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Dimeric 5-HMF derivatives have been used in a cascade 2 × [4 + 2] cycloaddition reaction with alkynes leading to a drastic increase in molecular complexity. The reaction proceeds under thermodynamic control, diastereoselectively and regioselectively.

The interaction between diphenylacetylene and dichlorophenylphosphine under various conditions is a simple method for the preparation of pentaphenylphosphole derivatives exhibiting fluorescence properties.

A simple methodology for testing FFF parts was developed to examine key factors for chemical applications. Carbon-filled polyamide (PA6-CF) was found superior for digital design of chemical reactors due to advantageous combination of properties.

The reaction space of the furanics-to-aromatics (F2A) conversion process for 5-hydroxymethylfurfural (HMF)-based platform chemicals has been explored both experimentally and by quantum chemistry methods. For the first time, a structure-activity relationship was established in furan-yne cycloaddition for a number of different HMF derivatives. Correlations between the activation energy of the cycloaddition stage and the structure of the substrates were established by molecular modeling methods. Analysis of the concerted and stepwise mechanisms of cycloaddition in the singlet and triplet electronic states of the molecular system was carried out. A series of biobased 7-oxanorbornadienes was obtained in the reaction with dimethyl acetylenedicarboxylate. Various methods of aromatization of the obtained [4+2] adducts have been examined. Rearrangement catalyzed by a Lewis acid leads to the formation of a phenol derivative, whereas reduction by diiron nonacarbonyl leads to the formation of functionalized benzene. Systematic study of the cycloaddition process has revealed a simple way to analyze and predict the relative reactivity of furanic substrates.

Smoothness/defectiveness of the carbon material surface is a key issue for many applications, spanning from electronics to reinforced materials, adsorbents and catalysis. Several surface defects cannot be observed with conventional analytic techniques, thus requiring the development of a new imaging approach. Here, we evaluate a convenient method for mapping such “hidden” defects on the surface of carbon materials using 1–5 nm metal nanoparticles as markers. A direct relationship between the presence of defects and the ordering of nanoparticles was studied experimentally and modeled using quantum chemistry calculations and Monte Carlo simulations. An automated pipeline for analyzing microscopic images is described: the degree of smoothness of experimental images was determined by a classification neural network, and then the images were searched for specific types of defects using a segmentation neural network. An informative set of features was generated from both networks: high-dimensional embeddings of image patches and statics of defect distribution., Defectiveness of carbon material surface is a key issue for many applications. Pd-nanoparticle SEM imaging was used to highlight “hidden” defects and analyzed by neural networks to solve order/disorder classification and defect segmentation tasks.

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.

Complexes of Pd(II) with NHC ligands can suffer facile decomposition in the presence of alkali metal hydroxides, alkoxydes and other strong oxygen-containing bases via the reductive elimination of the NHC and Pd-coordinated base anion, the so-called O–NHC coupling. O–NHC coupling can represent a serious problem for the stability of Pd/NHC catalytic systems in numerous practically important reactions conducted in the presence of bases. In the present study, a new approach to stabilizing the Pd–NHC bond against cleavage by strong bases was developed. The approach relies on the installation of an NH–acidic RNH substituent at position 3 of the triazole ring of the 1,2,4-triazol-5-ylidene ligand. A series of new Pd/NHCs containing RNH substituents (R = Ac, Ph, alkyl) in triazole NHC ligands were synthesized. These complexes undergo reversible deprotonation of the RNH group in strong alkaline media and demonstrate superior stability of the Pd–NHC bond, significantly higher than complexes of similar structure without the RNH group. DFT calculations revealed that the anionic Pd/NHC complex containing an N-deprotonated acetamido group (R = Ac) is more kinetically stable against O–NHC coupling and less prone to lose NHC via heterolytic dissociation of the Pd–NHC bond than the neutral complex. The new complexes with RNH-functionalized NHC ligands were tested as precatalysts in the Suzuki–Miyaura coupling of p-tolyl bromide with phenylboronic acid in the presence of KOH and revealed more than 2 times higher TONs than similar complexes without the RNH group or ligandless Pd system.

The ability to distinguish molecular catalysis from nanoscale catalysis provides a key to success in the field of catalyst development, particularly for the transition to sustainable economies. Complex evolution of catalyst precursors, facilitated by dynamic interconversions and leaching, makes the identification of catalytically active forms an important task, which is sometimes very difficult. We propose a simple method for in situ capturing of nanoparticles with carbon-coated grids directly from reaction mixtures. Application of this method to the Mizoroki-Heck reaction allowed visualization of dynamic changes of the dominant form of palladium particles in the reaction mixtures with homogeneous and heterogeneous catalyst precursors. Changes in the size and shape of the palladium particles reflecting the progress of the catalytic chemical reaction were demonstrated. Detailed computational modeling was carried out to confirm the generality of this approach and its feasibility for different catalytic systems. The computational models revealed strong binding of metal particles to the carbon coating comprising efficient binding sites. The approach was tested for trapping Cr, Co, Ag, Ni, Cu, Pd, Cd, Ir, Ru and Rh nanoparticles from solutions containing micromolar starting concentrations of the metal precursors. The developed approach provides a unique tool for studying intrinsic properties of catalytic systems.

Representative examples of the application of 3D printing in organic synthesis, biochemistry, biotechnology, analytical chemistry, pharmaceutics and chemical education are considered. It is shown that additive technologies open up new prospects for the development of these fields of science. The characteristics of widely used 3D printing methods (fused deposition modelling and stereolithography) are discussed in the context of chemical applications. It is noted that the key feature of these methods is the wide accessibility of technologies and materials. The bibliography includes 498 references.

Catalytic atom-economic hydrothiolation of cyclopropyl acetylenes was developed. Using Pd/NHC complex as a precatalyst, regioselective addition of thiols to cyclopropyl acetylenes was successfully ...

In recent years, the topic of catalysis by carbon materials (carbocatalysis) has experienced rapid growth. Every year the scope of application of carbocatalysts is expanding swiftly, spreading to areas in which metal catalysts seemed to have no alternative until recently. Due to their structural diversity and functionalization possibilities, carbon materials offer almost limitless possibilities for creating various catalytically active sites. It is of crucial importance to understand the mechanisms of action of chemically active sites of carbocatalysts for the development of this field. The latest discoveries have unveiled the complexity of this topic and the need to take into account the effects associated with the simultaneous presence of various active sites on the surface of carbon materials. Despite the significant advances in modern research in the field of carbocatalysis, it is important to remember the origins of the use of carbon materials in catalysis. New methods of studying old and almost forgotten reactions often lead to very interesting discoveries. This review focuses on the historical development of ideas about the catalytic activity of carbon materials, modern concepts of the mechanisms of carbocatalytic reactions, and recent studies of the role of carbene centers of graphene materials in catalytic processes.

Development of sustainable catalysts for synthetic transformations is one of the most challenging and demanding goals. The high prices of precious metals and the unavoidable leaching of toxic metal species leading to environmental contamination make the transition metal-free catalytic systems especially important. Here we demonstrate that carbene active centers localized on carbon atoms at the zigzag edge of graphene represent an alternative platform for efficient catalytic carbon-carbon bond formation in the synthesis of benzene. The studied acetylene trimerization reaction is an efficient atom-economic route to build an aromatic ring-a step ubiquitously important in organic synthesis and industrial applications. Computational modeling of the reaction mechanism reveals a principal role of the reversible spin density oscillations that govern the overall catalytic cycle, facilitate the product formation, and regenerate the catalytically active centers. Dynamic π-electron interactions in 2D carbon systems open new opportunities in the field of carbocatalysis, unachievable by means of transition metal-catalyzed transformations. The theoretical findings are confirmed experimentally by generating key moieties of the carbon catalyst and performing the acetylene conversion to benzene.

The development of new drugs is accelerated by rapid access to functionalized and D-labeled molecules with improved activity and pharmacokinetic profiles. Diverse synthetic procedures often involve the usage of gaseous reagents, which can be a difficult task due to the requirement of a dedicated laboratory setup. Here, we developed a special reactor for the on-demand production of gases actively utilized in organic synthesis (C2H2, H2, C2D2, D2, and CO2) that completely eliminates the need for high-pressure equipment and allows for integrating gas generation into advanced laboratory practice. The reactor was developed by computer-aided design and manufactured using a conventional 3D printer with polypropylene and nylon filled with carbon fibers as materials. The implementation of the reactor was demonstrated in representative reactions with acetylene, such as atom-economic nucleophilic addition (conversions of 19–99%) and nickel-catalyzed S-functionalization (yields 74–99%). One of the most important advantages of the reactor is the ability to generate deuterated acetylene (C2D2) and deuterium gas (D2), which was used for highly significant, atom-economic and cost-efficient deuterium labeling of S,O-vinyl derivatives (yield 68–94%). Successful examples of their use in organic synthesis are provided to synthesize building blocks of heteroatom-functionalized and D-labeled biologically active organic molecules.

The processes involving the capture of free radicals were explored by performing DFT molecular dynamics simulations and modeling of reaction energy profiles. We describe the idea of a radical recognition assay, where not only the presence of a radical but also the nature/reactivity of a radical may be assessed. The idea is to utilize a set of radical-sensitive molecules as tunable sensors, followed by insight into the studied radical species based on the observed reactivity/selectivity. We utilize this approach for selective recognition of common radicals—alkyl, phenyl, and iodine. By matching quantum chemical calculations with experimental data, we show that components of a system react differently with the studied radicals. Possible radical generation processes were studied involving model reactions under UV light and metal-catalyzed conditions.

It has recently been shown that palladium-catalyzed reactions with N-heterocyclic carbene (NHC) ligands involve R-NHC coupling accompanied by transformation of the molecular catalytic system into the nanoscale catalytic system. An important question appeared in this regard is whether such a change in the catalytic system is irreversible. More specifically, is the reverse nano-to-molecular transformation possible? In view of the paramount significance of this question to the area of catalyst design, we studied the capability of 2-substituted azolium salts to undergo the breakage of C-C bond and exchange substituents on the carbene carbon with corresponding aryl halides in the presence of Pd nanoparticles. The study provides important experimental evidence of possibility of the reversible R-NHC coupling. The observed behavior indicates that the nanosized metal species are capable of reverse transition to molecular species. Such an option, known for phosphine ligands, was previously unexplored for NHC ligands. The present study for the first time demonstrates bidirectional dynamic transitions between the molecular and nanostructured states in Pd/NHC systems. As a unique feature, surprisingly small activation barriers (18 kcal/mol) and noticeable thermodynamic driving force (-5 to -7 kcal/mol) were calculated for C-C bond oxidative addition to Pd(0) centers in the studied system. The first example of NHC-mediated Pd leaching from metal nanoparticles to solution was observed and formation of Pd/NHC complex in solution was detected by ESI-MS.

Magnetic stir bars are routinely used by every chemist doing synthetic or catalytic transformations in solution. Each bar lasts for months or years, as the regular PTFE (polytetrafluoroethylene) co...

The present article describes a conceptual view on the design of reusable bioderived high-value-added materials. The translation of a highly complex irregular structure of natural biopolymer into a well-defined hierarchically organized molecular chain led to the discovery of unique adhesive properties enhanced by a novel multiple binding effect. For practical applications, biomass-derived furanic polyesters were found as reusable thermoplastic adhesives. Examined poly(ethylene-2,5-furandicarboxylate) (PEF) and poly(hexamethylene-2,5-furandicarboxylate) (PHF) showed strong adhesion to aluminum in single-lap shear tests (1.47 ± 0.1 and 1.18 ± 0.1 kN/cm2, respectively). After the separation, the joints could be easily restored by reheating of the metal parts. Three consecutive cycles of regluing were successfully performed without a significant drop in the adhesive strength. Strong adhesion of the biomass-derived polymers to glass surfaces was also observed (0.93 ± 0.11 kN/cm2 for PEF and 0.84 ± 0.06 kN/cm2 for PHF). An in-depth study of the surfaces after the shear tests, carried out by means of scanning electron microscopy, revealed predominantly cohesive failure in the case of aluminum samples and adhesive failure in the case of glass samples. Computational modeling revealed a multiple oxygen binding mode for the interaction of furanic polyester molecules with the glass surface and metal atoms. Only sustainable materials were used as a carbon source for the production of target polymers, which showed excellent compatibility with the practically most demanding constructing materials (a universal reusable hot-melt adhesive for copper, brass, Be-copper, Mn-bronze, zinc, aluminum, titanium, and glass).

An associative electron upconversion is proposed as a key step determining the selectivity of thiol–yne coupling. The developed synthetic approach provided an efficient tool to access a comprehensive range of products – four types of vinyl sulfides were prepared in high yields and selectivity. We report practically important transition-metal-free regioselective thiol–yne addition and formation of the demanding Markovnikov-type product by a radical photoredox process. The photochemical process was directly monitored by mass-spectrometry in a specially designed ESI-MS device with green laser excitation in the spray chamber. The proposed reaction mechanism is supported by experiments and DFT calculations., An associative electron upconversion is proposed as a key step determining the selectivity of the thiol–yne coupling.

A well-established oxidative addition of organic halides (R-X) to N-heterocyclic carbene (NHC) complexes of palladium(0) leads to formation of (NHC)(R)PdII (X)L species, the key intermediates in a large variety of synthetically useful cross-coupling reactions. Typical consideration of the cross-coupling catalytic cycle is based on the assumption of intrinsic stability of these species, where the subsequent steps involve coordination of the second reacting partner. Thus, high stability of the intermediate (NHC)(R)PdII (X)L species is usually taken for granted. In the present study it is discussed that such intermediates are prone to non-classical R-NHC intramolecular coupling process (R = Me, Ph, Vinyl, Ethynyl) that results in removal of NHC ligand and generation of another type of Pd catalytic system. DFT calculations (BP86, TPSS, PBE1PBE, B3LYP, M06, wB97X-D) clearly show that outcome of R-NHC coupling process is not only determined by chemical nature of the organic substituent R, but also strongly depends on the type of solvent. The reaction is most favorable in polar solvents, whereas the non-polar solvents render the products less stable. © 2019 Wiley Periodicals, Inc.

This work reveals ambident nucleophilic reactivity of imidazolium cations towards carbonyl compounds at the C2 or C4 carbene centers depending on the steric properties of the substrates and reaction conditions. Such an adaptive behavior indicates the dynamic nature of organocatalysis proceeding via a covalent interaction of imidazolium carbenes with carbonyl substrates and can be explained by generation of the H-bonded ditopic carbanionic carbenes.

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.

The direct vinylation of an OH group in alcohols and phenols was carried out utilizing a novel CaC2/KF solid acetylene reagent in a simple K2CO3/KOH/DMSO system. The functionalization of a series of hydroxyl-group-containing substrates and the post-modification of biologically active molecules were successfully performed using standard laboratory equipment, providing straightforward access to the corresponding vinyl ethers. The overall process developed involves an atom-economical addition reaction employing only inorganic reagents, which significantly simplifies the reaction set-up and the isolation of products. A mechanistic study revealed a dual role of the F− additive, which both mediates the surface etching/renewal of the calcium carbide particles and activates the CC bond towards the addition reaction. The development of the fluoride-mediated nucleophilic addition of alcohols eliminates the need for strong bases and may substantially extend the areas of application of this attractive synthetic methodology due to increasing functional group tolerance. As a replacement for dangerous and difficult to handle high-pressure acetylene, we propose the solid reagent CaC2/KF, which is easy to handle, does not require dedicated laboratory equipment and demonstrates enhanced reactivity of the acetylenic triple bond. Theoretical calculations have shown that fluoride-mediated activation of the hydroxyl group towards nucleophilic addition significantly reduces the activation barrier and facilitates the reaction.

The first synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described. The Diels–Alder reaction was used to implement the transition from HMF to a non-planar framework, which possessed structural cores of naturally occurring biologically active compounds and building blocks of advanced materials. A one-pot, three-step sustainable synthesis in water was developed starting directly from HMF. The reduction of HMF led to 2,5-bis(hydroxymethyl)furan (BHMF), which could be readily involved in the Diels–Alder cycloaddition reaction with HMF-derived maleimide, followed by hydrogenation of the double bond. The described transformation was diastereoselective and proceeded with a good overall yield. The applicability of the chosen approach for the synthesis of analogous structures containing amine functionality on the side chain was demonstrated. To produce the target compounds, only platform chemicals were used with carbohydrate biomass as the single carbon source.

A thermally induced cascade process leading to the formation of stable micro- and nanometer-size phosphoric droplets was developed starting from a molecular precursor. Microwave-induced pyrolysis of 1,2,3,4,5-pentaphenylphosphole oxide proceeded through a series of subsequent transformations involving formation of phosphorus-doped graphene oxide layers, seeding of carbon surface with phosphorus centers, and assembling of stable droplets. A complex nanostructured organization of the material was established in a remarkably short time of 3 min, and the process was performed in a thermally induced manner using microwave irradiation. High stability of the liquid phosphoric structures on the surface of doped graphene oxide over a few-month period was demonstrated, as well as under challenging conditions in organic solvents (chloroform, methylene chloride, or toluene media) and even under sonication. Detailed examination of this material by electron microscopy and a number of analytical methods showed its unique organization at the nanoscale, whereas computational modeling revealed unusually strong binding of phosphorus oxide P

The possibility of rapid manufacturing of customized chemical labware and reactionware by three-dimensional (3D) printing is discussed. The advantages and disadvantages of this approach to the design of chemical equipment from different engineering plastics were demonstrated and the suitability of some materials for chemical applications was estimated: PP > PLA > > ABS > PETG (PP is polypropylene, PLA is polylactide, ABS is acrylonitrile butadiene styrene, and PETG is polyethylene terephthalate glycol). The procedure described is a powerful tool for the production of both typical and unique chemical labware; to date, the fused deposition modeling (FDM) method is already available for the everyday use in chemical laboratories. The examples of successful application of 3D-printed products were demonstrated: solvent resistance and impermeability were assessed, as well as Pd(OAc)2-catalyzed cross-coupling between p-bromotoluene and phenylboronic acid and Ni(acac)2-catalyzed hydrothiolation of alkyne with thiophenol were performed.

A novel synthetic methodology for the preparation of 1,3-disubstituted pyrazoles from in situ generated nitrile imines and acetylene is reported. The reactions are performed in a simple two-chamber reactor. One part of the reactor is loaded with hydrazonoyl chloride precursors of active nitrile imine species and a base. The other part is used to generate acetylene from CaC2 and water. Partitioning of the reactants improves the yields of desired pyrazoles up to 99% and simplifies their isolation to a simple procedure of solvent evaporation. The approach requires no complex equipment and utilizes inexpensive, safe, and easy to handle calcium carbide as a starting material. A model deuterium incorporation is carried out according to the developed methodology, producing a series of novel 4,5-dideuteropyrazoles with excellent deuterium enrichment. Theoretical calculations on reaction mechanism and characterization of possible intermediate structures were performed.

Vinyl sulfides represent an important class of compounds in organic chemistry and materials science. Atom-economic addition of thiols to the triple bond of alkynes provides an excellent opportunity for environmentally friendly processes. We have found that well-known and readily available Pd-NHC complex (IMes)Pd(acac)Cl is an efficient catalyst for alkyne hydrothiolation. The reported technique provides a general one-pot approach for the selective preparation of Markovnikov-type vinyl sulfides starting from tertiary, secondary, or primary aliphatic thiols, as well as benzylic and aromatic thiols. In all the studied cases, the products were formed in excellent selectivity and good yields.

The experimental study of dechlorination activity of a Au/Ag bimetallic system has shown formation of a variety of chlorinated bimetallic Au/Ag clusters with well-defined Au:Ag ratios from 1:1 to 4:1. It is the formation of the Au/Ag cluster species that mediated C–Cl bond breakage, since neither Au nor Ag species alone exhibited a comparable activity. The nature of the products and the mechanism of dechlorination were investigated by ESI-MS, GC-MS, NMR, and quantum chemical calculations at the M06/6-311G(d)&SDD level of theory. It was revealed that formation of bimetallic clusters facilitated dechlorination activity due to the thermodynamic factor: C–Cl bond breakage by metal clusters was thermodynamically favored and resulted in the formation of chlorinated bimetallic species. An appropriate Au:Ag ratio for an efficient hydrodechlorination process was determined in a joint experimental and theoretical study carried out in the present work. This mechanistic finding was followed by synthesis of molecular ...

Microwave irradiation of Ni, Co, Cu, Ag, and Pt metal salts supported on graphite and charcoal revealed a series of carbon surface modification processes that varied depending on the conditions used (inert atmosphere, vacuum, or air) and the nature of metal salt. Carbon materials, routinely used to prepare supported metal catalysts and traditionally considered to be innocent on this stage, were found to actively change under the studied conditions: etching and pitting of the carbon surface by metal particles as well as growth of carbon nanotubes were experimentally observed by FE-SEM analysis. Catalyst preparation under microwave irradiation led to the formation of complex metal/carbon structures with significant changes in carbon morphology. These findings are of great value in developing an understanding of how M/C catalysts form and evolve and will help to design a new generation of efficient and stable catalysts. The energy surfaces of carbon support modification processes were studied with theoretica...

Graphene can efficiently shield chemical interactions and gradually decrease the binding to reactive defect areas. In the present study, we have used the observed graphene shielding effect to control the reactivity patterns on the carbon surface. The experimental findings show that a surface coating with a tiny carbon layer of 1-2 nm thickness is sufficient to shield the defect-mediated reactivity and create a surface with uniform binding ability. The shielding effect was directly observed using a combination of microscopy techniques and evaluated with computational modeling. The theoretical calculations indicate that a few graphene layers can drastically reduce the binding energy of the metal centers to the surface defects by 40-50 kcal mol(-1). The construction of large carbon areas with controlled surface reactivity is extremely difficult, which is a key limitation in many practical applications. Indeed, the developed approach provides a flexible and simple tool to change the reactivity patterns on large surface areas within a few minutes.

A new efficient approach was developed for the synthesis of aromatic and heteroaromatic compounds based on [4 + 2] cycloaddition of unsubstituted and heteroatom-substituted alkyne and enyne units. The developed approach provides a practical Green chemical route to several types of important bicyclic products (indane, cyclopentapyridines, indole, isoindole, indolizine, isophosphindole, benzofuran, benzothiophene, benzoselenophene and corresponding dihydro derivatives) starting from simple linear compounds. The mechanism of the reactions was revealed by theoretical calculations using different methods, including CCSD(T) and MP4(SDTQ) for energy calculations and B3LYP, M052X, B3PW91, BLYP and MP2 levels for evaluation of molecular structures.

Additive manufacturing with fused deposition modeling (FDM) is currently optimized for a wide range of research and commercial applications. The major disadvantage of FDM-created products is their low quality and structural defects (porosity), which impose an obstacle to utilizing them in functional prototyping and direct digital manufacturing of objects intended to contact with gases and liquids. This article describes a simple and efficient approach for assessing the quality of 3D printed objects. Using this approach it was shown that the wall permeability of a printed object depends on its geometric shape and is gradually reduced in a following series: cylinder > cube > pyramid > sphere > cone. Filament feed rate, wall geometry and G-code-defined wall structure were found as primary parameters that influence the quality of 3D-printed products. Optimization of these parameters led to an overall increase in quality and improvement of sealing properties. It was demonstrated that high quality of 3D printed objects can be achieved using routinely available printers and standard filaments.

Experimental and theoretical investigation of the regiodivergent palladium-catalyzed dimerization of terminal alkynes is presented. Employment of N-heterocyclic carbene-based palladium catalyst in the presence of phosphine ligand allows for highly regio- and stereoselective head-to-head dimerization reaction. Alternatively, addition of carboxylate anion to the reaction mixture triggers selective head-to-tail coupling. Computational studies suggest that reaction proceeds via the hydropalladation pathway favoring head-to-head dimerization under neutral reaction conditions. The origin of the regioselectivity switch can be explained by the dual role of carboxylate anion. Thus, the removal of hydrogen atom by the carboxylate directs reaction from the hydropalladation to the carbopalladation pathway. Additionally, in the presence of the carboxylate anion intermediate, palladium complexes involved in the head-to-tail dimerization display higher stability compared to their analogues for the head-to-head reaction.

A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reac-tion was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation.

Experimental and theoretical investigation of the regiodivergent palladium-catalyzed dimerization of terminal alkynes is presented. Employment of N-heterocyclic carbene-based palladium catalyst in the presence of phosphine ligand allows for highly regio- and stereoselective head-to-head dimerization reaction. Alternatively, addition of carboxylate anion to the reaction mixture triggers selective head-to-tail coupling. Computational studies suggest that reaction proceeds via the hydropalladation pathway favoring head-to-head dimerization under neutral reaction conditions. The origin of the regioselectivity switch can be explained by the dual role of carboxylate anion. Thus, the removal of hydrogen atom by the carboxylate directs reaction from the hydropalladation to the carbopalladation pathway. Additionally, in the presence of the carboxylate anion intermediate, palladium complexes involved in the head-to-tail dimerization display higher stability compared to their analogues for the head-to-head reaction.

Understanding molecular interactions of graphene is a question of key importance to design new materials and catalytic systems for practical usage. Although for small models good accuracy was demonstrated in theoretical analysis with ab initio and density functional methods, the application to real-size systems with thousands of atoms is currently hardly possible on routine bases due to the high computational cost. In the present study we report that incorporation of dispersion correction led to the principal improvement in the description of graphene systems at a semi-empirical level. The accuracy and the scope of the calculations were explored for a wide range of molecules adsorbed on graphene surfaces (H2, N2, CO, CO2, NH3, CH4, H2O, benzene, naphthalene, coronene, ovalene and cyclohexane). As a challenging parameter, the calculated adsorption energy of aromatic hydrocarbons on graphene Eads = -1.8 ± 0.1 kcal mol(-1) (per one carbon atom) at the PM6-DH2 level was in excellent agreement with the experimentally determined value of Eads = -1.7 ± 0.3 kcal mol(-1). The dispersion corrected semi-empirical method was found to be a remarkable computational tool suitable for everyday laboratory studies of real-size graphene systems. Significant performance improvement (ca. 10(3) times faster) and excellent accuracy were found as compared to the ωB97X-D density functional calculations.