Development of Thermodynamic Criteria for Determining the Composition of Duplex Stainless Steels with High Corrosion Resistance.

One of the most popular methods for ranking duplex stainless steels (DSSs) and predicting their corrosion properties is the calculation of the pitting resistance equivalent number (PREN). However, since DSSs are two-phase materials with a significant fraction of secondary phases and precipitates, the application of the PREN can be highly limited. This article attempted to use a new approach to describe the corrosion resistance of these steels. The corrosion resistance of two DSSs of the same class was investigated. Under identical solution heat treatments in the temperature range of 1050-1200 °C, the crevice corrosion resistance of one steel increased, while that of the other decreased. It was demonstrated that the amounts of austenite and ferrite changed similarly in these steels, and the different corrosion resistances were associated with the behaviors of secondary phases: niobium carbonitride and chromium nitride. SEM-EDS analysis was conducted to analyze the redistribution of elements between phases in both cases, showing good agreement with the thermodynamic modeling results. The PREN was calculated for each phase depending on the treatment temperature, and a method for calculating the effective PREN (PRENeff), accounting for phase balance and secondary phases, was proposed. It was shown that this indicator described corrosion properties better than the classical PREN calculated for the average steel composition. This study demonstrated how the calculation of critical temperatures (the temperature of equal amounts of ferrite and austenite, the temperature of the beginning of chromium nitride formation, and the temperature of the beginning of σ-phase formation) could describe the corrosion resistance of DSSs. Maximum possible deviations from these temperatures were defined, allowing the attainment of the required corrosion properties for the steels. Based on the conducted research, an approach for selecting new compositions of DSSs was proposed.

Control of the Composition and Morphology of Non-Metallic Inclusions in Superduplex Stainless Steel.

Duplex stainless steel is a unique material for cast products, the use of which is possible in various fields. With the same chemical composition, melting, casting and heat treatment technology, pitting and crevice corrosion were observed at the interphase boundaries of non-metallic inclusions and the steel matrix. To increase the cleanliness of steel, it is necessary to carefully select the technology for deoxidizing with titanium or aluminum, as the most common deoxidizers, and the technology for modifying with rare earth metals. In this work, a comprehensive analysis of the thermodynamic data in the literature on the behavior of oxides and sulfides in this highly alloyed system under consideration was performed. Based on this analysis, a thermodynamic model was developed to describe their behavior in liquid and solidified duplex stainless steels. The critical concentrations at which the existence of certain phases is possible during the deoxidation of DSS with titanium, aluminum and modification by rare earth metals, including the simultaneous contribution of lanthanum and cerium, was determined. Experimental ingots were produced, the cleanliness of experimental steels was assessed, and the key metric parameters of non-metallic inclusions were described. In steels deoxidized using titanium, clusters of inclusions with a diameter of 84 microns with a volume fraction of 0.066% were formed, the volume fraction of which was decreased to 0.01% with the subsequent addition of aluminum. The clusters completely disappeared when REMs were added. The reason for this behavior of inclusions was interpreted using thermodynamic modeling and explained by the difference in temperature at which specific types of NMIs begin to form. A comparison of experimental and calculated results showed that the proposed model adequately describes the process of formation of non-metallic inclusions in the steel under consideration and can be used for the development of industrial technology.

Development of a Methodology for the Quality Management of Duplex Stainless Steels.

The use of traditional materials leads to failures and breakdowns of expensive equipment, so advanced materials are needed that can provide reliable and durable solutions. The ability to control the quality of duplex stainless steels (DSSs) can greatly help with the development of new compositions or choosing existing DSSs. In this case, it is necessary to consider the final consumer properties-corrosion resistance and mechanical properties, which depend on the phase composition, contamination with non-metallic inclusions (NMIs), and the presence of undesirable secondary phases. In this research, specimens of cast DSSs of different grades, produced at laboratory and industrial scales, were studied. A technique for quantifying the microstructure of DSSs was developed. A thermodynamic database was chosen that adequately describes the processes of phase formation in DSSs. The effects of heat treatment on the microstructure and corrosion properties of cast DSSs were studied. The effects of the structural state on the changes in consumer properties of the final product are shown. It is shown that using various deoxidation technologies, it is possible to obtain both NMIs that are dangerous in terms of corrosive activity and ones that are relatively safe.

The Canonical Table of the Genetic Code as a periodic system of triplets.

The Canonical Table of the Genetic Code (CTGC) is constructed theoretically on the basis of the similarity of PFs (PF) of proteins with the conformation of 4-arc chain graphs (Karasev, 2019). Of the 64 conformations of the graph, specified by the position of the connectivity edges, and the matrices of 6 variables (x1 … x6), xi = (0, 1), 4 blocks of 16 elements each were formed. Then they were coded in the form of triplets based on the correspondence of pairs of variables to four letters of the code: 00 = C, 01 = U, 10 = G, 11 = A, and supplemented based on the known triplet-amino acid assignment. The resulting table is compared with the Periodic Table of Chemical Elements (PTCE). As in the PTCE, this CTGC has an initial element - a triplet that encodes graphs with zero number of connected edges. Within each block, vacancies are filled with connectivity edges in two alternative ways, both in rows and in the columns. As we move from the initial block 00 to the final block 11, there is a sequential filling of vacancies for variables x3x4: 00, 01, 10, 11. In general, the CTGC can be considered as a periodic system of triplets. Comparison with the previously described variety of tables of the genetic code made it possible to conclude that the CTGC more adequately reflects the properties of the genetic code. Prospects for the possible application of this table are being discussed.

Toward Development of a Label-Free Detection Technique for Microfluidic Fluorometric Peptide-Based Biosensor Systems.

The problems of chronic or noncommunicable diseases (NCD) that now kill around 40 million people each year require multiparametric combinatorial diagnostics for the selection of effective treatment tactics. This could be implemented using the biosensor principle based on peptide aptamers for spatial recognition of corresponding protein markers of diseases in biological fluids. In this paper, a low-cost label-free principle of biomarker detection using a biosensor system based on fluorometric registration of the target proteins bound to peptide aptamers was investigated. The main detection principle considered includes the re-emission of the natural fluorescence of selectively bound protein markers into a longer-wavelength radiation easily detectable by common charge-coupled devices (CCD) using a specific luminophore. Implementation of this type of detection system demands the reduction of all types of stray light and background fluorescence of construction materials and aptamers. The latter was achieved by careful selection of materials and design of peptide aptamers with substituted aromatic amino acid residues and considering troponin T, troponin I, and bovine serum albumin as an example. The peptide aptamers for troponin T were designed in silico using the «Protein 3D¼ (SPB ETU, St. Petersburg, Russia) software. The luminophore was selected from the line of ZnS-based solid-state compounds. The test microfluidic system was arranged as a flow through a massive of four working chambers for immobilization of peptide aptamers, coupled with the optical detection system, based on thick film technology. The planar optical setup of the biosensor registration system was arranged as an excitation-emission cascade including 280 nm ultraviolet (UV) light-emitting diode (LED), polypropylene (PP) UV transparent film, proteins layer, glass filter, luminophore layer, and CCD sensor. A laboratory sample has been created.

Data on the application of the molecular vector machine model: A database of protein pentafragments and computer software for predicting and designing secondary protein structures.

Based on ideas about the molecular vector machine of proteins [1], a database of protein pentafragments has been created and algorithms have been proposed for predicting the secondary structure of proteins according to their primary structure and for designing the primary protein structure for a given secondary structure that it takes on. A comprehensive software suite (Predicto @ Designer) has been developed using the pentafragments database and the said algorithms. For the proteins used to create the pentafragments database, a high accuracy (close to 100%) in predicting the secondary protein structure as well as good prospects for its use for designing secondary structures of proteins have been demonstrated.

A model of molecular vector machine of proteins.

Based on the analysis of NiH⋯Oi-4C bond region of the proteins pentafragments using the quantum chemistry representations, a group of 20 vectors of action has been isolated. These vectors of action are reconstructed by a group of 20 side chains of amino acids being the irreducible representations of vectors. As a result, a model of molecular vector machine of proteins (MVM) has been proposed. This machine includes proteins pentafragments, a system of 20 vectors inside dodecahedron coming out of the Oi-4 atom as from the center and tetrahedral αi-carbon atom with the side chains of amino acids that change as the polypeptide chain grows. A model with the structured canonical set of amino acids based on the principles of antisymmetry was transferred onto the dodecahedron as an MVM element (Karasev et al., 2005; Karasev et al., 2007). The perspective of MVM application for predicting and designing the secondary structure of proteins has been discussed.

Electronic Structure and Energy Transfer in Europium(III)-Ciprofloxacin Complexes: A Theoretical Study.

The structure and ligand-localized excited states of [Eu(cfqH) (cfq)(H2O)4]Cl2 (cfqH is ciprofloxacin) are studied by XMCQDPT2/CASSCF with full geometry optimization. The complex includes one anionic and one zwitterionic ligand. Two low-lying triplet states, both localized on the anionic ligand, are found. One of them has sufficient energy to transfer to the (5)D1 sublevel of Eu(3+), because its T-S0 vertical transition energy is equal (or very close) to the (7)F0-(5)D1 Eu(3+) excitation energy. The other triplet state has a very small S0-T1 gap, which favors fast nonradiative relaxation. Two other triplet states are localized on the zwitterionic ligand. One low-lying excited singlet state (S1) is localized on the anionic ligand; the other excited singlet is localized on the zwitterionic one. Spin-orbit coupling constants were calculated for the relaxed geometry of each state (ground state, two low-lying triplets, and one low-lying excited singlet) by spin-orbit configuration interaction (CI) with Pauli-Breit Hamiltonian. Large spin-orbit coupling constants between S1 and both triplets together with small energy gaps are indicative of fast intersystem crossing (ISC) from the excited singlet state to the triplet manifold. This ISC process is followed by energy transfer from the ligand-localized triplet states to the (5)D1 sublevel of Eu(3+). However, relatively large spin-orbit coupling constants between S0 and one of the triplet states together with the small T-S0 energy gap shows that this state can decay without transferring its energy to Eu(3+). This mechanism is expected to be common for other Ln(3+)-fluoroquinolone complexes.

Photochemical Behavior and Photolysis of Protonated Forms of Levofloxacin.

The effect of intermolecular proton transfer on the spectral properties of levofloxacin in the ground and excited electronic states was studied. The preferred direction of possible protolytic reactions induced by UV irradiation in this compound was studied. It was found that the proton transfer processes have a considerable effect on the capability of the compound to emit light and occur on the nanosecond timescale. The photochemical reactions of the tree forms of levofloxacin (pH: 4.0, 7.0, 10.0) were studied by laser flash photolysis and product studies. Irradiation at pH 4 yielded a pulse and transient (λmax  = 395, 515, 575 nm) assigned to the protonated triplet. Irradiation at pH 7 yielded a transient species (λmax  = 525, 610 nm) assigned to the neutral form. Protonation of the anionic singlet excited state was also observed (λmax  = 440, 570, 680 nm).

Polymorphism and intramolecular proton transfer in fluoroquinolone compounds.

Electronic absorption, luminescence, IR and Raman spectra of polymorphous forms of fluoroquinolones were investigated. Assignment of the band maxima due to π→π* and n→π* electronic transitions were done. The structural changes are responsible for the absorption band modifications. One-electron transitions in the long wavelength region, excitation wavelengths, oscillator strengths and involved molecular orbitals for the zwitter-ionic and cationic protonated forms for different fluoroquinolones were calculated with quantum-chemical and molecular dynamic methods. The electron density redistributions on the FQs separate fragments during the photoexcitation to the S(1)*-state were carry out by Mulliken calculations. It was shown that the degree of neutral and zwitter-ion FQs penetration through the bacterium membrane is different.

Spectral-luminescent properties and molecular orbital treatment of some mono- and difluoroquinolones.

Electronic absorption and luminescent spectra of nonfluorinated nalidixic (nlqH) and pipemidic acid (pifqH), monofluoroquinolones - norfloxacin (nfqH) and pefloxacin (pfqH) as well as of their difluorinated analogs 1-ethyl-6,8-difluoro-1,4-dihydro-7-(1-(4-methylpiperazinyl) - 4-oxo-3-quinolinecarboxylic (mdfqH) acid and 1-ethyl-6,8-difluoro-1,4-dihydro-7-(1-piperazinyl) - 4-oxo-3-quinolinecarboxylic acid (dfqH) - were investigated. Quantum yields, lifetimes of excited states and rate constants of radiative and nonradiative transitions of the compounds were measured. The Mulliken charges of atoms from these compounds were calculated by quantum-chemical complex GAMESS. Differences in the electronic structures of these compounds and their spectral-luminescent characteristics were compared with the data of the phototoxicity degree of fluoroquinolones. Analysis of the Mulliken charges of the difluoroquinolones points to the changes of the redistribution of the electron density along π-conjugated system, and on the oxygen atoms of the carbonyl and carboxyl groups. The analysis of the molecular orbitals involved in the electronic transitions of the compounds revealed that both defluorination and piperazine photolysis are photodecomposition mechanisms which may take place in the excited states of these compounds. The relationship between the location order of the π-π* excited levels of the FQs and the degree of their phototoxicity has been determined.

Analgesic effect from Ibuprofen nanoparticles inhaled by male mice.

BACKGROUND: Aerosol lung administration is a convenient way to deliver water-insoluble or poorly soluble drugs, provided that small-sized particles are generated. Here, for the outbred male mice, we show that the pulmonary administration of ibuprofen nanoparticles requires a dose that is three to five orders of magnitude less than that for the orally delivered particles at the same analgesic effect. METHOD: The aerosol evaporation-condensation generator consisted of a horizontal cylindrical quartz tube with an outer heater. Argon flow was supplied to the inlet and aerosol was formed at the outlet. The particle mean diameter and number concentration varied from 10 to 100 nm and 10(3)-10(7) cm(-)3, respectively. The analgesic action and side pulmonary effects caused by the inhalation of ibuprofen nanoparticles were investigated. RESULTS: The chemical composition of aerosol particles was shown to be identical with the maternal drug. Using the nose-only exposure chambers, the mice lung deposition efficiency was evaluated as a function of the particle diameter. CONCLUSIONS: The dose-dependent analgesic effect of aerosolized ibuprofen was studied in comparison with the oral treatment. It was found that the dose for aerosol treatment is three to five orders of magnitude less than that required for oral treatment at the same analgesic effect. Accompanying effects were moderate venous hyperemia and some emphysematous signs.

Anti-inflammatory effect from indomethacin nanoparticles inhaled by male mice.

The respiratory system provides entry for drug nanoparticles to cure systemic diseases. The modern devices that are available on the market of therapeutic aerosol delivery systems have a number of disadvantages. There remains a need for an alternative means that is low cost, convenient, and capable of producing small-sized particles. On the other hand, one-third of the modern drugs are poorly water soluble. Many currently available injectable formulations of such drugs can cause side effects that originate from detergents and other agents used for their solubilization. The aerosol lung administration may by a good way for delivery of the water-insoluble drugs. We present here a new way for the generation of drug nanoparticles suitable for many water insoluble substances based on the evaporation-condensation route. In this paper the indomethacin nanoaerosol formation was studied and its anti-inflammatory effect to the outbred male mice was examined. The evaporation-condensation aerosol generator consisted of a horizontal cylindrical quartz tube with an outer heater. Argon flow was supplied to the inlet and the aerosol was formed at the outlet. The particle mean diameter and number concentration were varied in the ranges 3 to 200 nm and 10(3) to 10(7) cm(-3), respectively. The liquid chromatography and X-ray diffraction methods have shown the nanoparticles consist of the amorphous phase indomethacin. The aerosol lung administration experiments were carried out in the whole-body exposure chamber. Both the lung deposited dose and the particle deposition efficiency were determined as a function of the mean particle diameter for mice being housed into the nose-only exposure chambers. The anti-inflammatory action and side pulmonary effects caused by the inhalation of indomethacin nanoparticles were investigated. It was found that the aerosol administration was much more effective than the peroral treatment. The aerosol route required a therapeutic dose six orders of magnitude less than that for peroral administration.