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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.

Developments in chemistry, materials science and biology have been fuelled by our search for structure–property relationships in matter at different levels of organization. Transformations in chemical synthesis and living systems predominantly take place in solution, such that many efforts have focused on studying nanoscale systems in the liquid phase. These studies have largely relied on spectroscopic data, the assignment of which can often be ambiguous. By contrast, electron microscopy can be used to directly visualize chemical systems and processes with up to atomic resolution. Electron microscopy is most amenable to studying solid samples and, until recently, to study a liquid phase, one had to remove solvent and lose important structural information. Over the past decade, however, liquid-phase electron microscopy has revolutionized direct mechanistic studies of reactions in liquid media. Scanning electron microscopy and (scanning) transmission electron microscopy of liquid samples have enabled breakthroughs in nanoparticle chemistry, soft-matter science, catalysis, electrochemistry, battery research and biochemistry. In this Review, we discuss the utility of liquid-phase electron microscopy for studying chemical reaction mechanisms in liquid systems. Liquid-phase electron microscopy is a powerful method for the direct, real-time monitoring of chemical processes on nanometre and micrometre scales. This Review describes the liquid-phase electron-microscopy techniques available to us and their application to studying chemical processes.

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.

Comprehensive studies dedicated to the search for specific properties of matter at the micro- and nanoscales have greatly enriched the fields of chemistry and materials science. From the point of view of synthetic chemistry, discoveries in the field of nanoscale catalysis, in which the size effects of active centers are used to accelerate the reactions, are of particular importance. However, another approach for the promotion of chemical transformations based on the micro- or nanoconfinement of reacting molecules or even on the structuring of the reaction media as a whole is gaining interest as a highly valuable tool. Herein, we highlight the example of an increase in the efficiency of phenol alkylation and tert-butylation of benzyl alcohol in reaction media based on ionic liquids by the creation of acidic microdomains in the presence of small molecule additives.

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...

Biomass-derived poly(ethylene-2,5-furandicarboxylate) (PEF) has been used for fused deposition modeling (FDM) 3D printing. A complete cycle from cellulose to the printed object has been performed. The printed PEF objects created in the present study show higher chemical resistance than objects printed with commonly available materials (acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), glycol-modified poly(ethylene terephthalate) (PETG)). The studied PEF polymer has shown key advantages for 3D printing: optimal adhesion, thermoplasticity, lack of delamination and low heat shrinkage. The high thermal stability of PEF and relatively low temperature that is necessary for extrusion are optimal for recycling printed objects and minimizing waste. Several successive cycles of 3D printing and recycling were successfully shown. The suggested approach for extending additive manufacturing to carbon-neutral materials opens a new direction in the field of sustainable development.

A catalytic system based on OX-1 metal–organic framework nanosheets is reported, incorporating catalytically active palladium (Pd) species. The Pd@OX-1 guest@host system is rapidly synthesized via a one-step single-pot supramolecular assembly, with the possibility of controlling the Pd loading. The structures of the resulting framework and of the active Pd species before and after catalytic reactions are studied in detail using a wide variety of techniques including synchrotron radiation infrared spectroscopy, inelastic neutron scattering, and X-ray absorption spectroscopy. Crystals of the resulting Pd@OX-1 composite material contain predominantly atomic and small cluster Pd species, which selectively reside on benzene rings of the benzenedicarboxylate (BDC) linkers. The composites are shown to efficiently catalyze the Suzuki coupling and Heck arylation reactions under a variety of conditions. Pd@OX-1 further shows potential to be recycled for at least five cycles of each reaction as well as an ability to recapture active Pd species during both catalytic reactions.

Real-time field-emission scanning electron microscopy (FE-SEM) measurements and neural network analysis were successfully merged to observe the temperature-induced behavior of soft liquid microdomains in mixtures of different ionic liquids with water. The combination of liquid FE-SEM and in situ heating techniques revealed temperature-driven solution restructuring for ions/water systems with different water states and their critical point behavior expressed in a rapid switch between thermal expansion and shrinkage of liquid microphases at temperatures of ≈100-130 °C, which was directly recorded on electron microscopy videos. Automation of FE-SEM video analysis by a neural network approach allowed quantification of the morphological changes in ions/water systems during heating on the basis of thousands of images processed with a speed almost equal to the frame rate of original electron microscopy videos. Tracking and evolution of the micro-heterogeneous domains, hypothesized in the Ioliomics concept, was mapped and quantified for the first time. The present study describes the concept for quick acquisition of big data in electron microscopy, develops rapid neural network analysis and shows how to link microscopic data to fundamental molecular properties.

Copper-oxide-catalyzed cross-coupling reaction is a well-known strategy in heterogeneous catalysis. A large number of applications have been developed, and catalytic cycles have been proposed based on the involvement of the copper oxide surface. In the present work, we have demonstrated that copper(I) and copper(II) oxides served as precursors in the coupling reaction between thiols and aryl halides, while catalytically active species were formed upon unusual leaching from the oxide surface. A powerful cryo-SEM technique has been utilized to characterize the solution-state catalytic system by electron microscopy. A series of different experimental methods were used to reveal the key role of copper thiolate intermediates in the studied catalytic reaction. The present study shows an example of leaching from a metal oxide surface, where the leaching process involved the formation of a metal thiolate and the release of water. A new synthetic approach was developed, and many functionalized sulfides were synthe...

Water-containing organic solutions are widespread reaction media in organic synthesis and catalysis. This type of multicomponent liquid system has a number of unique properties because of the tendency for water to self-organize in mixtures with other liquids. The characterization of these water domains is a challenging task because of their soft and dynamic nature. In the present study, the morphology and dynamics of micrometer- and nanometer-scale water-containing compartments in ionic liquids were directly observed by electron microscopy. A variety of morphologies, including isolated droplets, dense structures, aggregates, and 2D meshworks, have been experimentally detected and studied. Using the developed method, the impact of water on the acid-catalyzed biomass conversion reaction was studied at the microscopic level. The process that produced nanostructured domains in solution led to better yields and higher selectivities compared with reactions involving the bulk system.

Usual oxygen bases decompose M/NHC complexes to give “NHC-free” metal species and azolones., Numerous reactions are catalyzed by complexes of metals (M) with N-heterocyclic carbene (NHC) ligands, typically in the presence of oxygen bases, which significantly shape the performance. It is generally accepted that bases are required for either substrate activation (exemplified by transmetallation in the Suzuki cross-coupling), or HX capture (e.g. in a variety of C–C and C-heteroatom couplings, the Heck reaction, C–H functionalization, heterocyclizations, etc.). This study gives insights into the behavior of M(ii)/NHC (M = Pd, Pt, Ni) complexes in solution under the action of bases conventionally engaged in catalysis (KOH, NaOH, t-BuOK, Cs2CO3, K2CO3, etc.). A previously unaddressed transformation of M(ii)/NHC complexes under conditions of typical base-mediated M/NHC catalyzed reactions is disclosed. Pd(ii) and Pt(ii) complexes widely used in catalysis react with the bases to give M(0) species and 2(5)-oxo-substituted azoles via an O–NHC coupling mechanism. Ni(NHC)2X2 complexes hydrolyze in the presence of aqueous potassium hydroxide, and undergo the same O–NHC coupling to give azolones and metallic nickel under the action of t-BuOK under anhydrous conditions. The study reveals a new role of NHC ligands as intramolecular reducing agents for the transformation of M(ii) into “ligandless” M(0) species. This demonstrates that the disclosed base-mediated O–NHC coupling reaction is integrated into the catalytic M/NHC systems and can define the mechanism of catalysis (molecular M/NHC vs. “NHC-free” cocktail-type catalysis). A proposed mechanism of the revealed transformation includes NHC-OR reductive elimination, as implied by a series of mechanistic studies including 18O labeling experiments.

The liquid-phase hydrogenation of diphenylacetylene over Pd catalysts supported on Al2O3 with different specific surface areas has been investigated. A decrease in the specific surface area of the support leads to a marked increase in the selectivity of the reaction. The observed increase in the selectivity is due to the increase in the size of Pd0 nanoparticles. As a result, the specific rate of triple bond hydrogenation increases over the rate of the undesired hydrogenation of the olefinic intermediate and the efficiency of kinetic control over the selectivity of the overall process is enhanced.

In the present study state-of-the-art experimental techniques involving ultra high resolution SEM/STEM microscopy (1 Å resolution), high brilliance X-ray absorption spectroscopy and theoretical calculations on truly nanoscale systems were utilized to reveal the role of carbon centers in the formation and nature of Pd/C catalytic materials., Gaining insight into Pd/C catalytic systems aimed at locating reactive centers on carbon surfaces, revealing their properties and estimating the number of reactive centers presents a challenging problem. In the present study state-of-the-art experimental techniques involving ultra high resolution SEM/STEM microscopy (1 Å resolution), high brilliance X-ray absorption spectroscopy and theoretical calculations on truly nanoscale systems were utilized to reveal the role of carbon centers in the formation and nature of Pd/C catalytic materials. Generation of Pd clusters in solution from the easily available Pd2dba3 precursor and the unique reactivity of the Pd clusters opened an excellent opportunity to develop an efficient procedure for the imaging of a carbon surface. Defect sites and reactivity centers of a carbon surface were mapped in three-dimensional space with high resolution and excellent contrast using a user-friendly nanoscale imaging procedure. The proposed imaging approach takes advantage of the specific interactions of reactive carbon centers with Pd clusters, which allows spatial information about chemical reactivity across the Pd/C system to be obtained using a microscopy technique. Mapping the reactivity centers with Pd markers provided unique information about the reactivity of the graphene layers and showed that >2000 reactive centers can be located per 1 μm2 of the surface area of the carbon material. A computational study at a PBE-D3-GPW level differentiated the relative affinity of the Pd2 species to the reactive centers of graphene. These findings emphasized the spatial complexity of the carbon material at the nanoscale and indicated the importance of the surface defect nature, which exhibited substantial gradients and variations across the surface area. The findings show the crucial role of the structure of the carbon support, which governs the formation of Pd/C systems and their catalytic activity.

In the present review we describe the emerging tendency for creating target-oriented analytical approaches designed to solve important chemical tasks by using a combination of analytical tools. The concept is illustrated by selected examples of advances of NMR spectroscopy, mass spectrometry and electron microscopy in the analysis and study of gas-phase, liquid-state and solid-state chemical systems. Comparative description of chemical applications of these analytical methods is presented and discussed. The bibliography includes 359 references.

A new approach for the catalytic carbon–sulfur bond formation via cross-coupling reaction is reported. For the first time nano-structured nickel organosulfides [Ni(SAr)2] n were used as a source of SAr groups in catalytic cross-coupling reaction. A unique effect of morphology control of the reactivity of SAr groups in cross-coupling reaction was found. Synthesized nano-structured particles were characterized by field-emission scanning electron microscopy and their reactivity was studied by NMR in solution. Cross-coupling reaction with Cu catalyst was shown to proceed in the liquid phase and involve leaching, whereas the reaction with Pd catalyst is more complex and may involve both—homogeneous and heterogeneous pathways.

Magnetron sputtering was successfully used to obtain nanosized metal films and metal nanoparticles, which can be useful for development of novel methods in organic chemistry. The morphology of the nanosized (5–100 nm) objects obtained was examined by SEM. The pattern of dependence of the morphology and size of the nanosized objects on the nature of the support surface, the metal, and the sputtering conditions is described.

The great impact of the nanoscale organization of reactive species on their performance in chemical transformations creates the possibility of fine-tuning of reaction parameters by modulating the nano-level properties. This methodology is extensively applied for the catalysts development whereas nanostructured reactants represent the practically unexplored area. Here we report the palladium- and copper-catalyzed cross-coupling reaction involving nano-structured nickel thiolate particles as reagents. On the basis of experimental findings we propose the cooperative effect of nano-level and molecular-level properties on their reactivity. The high degree of ordering, small particles size, and electron donating properties of the substituents favor the product formation. Reactant particles evolution in the reaction is visualized directly by dynamic liquid-phase electron microscopy including recording of video movies. Mechanism of the reaction in liquid phase is established using on-line mass spectrometry measurements. Together the findings provide new opportunities for organic chemical transformations design and for mechanistic studies., Direct visualization and characterization of the influence of nanoscale organization on the reactivity of organic functional groups in solution remain a challenge. Here, the authors report the real-time observation of the involvement of a nanostructured reagent in a cross-coupling reaction using advanced liquid-phase electron microscopy.

Soluble gold precatalysts, aimed for homogeneous catalysis, under certain conditions may form nanoparticles, which dramatically change the mechanism and initiate different chemistry. The present study addresses the question of designing gold catalysts, taking into account possible interconversions and contamination at the homogeneous/heterogeneous system's interface. It was revealed that accurate localization of boundary experimental conditions for formation of molecular gold complexes in solution versus nucleation and growth of gold particles opens new opportunities for well-known gold chemistry. Within the developed concept, a series of practical procedures was created for efficient synthesis of soluble gold complexes with various phosphine ligands (R3P)AuCl (90-99% yield) and for preparation of different types of gold materials. The effect of the ligand on the particles growth in solution has been observed and characterized with high-resolution field-emission scanning electron microscopy (FE-SEM) study. Two unique types of nanostructured gold materials were prepared: hierarchical agglomerates and gold mirror composed of ultrafine smoothly shaped particles.