The rapid development of additive technologies in recent years is accompanied by their intensive introduction into various fields of science and related technologies, including analytical chemistry. The use of 3D printing in analytical instrumentation, in particular, for making prototypes of new equipment and manufacturing parts having complex internal spatial configuration, has been proved as exceptionally effective. Additional opportunities for the widespread introduction of 3D printing technologies are associated with the development of new optically transparent, current- and thermo-conductive materials, various composite materials with desired properties, as well as possibilities for printing with the simultaneous combination of several materials in one product. This review will focus on the application of 3D printing for production of new advanced analytical devices, such as compact chromatographic columns for high performance liquid chromatography, flow reactors and flow cells for detectors, devices for passive concentration of toxic compounds and various integrated devices that allow significant improvements in chemical analysis. A special attention is paid to the complexity and functionality of 3D-printed devices.
The paper describes synthesis and testing of novel biodegradable polylactide-based polymer membranes with desired mechanical properties, which are capable of sustained and directed release of biomacromolecules with high molecular weight (in particular, streptokinase; m.w. 47 kDa). Streptokinase is a pharmaceutical agent, possessing a pronounced thrombolytic activity. The membranes synthesized had a percentage elongation of 2–11% and tensile strength of 25–85 MPa. They were biodegradable – yet being stored in aqueous media in the absence of biological objects, would be dissolved by no more than 10% in 6 months. The synthesized membranes were capable of controlled release of streptokinase into the intercellular space, with the enzyme retaining more than 90% of its initial activity. The rate of streptokinase release from the membranes varied from 0.01 to 0.04 mg/day per cm2 of membrane surface. The membrane samples tested in the work did not have any short-term toxic effects on the cells growing de novo on the membrane surface. The mitotic index of those cells was approximately 1.5%, and the number of non-viable cells on the surface of the polymer films did not exceed 3–4% of their total amount. The implantation of the synthesized polymers – as both individual films and coatings of nitinol stents – was not accompanied by any postoperative complications. The subsequent histological examination revealed no abnormalities. Two months after the implantation of polymer films, only traces of polylactide were found in the implant-surrounding tissues. The implantation of stents coated with streptokinase-containing polymers resulted in the formation of a mature and thick connective-tissue capsules. Thus, the polylactide membranes synthesized and tested in this work are biodegradable, possess the necessary mechanical properties and are capable of sustained and directed release of streptokinase macromolecules.
The Mendeleev Periodic Table of Chemical Elements delivered a strong impetus to the development of fundamental and applied chemistry, chemical technology, analytical chemistry, and material sciences. Each element under the Periodic Table is an idealized substance with a certain structure and properties as defined by existing theoretical frameworks. In the real world, we deal with substances that are close in composition to the element of Periodic Table under study but differ in the presence of different elements in them – impurities that distort (sometimes radically) the structure and properties of the target research object. For many centuries, humanity has sought to obtain pure substances in order to achieve desired properties. In the second half of the 20th century, a unique collection of high purity substances was created, which includes samples representing material artifacts, prototypes of elements of Periodic Table that contain record low contents of impurity elements. With ongoing scientific and technological progress, the achieved purity of substances continuously increases and, therefore, their approximation to idealized elements of Periodic Table. This is facilitated by: new technological processes for the production and storage of high purity substances with a constant decrease in the level of impurities; the creation of isotope-friendly substances; complexes of more highly sensitive multi-element analysis methods; identification of the unique properties of high purity substances, bringing them closer to the capabilities of analog elements of Periodic Table and much more. This article is devoted to progress in these areas. Special attention is also paid to the problems in modern analytical chemistry of high purity substances and the use of the latter in the metrology of chemical analysis as the standards of comparison.
Solution chemistry is commonly regarded as the physical chemistry of reactions and chemical equilibria taking place in the bulk of a solvent, and between solutes in solution, and solids or gases in contact with the solution. Our knowledge about such reactions and equilibria in aqueous solution is very detailed such as their physico–chemical constants at varying temperature, pressure, ionic medium and strength. In this paper the solution chemistry in the surface region of aqueous solutions, down to ca. 10 Å below the water–air interface, will be discussed. In this region, the density and relative permittivity are significantly smaller than in the aqueous bulk strongly affecting the chemical behaviour of solutes. Surface sensitive X-ray spectroscopic methods have recently been applicable on liquids and solutions by use of liquid jets. This allows the investigation of the speciation of compounds present in the water–air interface and the surface region, a region hardly studied before. Speciation studies show overwhelmingly that neutral molecules are accumulated in the surface region, while charged species are depleted from it. It has been shown that the equilibria between aqueous bulk, surface region, solids and/or air are very fast allowing effective transport of chemicals over the aqueous surface region.
A kinetic model of the heavy oil feedstock hydroconversion performed in continuous flow reactor in the presence of in-situ synthesized dispersed nanosize catalyst Molybdenum disulfide (MoS2) has been proposed. The kinetic parameters of heavy oil feedstock with different properties have been determined for the two process versions: with coke formation and without appreciable coke formation. It has been stated that hydroconversion in the presence of in-situ synthesized dispersed MoS2 (C(Mo) = 0.05% wt. (per feed)) corresponds to a first-order reaction for all studied feedstock samples. The rate and activation energy constants have been determined. It has been shown that the conditions of polycondensation products (coke) formation result in increasing process rate and decreasing activation energy.
A mini-review describes the development of the catalysis by Cu(I) complexes aimed at the formation of C–N bond at the Lomonosov MSU during 2010s. The main approach employs the amination of aryl and heteroaryl halides with the amines and polyamines, in this direction a great versatility of starting compounds was achieved: adamantane-containing amines, linear diamines, oxadiamines and polyamines, various aryl iodides and bromides, derivatives of pyridine, and quinoline were used for this purpose. In more peculiar cases, the copper catalysis was used for steroids transformations, including vinylation of azoles, wide-spread “click” reactions for the conjugate syntheses, and successful heterogenezation of the copper catalysts were also undertaken.
One of the essential themes in modern catalysis is that of bridging the gap between its homogeneous and heterogeneous counterparts to combine their individual advantages and overcome shortcomings. One more incentive can now be added to the list, namely the ability of transition metal complexes to provide strong nuclear magnetic resonance (NMR) signal enhancement upon their use in homogeneous hydrogenations of unsaturated compounds with parahydrogen in solution. The addition of both H atoms of a parahydrogen molecule to the same substrate, a prerequisite for such effects, is implemented naturally with metal complexes that operate via the formation of a dihydride intermediate, but not with most heterogeneous catalysts. Despite that, it has been demonstrated in recent years that various types of heterogeneous catalysts are able to perform the required pairwise H2 addition at least to some extent. This has opened a major gateway for developing highly sensitive and informative tools for mechanistic studies of heterogeneous hydrogenations and other processes involving H2. Besides, production of catalyst-free fluids with NMR signals enhanced by 3-4 orders of magnitude is essential for modern applications of magnetic resonance imaging (MRI), including biomedical research and practice. The ongoing efforts to design heterogeneous catalysts which can implement the homogeneous (pairwise) hydrogenation mechanism are reported.
In this study, two oil fractions – straight-run diesel and light cycle oil (LCO) – and the products of their hydrotreatment with sulfide catalysts, synthesized in the pores of porous aromatic frameworks, were analyzed by comprehensive two-dimensional gas chromatography (GC) with time of flight mass spectrometry (GC × GC–TOFMS). Effective separation of numerous compounds in the analyzed multicomponent mixtures and high resolution of mass spectra of reaction products made it possible to study the features of the activity of sulfide catalysts.
Recent results obtained in studying mono- and bimetallic catalysts for selective hydrogenation of unsaturated carbonyl compounds, even unsaturated ones, acetylenic and nitro compounds as well as CO and bio-available alcohols oxidation are reviewed from the standpoint of the strong interaction between the metal nanoparticles, on the one hand, and two metals in the composition of bimetallic nanoparticles, on the other hand. Such interactions were demonstrated to result in partial positive or negative charging of metal nanoparticles, which, in turn, changes their adsorption and catalytic properties, especially with respect to the reactions involving hydrogen. Among the systems studied, Au–Pt, Au–Pd, Au–Cu, Au–Fe, Pt–WOx, Fe–Pd, Fe–Pt, Fe–Cu nanoparticles prepared by the redox procedure are considered to be most perspective in diverse catalytic applications because of the proper combination of the particle size and the electronic state of the metals.