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In this paper, we study the properties and destruction mechanisms of ultra-high molecular weight polyethylene (UHMWPE) fiber and composite material (CM) based on it with a rigid and flexible matrix at the low-speed impact by the “impact break” (IB) method. A significant difference in the deformation behavior and destruction mechanisms upon impact of Dyneema®SK-75 UHMWPE fiber and the CM based on this fiber was experimentally found. The impact was found to have little effect on the properties of an isotropic UHMWPE fiber, while the properties of a fiber without a matrix under impact loading are several times higher than the properties of the CM based on this fiber. Upon impact, interaction occurs between the components of the CM, and such CM is an anisotropic material in which, from the first moment of impact loading to the CM destruction, a stepwise deformation mechanism is implemented: the so-called “stepwise ladder of deformation.” Step deformation is the main mechanism of deformation and destruction of anisotropic composite materials upon impact.

A theoretical and experimental study was performed on the heat exchange, hydrodynamics and diffusion during the transition of methane through a layer of tin melt with the aim of intensifying the pyrolysis process in a reactor filled with metal melt. Analysis of the experiment data shows that, as the methane supply rate increases from 25 to 250 ml/min, the duration of the contact between the gas bubbles and tin melt shortens, which leads to a decrease in the mole fraction of hydrogen in the resulting gas from 12% to 4.4% (for a reactor 10 cm in height). Using a cascade of mesh diaphragms is suggested to intensify the pyrolysis process for high methane supply rates. A unique float-type structure may be placed inside the reactor to solve the problem of continuous removal of the hard carbon deposits generated during methane pyrolysis and to control the metal melt level.

Mathematical models of methane decomposition during its pyrolysis, including nonstationary diffusion equations with and without taking into account the convective component of the decomposition process, have been developed and verified. Their exact analytical solutions have been obtained and further used in the study of a mathematical model of the formation of solid carbon particles arising during methane heating to the pyrolysis temperature. By studying the rate and intensity of the formation of solid carbon particles, it has been shown that particles of the smallest size are obtained at higher decomposition temperatures and for a shorter time.

Background and aims Based on the developed technology of preparation of ultra-small size phospholipid (PL) nanoparticles without the use of detergents/surfactants and stabilizers drug preparation, exhibiting hypolipidemic properties has been obtained. Preclinical and clinical studies have shown that phospholipid nanoparticles of 20–30 nm (PLN) have activated reverse cholesterol transport and reduced non-high-density lipoprotein cholesterol levels. The aim of the study was to compare the effect of PLN relative to placebo on the selected parameters of carbohydrate and fat metabolism in patients with combined hyperlipidemia. Methods This Phase III, randomized, double-blind, placebo-controlled, parallel-group study was conducted at 4 centers. The patients (pts) received PLN or placebo (1:1), powder for oral solution preparation (500 mg PL/dose) orally 2 times per day for 12 weeks. Biochemical parameters of carbohydrate and fat metabolism were measured. The data is presented in M (s). Statistical analysis was performed using the Mann-Whitney U-test and the Wilcoxon sign rank test. P-value Results A total of 100 pts with combined hyperlipidemia were randomized (age 35–70 years, males 58%). The mean age of patients was 56.4 (10.2) years, body-mass index (BMI) – 30.4 kg/m (2). Mean glucose, triglyceride (TG), fasting insulin (INS) and adiponectin (ADN) serum levels at baseline were 5.58 (0.9) mmol/l, 2.38 (0.6) mmol/l, 13.71 (6.03) mU/ml and 7.07 (2.25) μg/ml, respectively. At Week 12, PLN significantly reduced TG and insulin (p=0.03 and p=0.02, respectively). At the same time, the mean adiponectin level was increased (ns). The drug was well tolerated, and no clinically significant laboratory abnormalities were detected. Conclusions PLN therapy is well tolerated with a favorable effect on the chosen parameters of carbohydrate and fat metabolism in patients with moderate combined hyperlipidemia. Funding Acknowledgement Type of funding sources: Public Institution(s). Main funding source(s): Ministry of industry and trade, Ministry of Healthcare of the Russian Federation

The efficiency of cholesterol efflux from cells promoted by high-density lipoproteins (HDLs) depends on HDL concentration and functional properties. The term “dysfunctional HDL” describes HDLs with impaired protective properties. Cholesterol efflux capacity (CEC) of HDL is reduced in patients with atherosclerosis, but the exact mechanisms underlying this impairment are not well characterized. Enriching HDLs with phospholipids (PLs) improves CEC. Herein, we assessed the potential of PL nanoparticles in improving HDL functionality. We lipidated HDL subfractions by incubating with PL nanoparticles containing soybean polyunsaturated phosphatidylcholine. Incubating blood plasma with PL nanoparticles resulted in the dose-dependent lipidation of all HDL subfractions. Changes in apolipoprotein A1 (apoA-1) and PL concentrations were the most prominent in the HDL2 fraction. Concentrations of PL in the HDL3 fraction and the fraction with a density > 1.21 g/mL increased by 30–50%, whereas apoA-1 levels decreased. We hypothesized that PL nanoparticles may cause HDL remodeling that can improve their functions. The CECs of lipidated HDLs were analyzed by incubating apolipoprotein B (apoB)-depleted plasma with 3H-cholesterol-labeled THP-1 macrophages. The findings revealed a two-fold increase in cholesterol efflux compared with native apoB-depleted plasma. Moreover, intravenous administration of PL nanoparticles restored lipid profiles and effectively protected blood vessels from atherosclerosis progression in cholesterol-fed rabbits compared with that of fenofibrate and atorvastatin. PL nanoparticles also protected against atherosclerosis and decreased the atherogenic index. Altogether, these results indicate that PL nanoparticles can be used to correct the lipid composition and CEC of HDLs. Data Availability Additional data can be provided upon reasonable request from the date of publication of this article within 5 years. The request should be sent to the author-correspondent at the address cd95@mail.ru.

A method is suggested for calculating the density of single-component aqueous solutions of nitric acid and nitrate salts contained in solutions used in hydrometallurgical processes on the nuclear fuel cycle. The method uses apparent molar volumes and the water concentration. The method makes it possible to calculate the density of nitric acid solutions up to 17 M (HNO3 dihydrate) and salts to the point of formation of saturated solutions with an error not exceeding 0.2%. The values of the apparent molar volumes linearly depend on the concentration of water, and the apparent molar values approximated to the infinite dilution correspond to the Pitzer values.

The extraction of trivalent REE and TPE nitrates with tributyl phosphate and its solutions in paraffins at room temperature in the presence of HNO3 is described mathematically using a unified model involving parallel occurrence of several equilibrium reactions, suggested previously for modeling the extraction equilibria with REE and TPE in neutral systems and with hexavalent actinide nitrates in acid systems. The previously suggested set of equations was supplemented by the equation of the formation of a complex acid in the organic phase via addition of the HNO3 molecule to the element trisolvate.

Extraction of 241Am and 154Eu by 50% tributyl phosphate (TBP) in C13 fraction from nitric acid solutions containing 6 mol L−1 nitrate-ion of ammonium, aluminum, and iron salts has been inve...

A unified model based on published data and authors’ experimental results was suggested for describing the extraction of An(VI) (An = U, Np, Pu, Am) from HNO3 solutions into TBP solutions of various concentrations. Parallel occurrence of several extraction reactions and of nonstoichiometric physicochemical interaction of the components is assumed. The calculated parameters of the dependence of the concentration equilibrium constants on the total TBP concentration allowed expansion of the range of extractant concentrations described by the model (from 2.7 to 100%) and reduction of the uncertainty in calculation of the HNO3 and An(VI) distribution ratios. The parameter of apparent hydration of nitrate salt cations in the aqueous phase was used for describing the salting-out effect of these salts.

A mathematical model based on the published data was developed for the extraction of REE (from La to Lu, including also Y) nitrates in a wide concentration range in weakly acidic ([H+] ≪ [REE]) systems with TBP, taking into account the dilution of TBP with paraffins and including systems with salting-out agents. Parallel occurrence of several complexation reactions in the aqueous and organic phases and of nonstoichiometric physicochemical interaction of the components is assumed. The formation of REE trisolvate, tetrasolvate, and hydrate solvate, the coextraction of cerium- and yttrtium-group REEs in the form of an ion pair, and the self-salting-out effect caused by the apparent hydration of Ln3+ in the aqueous phase are taken into account. The model considers the effect of ammonium, sodium, and aluminum nitrates as salting-out agents. The influence of temperature on the REE extraction in these systems is also described. The error of calculating the distribution ratios is ≤10%.

Background and aims Based on the developed technology of prerparation of ultra small size phospholipid nanoparticles without the use of detergents/surfactants and stabilizers drug preparation, exhibiting hypolipidemic properties has been obtained. Preclinical studies have shown that phospholipid nanoparticles of 20–30 nm (PLN) activate reverse cholesterol transport. PLN is now at the stage of clinical trials (Phase II study completed). The aim of the study was to compare the efficacy, safety and tolerability of PLN relative to placebo in the treatment of combined hyperlipidemia. Methods This Phase III, multicenter, randomized, double-blind, placebo-controlled, parallel-group study was conducted at 4 centers. The patients (pts) received PLN or placebo (1:1), powder for oral solution preparation (in an aqueous environment is a nanoemulsion with a particle size of 20–30 nm), 500 mg (sachet) orally 2 times a day for 12 weeks. Lipid parameters, safety and tolerability were measured. The data is presented in M (s), Me (lq; hq). Mann-Whitney U Test was to compare the significant difference of groups. P value Results A total of 100 pts with combined hyperlipidemia were randomized (age 35–70 years, males 58%).The mean age of patients was 56.4 (10.2) years. Mean total cholesterol, non-high-density lipoprotein cholesterol (non-HDL-C), TG, and apolipoprotein B 100 (apoB) levels at baseline were 5.59 (0.8) mmol/l, 4.51 (0.75) mmol/l, 2.38 (0.6) mmol/l and 114.26 (24.96) mg/dl, respectively (n=100). Mean high-density lipoprotein cholesterol (HDL-C) and Lp(a) levels at baseline were 1.0 (0.25) mmol/l and 21.1 (3.9; 20.3)mg/dl, respectively (n=100). At Week 12, PLT significantly reduced total cholesterol, non-HDL-C levels, TG and apo B compared to placebo (p=0.02, p=0.03, p=0.001 and p=0.02, respectively). At the same time, the mean HDL-C level was significantly increased (p=0.03). The drug was well tolerated and no clinically significant laboratory abnormalities were detected. Conclusions This study demonstrates that therapy with PLT is well tolerated in additional beneficial effects on key lipid parameters in patients with moderate combined hyperlipidemia. Funding Acknowledgement Type of funding source: Public Institution(s). Main funding source(s): Ministry of industry and trade

Among blood plasma lipoproteins that transport lipids in the organism, a significant role belongs to high-density lipoproteins (HDL). They protect against atherosclerosis progression, mainly through their ability to accept cholesterol from cell membranes and subsequently deliver it to the liver for catabolism. Recently, it has been found that this HDL property is often disrupted, regardless of their concentration in the blood, and this is associated with a greater predisposition to cardiovascular diseases. The causes of these disorders associated with any modifications of proteins and/or lipids composing the HDL particles have not yet been revealed. Many data indicate the significance of possible changes in phospholipids (PL) of HDL. This review examines how cellular cholesterol is excreted to HDL with the participation of membrane proteins, ABCA1, ABCG1, and SR-B1, as well as components of the surface monolayer of HDL, apoprotein A1 (apoAl) and PL, particularly the predominant phosphatidylcholine (PC). The possibilities of correcting the dysfunctionality of HDL by phospholipidation, using apoA1-PC complexes or detergent PC emulsions, are also reviewed. Data of our research using soy PC nanoparticles less than 30 nm in size that activates the [3Н]cholesterol efflux from macrophages to plasma HDL are presented. Prospective new pharmacological approaches in PL therapy for normalization of HDL properties through their enrichment with PC are discussed.

(C 4 Me 4 )Co-containing triple-decker complexes with bridging boron and phosphorus heterocyclic ligands [(C 4 Me 4 )Co(μ-η:η-L)MCp*] + ( 1 : M = Fe, L = C 5 H 5 BMe; 2 : M = Fe, L = C 4 Me 4 P; 3a : M = Fe, L = cyclo -P 5 ; 3b : M = Ru, L = cyclo -P 5 ) were synthesized by photochemical reaction of [(C 4 Me 4 )Co(C 6 H 6 )] + with sandwich compounds Cp*ML. They were isolated as salts with PF 6 − anion, and the structures of 1 PF 6 , 2 PF 6 , and 3a PF 6 were determined by X-ray diffraction. The μ-pentaphospholyl complex 3a was also synthesized by exchange of sandwich compounds in the μ-cyclopentadienyl triple-decker complexes [(μ-η:η-Cp){Co(C 4 Me 4 )} 2 ] + or [(C 4 Me 4 )Co(μ-η:η-Cp)FeCp] + . Complexes 1 , 2 , and 3a undergo nucleophilic degradation by acetone and acetonitrile with selective elimination of the [(C 4 Me 4 )Co] + fragment giving the starting sandwich compounds. The rate of the nucleophilic degradation depends on the nature of the bridging ligand and decreases in the following order: C 4 Me 4 P ≥ C 5 H 5 BMe > cyclo -P 5 . The bonding in 1 , 2 , and 3a was analyzed and compared with that in the cyclopentadienyl analog [(C 4 Me 4 )Co(μ-η:η-Cp)FeCp*] + using energy decomposition analysis.

In recent years the number of articles on damages of high-density lipoproteins (HDL) properties in patients with atherosclerosis has sharply increased. First, it concerns their ability to accept cholesterol (CH) from macrophages - the basis of antiatherogenic action of HDL. This ability was assessed ex vivo - by activity of cell cholesterol (CH) efflux to HDL or into patient's serum. In many works inverse relationship was shown between CH acceptor capacity of HDL and severity of atherosclerotic disease or frequency of its exacerbations during long-term observation, independent from HDL CH concentration. This led to the emergence of the concept of importance of "not only HDL quantity but also of their quality", i. e. functionality. In this review we consider pathways of cellular CH efflux (mainly mediated by cell proteins), methods used for detection of dysfunctional HDL, and results of relevant studies in various categories of patients. These studies directed to identification of mechanisms of damages of HDL properties by means of analysis of their composition, used various approaches including those of proteomics and lipidomics. However, now there are no proven targets for correction of HDL dysfunctionality. The only factor, that is underlined by many authors, is the significance of HDL phospholipids, which level correlates with activity of cellular CH efflux. This allows to take a fresh look at previously used phospholipid therapy of atherosclerosis. Its mechanism is apparently not lowering of plasma CH, as was previously expected, but the improvement of HDL antiatherogenic properties. For its practical usage it is necessary to elaborate principally novel formulations with high bioavailability of phospholipids - for HDL enrichment by phospholipid and thereby normalization of their ability to remove CH from tissues.

Gold nanoparticles and their conjugates have significant potential in the field of diagnosis of various diseases due to their SPR, which enhances light scattering and absorption. Conjugates of gold nanoparticles with various ligands can be used for imaging biomolecules or detecting malignant neoplasms at an early stage. This study focuses on the construction of composite (or hybrid) phospholipid-gold nanoparticles using soy phosphatidylcholine and a targeted ligand (folic acid derivative) to attach specific targeting properties. According to the method of dynamic light scattering, the diameter of the obtained nanoparticles was less than 100 nm, the results of the MTT test indicated their moderate cytotoxicity. In vitro and in vivo experiments showed a significant increase in the accumulation of phospholipid-gold nanoparticles with a targeted fragment compared to those without a targeted fragment both in HeLa cells and in a tumor (in BDF mice with an injected LLC tumor). The resulting nanoparticles are suitable for specific delivery into tumor cells and visualization of various malignant neoplasms, including at early stages, due to the increased expression of the folate receptor characteristic of cells of a wide range of tumors.

Using the equations of physicochemical hydrodynamics and experimental results regarding the surface and interphase properties of metallic and oxide melts, the conditions in which metallic phase is formed in the bubbling of carbon monoxide through molten oxidized nickel ore are described. The critical dimensions of the gas bubble (Rb.cr) and the metal droplet (rd.cr) moving in oxide melt without change in size are determined in the range 1550–1750°C. It is found that Rb.cr increases slightly from 6.35 × 10–2 m at 1550°C to 6.58 × 10–2 m at 1750°C. With change in the droplet composition and the temperature, rd.cr varies from 2.1 × 10–3 to 2.9 × 10–3 m. The dimensions of the metal droplet formed at a single bubble during the reduction of nickel and iron from oxide melt are determined. As the content of nickel and iron oxides in the melt decreases with increase in the overall CO consumption, the nickel content in the ferronickel droplets falls from 89 to 18%, while the droplet diameter decreases from 1.4 × 10–3 to 8.0 × 10–4 m. The droplet mass falls correspondingly from 9.4 × 10–5 to 1.6 × 10–5 kg. The conditions in which the bubble–droplet system rises through the melt are determined. Over the whole range of temperature and Ni content, the bubble–droplet system begins to rise through the oxide melt when rd/Rb is less than 0.68–0.78. To assess the stability of the bubble–droplet system, with the given bubble and droplet dimensions, the parameters determining their joint motion are calculated. It is found that breakaway of the metal droplet from the bubble is not possible in pyrometallurgical systems. The formation of metal phase as a result of the bubbling of carbon monoxide through the oxide melt is described. In this process, the interaction of the oxide melt with the gas is accompanied by the formation of metal droplets, which become attached to the surface of gas bubbles and move to the surface of the oxide melt. Metal with 80–90% Ni is formed at first. With decrease in the nickel content in the oxide melt, its content in the metal declines to 20%. At the surface of the oxide melt, the metal droplets coalesce. When their diameter is greater than 5 × 10–3 m, they break away from the surface and fall to the bottom. If the falling drop collides with ascending bubble–droplet systems, they may coalesce with it or flow around it. On coalescence, the small droplets will be assimilated and rise to the surface. The breakaway force of the droplet from the bubble significantly exceeds the gravitational force on the droplet. Therefore, the bubble–droplet system is stable for all the size ratios considered.

Demethylation of cyclohexadienyl complexes (η-X-SMe2-7,8-C2B9H10)Fe(η5-C6H7) (1a,b; X = 9 (a), 10 (b), where X is number of the substituent position) with PhCH2SNa in DMF (dimethylformamide) and subsequent protonation by acetic acid lead to iron benzene complexes (η-X-SMe-7,8-C2B9H10)Fe(η-C6H6) (2a,b). Visible light irradiation of 2a in the presence of tBuNC or Cp*Fe(η-cyclo-P5) affords neutral half-sandwich (η-9-SMe-7,8-C2B9H10)Fe(tBuNC)3 (3) or triple-decker (η-9-SMe-7,8-C2B9H10)Fe(μ-η:η-cyclo-P5)FeCp* (4) complexes. Reaction of 2b with (THF)W(CO)5 selectively gives the iron-tungsten dinuclear complex (η-10-SMe(W(CO)5)-7,8-C2B9H10)Fe(η-C6H6) (5). Structures of 2a, 4 and 5 were determined by X-ray diffraction. Electrochemistry reveals that the redox processes of the SMe-substituted ferracarboranes are cathodically shifted (by 350 mV) with respect to the corresponding redox changes of the SMe2-analogs. The Fe-C6H6 bonding in 2a and the related benzene complexes [(η-9-SMe2-7,8-C2B9H10)Fe(η-C6H6)]+ and (η-7,8-C2B9H10)Fe(η-C6H6) was analyzed by energy decomposition analysis.

Iron ore reserves of the Bakal ore field are estimated. Chemical and phase compositions are provided for the main deposits. The efficiency of Bakal deposit utilization in blast furnace and steel smelting processes with different preparation methods is evaluated. It is shown that siderite may only be used as a combined raw material containing iron and magnesium.

Reaction of bis(p-tolyl-propargyl)-tosylamide with [(cod)RhCl]2 in the presence of CO gives the cyclopentadienone complex [(Cpd’)Rh(CO)Cl]n (Cpd’ = TsN(CH2)2C4(Tol)2CO). Its dissolution in DMSO or pyridine leads to decarbonylation and formation of the adducts (Cpd’)Rh(DMSO)2Cl and (Cpd’)Rh(Py)2Cl. The reaction of [(Cpd’)Rh(CO)Cl]n with AgPF6 and p-xylene produces the sandwich arene complex [(Cpd’)Rh(p-xylene)]PF6, in which the arene can be substituted by tBuNC ligand to give [(Cpd’)Rh(tBuNC)3]PF6. The arene complex acts as an efficient catalyst for the reductive amination of carbonyl compounds in the presence of CO as deoxygenation agent, producing various amines in 75–85% yields.

The indenyl-benzene complex [(η5-indenyl)Fe(η-C6H6)]+ (2) was synthesized by photochemical reaction of the cyclohexadienyl derivative [(η5-C6H7)Fe(η-C6H6)]+ and indenyl anion with the subsequent treatment of complex (η5-C6H7)Fe(η5-indenyl) formed by acetic acid. Visible light irradiation of cations [(η5-indenyl)Fe(η6-indene)]+ (1) or 2 in the presence of substituted benzenes in CH2Cl2 results in arene exchange giving [(η5-indenyl)Fe(η6-arene)]+ (arene=o-xylene (3 a), mesitylene (3 b), hexamethylbenzene (3 c) and [2.2]paracyclophane (3 d)). The rate of this reaction is lower than for the related cyclopentadienyl complex [CpFe(η-C6H6)]+. μ-Pentaphospholyl triple-decker complex [(η5-indenyl)Fe(μ-η:η-cyclo-P5)FeCp*]+ (4) was synthesized by photochemical reaction of 1 with Cp*Fe(η-cyclo-P5). The structures of 2PF6, 3 cPF6 and 4PF6 were determined by X-ray diffraction. According to energy decomposition analysis, the metal-benzene bonding in 2 is weaker than in [CpFe(η-C6H6)]+ but stronger than in [Cp*Fe(η-C6H6)]+. The mechanism of thermal benzene replacement in 2 and [CpFe(η-C6H6)]+ as well as structure of excited state were analyzed by DFT calculations.

The effect of a series of halogenated diluents [bis(octafluoroamyloxy)methane, phenyl trifluoromethyl sulfone, methyl dodecafluoroheptyl ether, m-nitrobenzotrifluoride, hexachlorobutadiene, CHCl3, CCl4] on the extraction of spent nuclear fuel solution components [HNO3, U(VI), An(IV), Zr, and Tc] into 30% TBP was studied and mathematically described using improved A.M. Rozen’s model. Comparison with the TBP–paraffins extraction system was made.

Polyhedral rearrangement of iridacarborane 1,2-Me2-3,3-(cod)-4-SMe2-3,1,2-closo-IrC2B9H8 (1) proceeds in a solution at RT and affords a product of 1,2 → 1,7 isomerization 1,8-Me2-2,2-(cod)-7-SMe2-2,1,8-closo-IrC2B9H8 (2). Rhodium derivative 1,2-Me2-3,3-(cod)-4-SMe2-3,1,2-closo-RhC2B9H8 (3) is significantly more stable toward heating than iridium complex 1 and isomerizes at 110 °C by 1,2 → 1,2 and 1,2 → 1,7 reaction schemes with 1,2 → 1,2 being the predominant route forming 1,2-Me2-4,4-(cod)-8-SMe2-4,1,2-closo-RhC2B9H8 (4) and 1,8-Me2-2,2-(cod)-7-SMe2-2,1,8-closo-RhC2B9H8 (5). Complexes 4 and 5 were characterized by 11B{1H}–11B{1H} COSY NMR spectrometry. A mechanism of 1,2 → 1,2 isomerization of 3 to 4 was proposed on the basis of DFT calculations. Reaction of the thallium salt Tl[7,8-Me2-9-SMe2-7,8-nido-C2B9H8] (CarbTl) with [Cp*RuCl]4 in THF furnishes new ruthenacarborane 1,2-Me2-3-(Cp*)-4-SMe2-3,1,2-closo-RuC2B9H8 (6). Heating of 6 at 80 and 144 °C leads to the partial and complete decomposition, respec...

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Reaction of dimethylamine adduct of 1-methyl-3-borolene with [(C2H4)2RhCl]2 gives the triple-decker complex (η-C4H4BMe)Rh(μ-η:η-C4H4BMe)Rh(η-C4H4BMe) (1a) in 62% yield and trace amount (

The density and surface tension of melts of ferronickel (0–100% Ni) and oxidized nickel ore are measured by the sessile-drop method, as well as the interface tension at their boundary in the temperature range 1550–1750°C. The composition of the nickel ore is as follows: 14.8 wt % Fetot, 7.1 wt % FeO, 13.2 wt % Fe2O3, 1.4 wt % CaO, 16.2 wt % MgO, 54.5 wt % SiO2, 4.8 wt % Al2O3, 1.5 wt % NiO, and 1.2 wt % Cr2O3. In the given temperature range, the density of the alloys varies from 7700 to 6900 kg/m3; the surface tension from 1770 to 1570 mJ/m2; the interface tension from 1650 to 1450 mJ/m2, the density of the oxide melt from 2250 to 1750 kg/m3; and its surface tension from 310 to 290 mJ/m2. The results are in good agreement with literature data. Functional relationships of the density, surface tension, and interphase tension with the melt temperature and composition are derived. The dependence of the alloy density on the temperature and nickel content corresponds to a first-order equation. The temperature dependence of the surface tension and interphase tension is similar, whereas the dependence on the nickel content corresponds to a second-order equation. The density and surface tension of the oxide melt depend linearly on the temperature. The results may be used to describe the formation of metallic phase when carbon monoxide is bubbled into oxide melt.

Purpose: Small cell lung cancer (SCLC) is a highly aggressive disease representing 12% to 13% of total lung cancers, with median survival of Experimental Design: To avoid DLT for useful cytotoxic agents, the recently developed drug STA-8666 combines a chemical moiety targeting active HSP90 (concentrated in tumors) fused via cleavable linker to SN38, the active metabolite of irinotecan. We compare potency and mechanism of action of STA-8666 and irinotecan in vitro and in vivo. Results: In two SCLC xenograft and patient-derived xenograft models, STA-8666 was tolerated without side effects up to 150 mg/kg. At this dose, STA-8666 controlled or eliminated established tumors whether used in a first-line setting or in tumors that had progressed following treatment on standard first- and second-line agents for SCLC. At 50 mg/kg, STA-8666 strongly enhanced the action of carboplatin. Pharmacokinetic profiling confirmed durable STA-8666 exposure in tumors compared with irinotecan. STA-8666 induced a more rapid, robust, and stable induction of cell-cycle arrest, expression of signaling proteins associated with DNA damage and cell-cycle checkpoints, and apoptosis in vitro and in vivo, in comparison with irinotecan. Conclusions: Together, these results strongly support clinical development of STA-8666 for use in the first- or second-line setting for SCLC. Clin Cancer Res; 22(20); 5120–9. ©2016 AACR.

There has been significant recent interest in combining radiation therapy and photodynamic therapy for cancer treatment. One proposed method involves conjugating photosensitizers (PS) to scintillating nanoparticles. However, the production of nanoscintillators that are stable in biological media is problematic since many of the commonly used compositions chelate phosphate. In this paper, the problem was solved by first synthesizing LaF3 nanoparticles, followed by surface modification with alendronate, which serves as a stable anchor for conjugation of molecules of interest. The nanoparticles had an average diameter of 4 nm, and were doped with either Ce^(3+), Tb^(3+), or both. In every case, a LaF3 shell was added. In subsequent steps, poly(ethylene) glycol (PEG) and photosensitizers (either chlorin e6 or rose bengal) were covalently linked to the alendronate ligand via an amide bond. This new formulation is stable in several solutions and buffers used commonly in the laboratory for cell culture. Moreover, cellular uptake and lack of toxicity up to a concentration of 50 μM were observed in B16 murine melanoma cells. Energy transfer between the doped nanoparticle core and the conjugated photosensitizers was demonstrated using UV excitation, and scintillation was demonstrated using x-rays.

A model is proposed for the formation of metallic phase when gaseous reducing agent is bubbled through multicomponent oxide melt. The model includes the following stages: the formation of bubbles when gas is injected in the melt; the reduction of metal at the surface of the bubbles and its concentration in droplet form at the rear of the bubble; motion of the bubble–droplet system in a direction determined by the ratio of the uplift forces on the bubble and the gravitational forces on the droplet; entrainment of the droplets to the surface; and coalescence of the droplets and their descent on reaching a size such that the gravitational forces exceed the sum of the hydrostatic collision forces and the surface tension forces. Equations are presented for estimating the size of the gas bubble and the droplet moving in oxide melt without decrease in size; the direction of motion of the bubble–droplet system; its rate of ascent or descent; and the conditions in which the bubble–droplet system breaks down. The factors responsible for separation of the bubble and the droplet are identified: the surface properties of the oxide melt and the metallic melts and their interphase characteristics. By adjusting these parameters, the formation of metallic phase at the bottom of the vessel may be regulated.

Reactions of [(C2H4)2RhCl]2 or [(coe)2RhCl]2 (coe = cyclooctene) with AgPF6 and arenes, followed by addition of 3-hexyne, give the cyclobutadiene complexes [(C4Et4)Rh(arene)]+ in 40–65% yield (arene = tert-butylbenzene, p-xylene, mesitylene, 4-mesitylbutanoic acid). In the absence of arenes, the hexaethylbenzene complex [(C4Et4)Rh(C6Et6)]+ is formed in 70% yield as a result of cyclotrimerization of 3-hexyne in the coordination sphere of rhodium. Similar reaction of [(coe)2IrCl]2 with AgPF6 and 3-hexyne leads to [(C4Et4)Ir(C6Et6)]+, which is apparently the first reported cyclobutadiene iridium complex. DFT calculations suggest that formation of the model cyclobutadiene complex [(C4Me4)Rh(C6H6)]+ from bis(alkyne) intermediate [(C2Me2)2Rh(C6H6)]+ can proceed via a metallacycle transition state with a low energy barrier of 14.5 kcal mol–1.

Databases on the coextraction of Th or Pu with Tc into 30% TBP in hydrocarbon diluent at 25°С are presented. The coextraction leads to mutual enhancement of the extraction of all the elements. The interactions in the system are described within the framework of a new approach to modeling, using the previously suggested and additional equations of concurrently occurring chemical reactions. The apparent equilibrium constants of these reactions are calculated.

Equilibrium distribution of molybdenum, uranium, and certain fission products in extraction from nitric acid solutions with 0.2% solutions of hydroxamic acids in alcohols poorly soluble in water and the process kinetics were studied. Methods for the Mo stripping were examined. A small-size flowsheet allowing ~98% isolation of Mo in 6 h and its preconcentration by a factor of 15 with efficient separation from the main impurities (separation factors 500–10 000) was tested on an extraction rig with a model solution spiked with 99Mo and 125I. A batch procedure ensuring the 99Mo preconcentration by a factor of ~180 and separation from the impurities with the separation factor of 103–108 at a process time of 2 h was suggested and checked.

The behavior of the initial ore and the concentrate of magnetoroasting beneficiation during metallization under the conditions that are close to those for reducing roasting of iron ores in a rotary furnace is studied in terms of works on extending the field of application of Bakal siderites. A difference in the mechanisms of the metallization of crude ore and the roasted concentrate is observed. The metallization of roasted concentrate lumps is more efficient than that of crude siderite ore. In this case, the process ends earlier and can be carried out at higher temperatures (1250–1300°C) without danger of skull formation.

Metallacarborane [1,8-Me2-2,2-(C2H4)2-7-SMe2-2,1,8-IrC2B9H8] (1) was obtained by an interaction of [(C2H4)2IrCl]2 with Tl[9-SMe2-7,8-Me2-7,8-C2B9H8]. Reaction proceeds with a low temperature “1,2 → 1,7” polyhedral rearrangement. Ethene complex 1 reacts with iodine in toluene with the formation of ionic compound 3, consisting of cationic [(1,8-Me2-7-SMe2-2,1,8-IrC2B9H8)2I3]+ (3a+) and anionic [(1,8-Me2-7-SMe-2,1,8-IrC2B9H8)2I3]− (3b–) iodide species. The structures of 1 and 3 were determined by X-ray diffraction.

A catalyst of a new type, cyclobutadiene complex [(C4Et4)Rh(p-xylene)]PF6, was found to promote selective reductive amination in the presence of carbon monoxide under mild conditions (1–3 bar, 90 °C). The reaction demonstrated perfect compatibility with a wide range of functional groups prone to reduction by conventional reducing agents. The developed system represents the first systematic investigation of cyclobutadiene metal complexes as catalysts.

Shockwave compression of methane was simulated using the molecular dynamics method with Hugoniostat and MSST approach. The calculation was carried out employing ReaxFFlg potential. We show comparison of simulated Hugoniots for pressure range 0,1-44 GPa and times required for simulation run of two different methods. We also compare two ReaxFF potentials: ReaxFF(2008) and ReaxFF-lg

Thermal decomposition of methane was simulated at high temperature and pressure using the molecular dynamics method. The calculation was carried out employing ReaxFFlg potential. We show the dependence of the decomposition products on time and the results of methane polymerization at constant temperature. We also show the influence of gradual temperature decrease at the size of the polymers.

Based on analytical and numerical methods, the detailed studies of the temperature and thermostressed condition of quartz reactor intended for production of hydrogen by pyrolysis of methane passed through the molten tin, are performed. Heating of tin contained in the reactor is realized by the application of electromagnetic field generated by the inductor. The analysis of the study results allows concluding that the values of radial, circular and axial stresses during a uniform movement of the reactor along its height even in the most unfavourable conditions when the temperature drop along the wall of the quartz reactor is maximum and is equal to the difference of temperatures between molten tin and environment (ΔT ≈ 1500 °C) are within the tensile strength limit for quartz σ p = 50Mpa (5 kg / mm 2). In case of non-uniform heating of the reactor along its height observed at its partial filling with molten tin, in the area of transfer from the filled part of the reactor to its non-filled part, there are high axial temperature gradients, which result in temperature stresses exceeding the tensile strength limit. By using the obtained results, the recommendations connected with the reactor heating rate and essential for ensuring its safe operation have been developed.

The article discusses a method for predicting a methane explosion in underground workings by observing simultaneously electrical and acoustic noises of the Earth on the surface of a mine field, highlighting their mutual correlation function. When used in the observation of acoustic noises by three-coordinate seismic receivers in two spaced along the Earth’s surface, an algorithm for determining the coordinates of the expected explosion site is described. The results of field tests of the method at the Minusinsk gas condensate field are presented.

In connection with recent data about antiatherogenic importance of not only plasma HDL concentration, but of their cell cholesterol efflux capacity as well, the possibility of its correction by phospholipid (PL) nanoparticles was studied. Blood plasma was incubated with earlier elaborated PL nanoparticles emulsion with the particle diameter up to 30 nm, and HDL cholesterol efflux capacity of apo B-depleted plasma was studied. Using macrophages THP-1 preloaded 3H-cholesterol were used. The addition of incubated plasma supernatants with the elevated PL/apo A-1 ratio to cell media resulted in almost increase in two fold 3H-cholesterol efflux as compared with native HDL. The maximal efflux was observed at the PL/apo A-1 ratio of 1.06 as compared with native apo B-depleted plasma (the PL/apo A-1 ratio of 0.85). Results suggest possible usage of ultrasmall PL nanoparticles for regeneration of impaired antiatherogenic HDL functionality. This approach seems to be predominant compared with the usage of PL emulsions with detergent or apoprotein A1.Issledovali vozmozhnost' povysheniia sposobnosti lipoproteinov vysokoĭ plotnosti (LVP) k vyvedeniiu kholesterina (KhS) s pomoshch'iu ul'tramalykh chastits fosfolipdov (FL) diametrom do 30 nm. Plazmu inkubirovali s razrabotannoĭ ranee stabil'noĭ émul'sieĭ takikh nanochastits i issledovali sposobnost' fraktsiĭ plazmy posle udaleniia apo V-lipoproteinov izvlekat' 3H-KhS iz makrofagov THR-1. Pri dobavlenii v kletochnuiu sredu inkubirovannoĭ plazmy s povyshennym otnosheniem FL/apoprotein A1 vykhod 3H-KhS byl pochti vdvoe vyshe, chem pod deĭstviem nativnykh LVP, dostigaia maksimuma uzhe pri nebol'shom povyshenii otnosheniia FL/apoprotein A-1 – do 1,06 (po sravneniiu s iskhodnym otnosheniem – 0,85.) Rezul'taty ukazyvaiut na vozmozhnost' ispol'zovaniia ul'tramalykh chastits FL dlia vosstanovleniia narushennykh pri ateroskleroze funktsional'nykh antiaterogennykh svoĭstv LVP.

Metallic phase formation model in the barbotage process of oxide melt by gas-reducing is considered. The model includes following stages: bubbles formation during gas injection into the melt, redu cing of the metal on the bubble surface and its drops concentration on bubble stern and this system “gas bubble – metal drop” movement. The direc tion of this movement was determined by the balance of forces that provide bubble fl oating and metal drop sinking, drops ejection onto the surface, its coalescence and sinking after reaching sizes that provide excess over the sum of the gravity force and the hydrostatic ejection surface tension. The equations related to estimation of the sizes of gas bubble and metal drops moving in the oxide melt without fragmentation, direction of the “gas bubble – metal drop” system movement, the rate of its fl oating and sedimentation and separation conditions. The factors that aff ect stratifi cation processes were determined – that are surface properties of the oxide and metal melts and their interfacial characteristics. These parameters variation controls the formation processes of metal bottom phase.

Room temperature reactions of the rhodium and iridium bromides (η-9-SMe2-7,8-Me2-7,8-C2B9H8)MBr2 (M = Rh (1a), Ir (1b)) with CpTl give the dicarbollide thioether complexes (η-9-SMe-7,8-Me2-7,8-C2B9H8)MCp (2a,b), as a result of demethylation of the SMe2 substituent. These reactions are accompanied by transformation of cage structure from pseudocloso to closo. Refluxing of the sulfonium derivatives [(η-9-SMe2-7,8-Me2-7,8-C2B9H8)MCp]+ (3a,b) with [Bu4N]Br also affords 2a,b. In the same manner ruthenacarboranes [(η-9-SMe2-7,8-C2B9H10)Ru(η-C6H6)]+ (4a) and [(η-10-SMe2-7,8-C2B9H10)Ru(η-C6H6)]+ (4b) react with halide ions giving the thioether complexes (η-9-SMe-7,8-C2B9H10)Ru(η-C6H6) (5a) and (η-10-SMe-7,8-C2B9H10)Ru(η-C6H6) (5b). Dependence of the demethylation rate on the nature of halide ion and solvent was studied both experimentally and theoretically. The structures of 2a and 3aPF6 were determined by X-ray diffraction.

The efficient (turnover numbers attained 1200) oxidation of alkanes to the corresponding alkyl hydroperoxides by H2O2 in the presence of catalytic amounts of ferrocene proceeds in MeCN at 40–50 °C. Benzene is oxidized in the same system to phenol. An obligatory component of the catalytic system for both reactions is pyrazine-2-carboxylic acid (PCA) or trifluoroacetic acid (TFA). Kinetic study as well as selectivity parameters testified that the oxidation proceeds with the participation of hydroxyl radicals. In the case of PCA as a co-catalyst the initial rate W0 of the reaction with both cyclohexane and benzene depends quadratically on [Cp2Fe]0 whereas the two reactions in the presence of TFA are of half order in ferrocene. The ferrocene-catalyzed reaction of cyclohexane with H 2 O 2 16 in an atmosphere of labeled 18O2 gave after 2 h a mixture of labeled and unlabeled cyclohexyl hydroperoxide (total yield 20% based on starting cyclohexane) containing up to 69% of 18O (the analysis was after reduction of cyclohexyl hydroperoxide into cyclohexanol with PPh3).

(Arene)iridacarboranes [3-(arene)-3,1,2-IrC 2 B 9 H 11 ] + (arene = benzene ( 1a ), toluene ( 1b ), o -xylene ( 1c ), m -xylene ( 1d ), durene ( 1e )) were synthesized by reaction of [(cod)IrCl] 2 with Tl[Tl(η-7,8-C 2 B 9 H 11 )] with the subsequent treatment of the anion [3-(cod)-3,1,2-IrC 2 B 9 H 11 ] − formed by arenes in refluxing trifluoroacetic acid. Cation 1a reacts with acetonitrile giving complex [3-(MeCN) 3 -3,1,2-IrC 2 B 9 H 11 ] + ( 2 ). Reactions of 2 with Cp – anions and arenes afford the cyclopentadienyl and arene derivatives 3-(η-C 5 H 4 R)-3,1,2-IrC 2 B 9 H 11 (R = H ( 3a ), C(O)Me ( 3b )) and [3-(arene)-3,1,2-IrC 2 B 9 H 11 ] + (arene = mesitylene ( 1f ), [2,2]paracyclophane ( 1g )). The structures of 1e PF 6 and 2 BF 4 were determined by X-ray diffraction. According to energy decomposition analysis, the metal-benzene bonding in the iridium cation 1a is stronger than in the rhodium analog [3-(η-C 6 H 6 )-3,1,2-RhC 2 B 9 H 11 ] + but weaker than in [(C 5 R 5 )Ir(C 6 H 6 )] 2+ . In the presence of Ag 2 CO 3 , iridacarboranes 1a and 2 catalyze the oxidative coupling of benzoic acid with diphenylacetylene selectively giving 3,4-diphenylisocoumarin in 40–50% yields. In contrast, the reactions catalyzed by [3,3-Cl 2 -4-SMe 2 -3,1,2-IrC 2 B 9 H 10 ] 2 and [CpIrI 2 ] 2 afford only 1,2,3,4-tetraphenylnaphthalene in 10 and 35% yields, respectively. The iridium catalyzed decarboxylation of benzoic acid was analyzed by DFT calculations.

A new generation of plant phosphatidylcholine (PC)-based pharmacological agents has been developed under academician A.I. Archakov leadership at the Institute of Biomedical Chemistry (IBMC). For their production a unique technology allowing to obtain dry lyophilized phospholipid nanoparticles of 30 nm was elaborated. The successful practical application of PC nanoparticles as a drug agent may be illustrated by Phosphogliv (oral and injection formulations). Being developed at IBMC for the treatment of liver diseases, including viral hepatitis, Phosphogliv (currently marketed by the "Pharmstandard" company) is approved for clinical application in 2000, and is widely used in medical practice. Based on the developed and scaled in IBMC technology of prerparation of ultra small size phospholipid nanoparticles without the use of detergents/surfactants and stabilizers another drug preparation, Phospholipovit, exhibiting pronounced hypolipidemic properties has been obtained. Recently completed preclinical studies have shown that PC nanoparticles of 20-30 nm activate reverse cholesterol transport (RCT) and in this context it is more active than well known foreign preparation Essentiale. Phospholipovit is now at the stage of clinical trials (phase 1 completed). PC was also used as a basis for the development of a transport nanosystem with a particles size of 20-25 nm in diameter and incorporation of various drug substances from various therapeutic groups. Using several drugs substances as an example, increased bioavailability and specific activity were demonstrated for the formulations equipped with such transport nanosystem. Formulations equipped with the transport nanosystems have been developed for such pharmacological agents as doxorubicin, rifampin, budesonide, chlorin E6, prednisone, and others.V IBMKh pod rukovodstvom akademika RAN A.I. Archakova v techenie riada let vedutsia razrabotki lekarstv novogo pokoleniia na osnove fosfatidilkholina (FKh) rastitel'nogo proiskhozhdeniia. Dlia proizvodstva lekarstv razrabotana original'naia ne imeiushchaia analogov tekhnologiia, kotoraia pozvoliaet poluchat' v sukhom liofilizirovannom vide fosfolipidnye nanochastitsy razmerom do 30 nm. Primerom ispol'zovaniia nanochastits FKh kak lekarstva iavliaetsia razrabotannyĭ v IBMKh lekarstvennyĭ preparat Fosfogliv (peroral'naia i in"ektsionnaia formy) dlia lecheniia zabolevaniĭ pecheni, v tom chisle virusnykh gepatitov. Preparat razreshen k primeneniiu s 2000 g., v nastoiashchee vremia vypuskaetsia firmoĭ “Farmstandart” i shiroko primeniaetsia v meditsinskoĭ praktike. Na osnove razrabotannoĭ i masshtabirovannoĭ v IBMKh tekhnologii polucheniia fosfolipidnykh nanochastits predel'no malogo razmera be z ispol'zovaniia detergentov/surfaktantov i stabilizatorov poluchen lekarstvennyĭ preparat Fosfolipovit, obladaiushchiĭ vyrazhennymi gipolipidemicheskimi svoĭstvami. V zakonchennykh doklinicheskikh issledovaniiakh pokazano, chto FKh v forme nanochastits, razmerom 20-30 nm aktiviruet obratnyĭ transport kholesterina (OTKhS) luchshe, chem izvestnyĭ zarubezhnyĭ preparat Éssentsiale. Fosfolipovit nakhoditsia na stadii klinicheskikh issledovaniĭ (zakonchena 1 faza). Na osnove FKh byla razrabotana transportnaia nanosistema s diametrom chastits 20-25 nm i opredeleny osnovnye printsipy vstraivaniia v nee lekarstvennykh soedineniĭ razlichnykh terapevticheskikh grupp. Na primere riada lekarstv, snabzhennykh takoĭ nanosistemoĭ transporta, pokazano sushchestvennoe uvelichenie biodostupnosti i spetsificheskoĭ aktivnosti. Razrabotany gotovye lekarstvennye formy dlia riada lekarstv, snabzhennykh nanosistemoĭ transporta, takikh, kak doksorubitsin, rifampitsin, budesonid, khlorin E6, prednizolon i dr.