chemical derivatives of platinum group metals have not been in a systematic direct contact with living organisms. The situation has changed dramatically due to anthropogenic activity, which has led to significant redistribution of these metals in the biosphere. Millions of modern cars are equipped with automotive catalytic converters, which contain rhodium, palladium and platinum as active elements. Everyday usage of catalytic technologies promotes the propagation of catalyst components in the environment. Nevertheless, we still have not accumulated profound information on possible ecotoxic effects of these metal pollutants. In this study, we report a case of an extraordinarily rapid development of lethal toxicity of a rhodium (III) salt in the terrestrial plants Pisum sativum, Lupinus angustifolius and Cucumis sativus. The growth stage, at which the exposure occurred, had a crucial impact on the toxicity manifestation: at earlier stages, RhCl3 killed the plants within 24 h. In contrast, the salt was relatively low-toxic in human fibroblasts. We also address phytotoxicity of other common metal pollutants, such as palladium, iron, nickel and copper, together with their cytotoxicity. None of the tested compounds exhibited phytotoxic effects comparable with that of RhCl3. These results evidence the crucial deficiency in our knowledge on environmental dangers of newly widespread metal pollutants.

Inorganic and organic "solvent-in-salt" (SIS) systems have been known for decades but have attracted significant attention only recently. Molten salt hydrates/solvates have been successfully employed as non-flammable, benign electrolytes in rechargeable lithium-ion batteries leading to a revolution in battery development and design. SIS with organic components (for example, ionic liquids containing small amounts of water) demonstrate remarkable thermal stability and tunability, and present a class of admittedly safer electrolytes, in comparison with traditional organic solvents. Water molecules tend to form nano- and microstructures (droplets and channel networks) in ionic media impacting their heterogeneity. Such microscale domains can be employed as microreactors for chemical and enzymatic synthesis. In this review, we address known SIS systems and discuss their composition, structure, properties and dynamics. Special attention is paid to the current and potential applications of inorganic and organic SIS systems in energy research, chemistry and biochemistry. A separate section of this review is dedicated to experimental methods of SIS investigation, which is crucial for the development of this field.

Storage and handling of toxic wastes is a top-priority challenge for sustainable development and public health. In recent years, the risk of irreversible environmental pollution has been increasing gradually, necessitating the development of new concepts in this highly demanding area. Here, we report a flexible approach to address the problem using tunable ionic liquids as a carrier and storage medium for chemicals. Encapsulation in microscale tunable media surrounded by an inert ionic liquid facilitates the efficient capture of chemicals. The adaptive character of the designed microscale compartments opens new possibilities for the waste management of chemicals of a diverse nature. Real-time field-emission scanning electron microscopy was used to visualize the formation of microscale compartments upon the sequestration of chemicals in ionic liquids. Ionic liquids captured the chemicals better than traditional organic solvents or water; moreover, the chemicals subsequently could be effectively extracted f...

Ionic liquids are remarkable chemical compounds, which find applications in many areas of modern science. Because of their highly tunable nature and exceptional properties, ionic liquids have become essential players in the fields of synthesis and catalysis, extraction, electrochemistry, analytics, biotechnology, etc. Apart from physical and chemical features of ionic liquids, their high biological activity has been attracting significant attention from biochemists, ecologists, and medical scientists. This Review is dedicated to biological activities of ionic liquids, with a special emphasis on their potential employment in pharmaceutics and medicine. The accumulated data on the biological activity of ionic liquids, including their antimicrobial and cytotoxic properties, are discussed in view of possible applications in drug synthesis and drug delivery systems. Dedicated attention is given to a novel active pharmaceutical ingredient-ionic liquid (API-IL) concept, which suggests using traditional drugs in the form of ionic liquid species. The main aim of this Review is to attract a broad audience of chemical, biological, and medical scientists to study advantages of ionic liquid pharmaceutics. Overall, the discussed data highlight the importance of the research direction defined as "Ioliomics", studies of ions in liquids in modern chemistry, biology, and medicine.

Glycoinformatics is an actively developing scientific discipline, which provides scientists with the means of access to the data on natural glycans and with various tools of their processing. However, the informatization of glycomics has a long way to go before catching up with genomics and proteomics. In this Viewpoint, we review the current situation in glycoinformatics and discuss its achievements and shortcomings, emphasizing the major drawbacks: the lack of recognized standards, protocols, data indices and tools, and the informational isolation of the existing projects. We reiterate possible solutions of the persistent issues and describe our vision of an ideal glycoinformatics project.

Carbohydrate Structure Database (CSDB) is a regularly updated database containing structural, taxonomic, bibliographic, NMR spectroscopic, and other information on carbohydrates and their derivatives obtained from prokaryotes, plants, and fungi. CSDB claims for full coverage and high data quality. It serves as a platform for various search strategies, tools for NMR spectrum and structure prediction, and instruments for statistical analysis. CSDB is freely available via the Internet at http://csdb.glycoscience.ru.

The extraction of peptides was studied in a two-phase ionic liquid (IL)/organic solvent system, which displayed outstanding chain length sensitivity (dipeptide vs tripeptide) and separation ability, even for structurally similar peptides (divaline vs dialanine). The extraction process could be performed under substoichiometric conditions; an IL-to-peptide ratio as low as 3:1 led to a high extraction selectivity of divaline/dialanine = 6. For practical applications, two systems were developed for the extraction of peptides from ILs under heterogeneous and homogeneous conditions, with selectivities of 6 and 3.5, respectively. The developed system has shown excellent recycling properties and was reused several times without any visible changes in the selectivity and extraction efficiency. A nuclear magnetic resonance (NMR) experiment with molecular-level spatial resolution was successfully performed to study the mechanism of the extraction process and to visualize the two-phase system.

Carbohydrates play an immense role in different aspects of life. NMR spectroscopy is the most powerful tool for investigation of these compounds. Nowadays, progress in computational procedures has opened up novel opportunities giving an impulse to the development of new instruments intended to make the research simpler and more efficient. In this paper, we present a new approach for simulating (13)C NMR chemical shifts of carbohydrates. The approach is suitable for any atomic observables, which could be stored in a database. The method is based on sequential generalization of the chemical surroundings of the atom under prediction and heuristic averaging of database data. Unlike existing applications, the generalization scheme is tuned for carbohydrates, including those containing phosphates, amino acids, alditols, and other non-carbohydrate constituents. It was implemented in the Glycan-Optimized Dual Empirical Spectrum Simulation (GODESS) software, which is freely available on the Internet. In the field of carbohydrates, our approach was shown to outperform all other existing methods of NMR spectrum prediction (including quantum-mechanical calculations) in accuracy. Only this approach supports NMR spectrum simulation for a number of structural features in polymeric structures.

Environmental profiles for the selected metals were compiled on the basis of available data on their biological activities. Analysis of the profiles suggests that the concept of toxic heavy metals and safe nontoxic alternatives based on lighter metals should be re-evaluated. Comparison of the toxicological data indicates that palladium, platinum, and gold compounds, often considered heavy and toxic, may in fact be not so dangerous, whereas complexes of nickel and copper, typically assumed to be green and sustainable alternatives, may possess significant toxicities, which is also greatly affected by the solubility in water and biological fluids. It appears that the development of new catalysts and novel applications should not rely on the existing assumptions concerning toxicity/nontoxicity. Overall, the available experimental data seem insufficient for accurate evaluation of biological activity of these metals and its modulation by the ligands. Without dedicated experimental measurements for particular metal/ligand frameworks, toxicity should not be used as a "selling point" when describing new catalysts.

Systematization and classification of carbohydrates contribute greatly to development of modern biomedical sciences. CCSD (CarbBank) data constitute the significant part of nearly all existing carbohydrate databases. However, these data have not been verified from their original deposit. During the expansion of Bacterial Carbohydrate Structure Database (BCSDB) project, we checked CCSD data quality and found that about 35% of records contained errors. The CCSD data cannot be used without manual verification, while CCSD errors migrate from database to database.