Evaluation of the In Vitro and In Vivo Efficacy of Ruthenium Polypyridyl Compounds against Breast Cancer

The clinical success of cisplatin, carboplatin, and oxaliplatin has sparked the interest of medicinal inorganic chemistry to synthesize and study compounds with non-platinum metal centers. Despite Ru(II)–polypyridyl complexes being widely studied and well established for their antitumor properties, there are not enough in vivo studies to establish the potentiality of this type of compound. Therefore, we report to the best of our knowledge the first in vivo study of Ru(II)–polypyridyl complexes against breast cancer with promising results. In order to conduct our study, we used MCF7 zebrafish xenografts and ruthenium complexes [Ru(bipy)2(C12H8N6-N,N)][CF3SO3]2Ru1 and [{Ru(bipy)2}2(μ-C12H8N6-N,N)][CF3SO3]4Ru2, which were recently developed by our group. Ru1 and Ru2 reduced the tumor size by an average of 30% without causing significant signs of lethality when administered at low doses of 1.25 mg·L−1. Moreover, the in vitro selectivity results were confirmed in vivo against MCF7 breast cancer cells. Surprisingly, this work suggests that both the mono- and the dinuclear Ru(II)–polypyridyl compounds have in vivo potential against breast cancer, since there were no significant differences between both treatments, highlighting Ru1 and Ru2 as promising chemotherapy agents in breast cancer therapy.

Monitoring of Flotation Systems by Use of Multivariate Froth Image Analysis

Froth image analysis has been considered widely in the identification of operational regimes in flotation circuits, the characterisation of froths in terms of bubble size distributions, froth stability and local froth velocity patterns, or as a basis for the development of inferential online sensors for chemical species in the froth. Relatively few studies have considered flotation froth image analysis in unsupervised process monitoring applications. In this study, it is shown that froth image analysis can be combined with traditional multivariate statistical process monitoring methods for reliable monitoring of industrial platinum metal group flotation plants. This can be accomplished with well-established methods of multivariate image analysis, such as the Haralick feature set derived from grey level co-occurrence matrices and local binary patterns that were considered in this investigation.

PLATINUM METAL MINERALIZATION OF THE SOUTH URALS MAGMATIC COMPLEXES: GEOLOGICAL AND GEODYNAMIC CHARACTERISTICS OF FORMATIONS, PROBLEMS OF THEIR GENESIS, AND PROSPECTS

In the South Urals, we have identified and investigated two platinum-bearing formations – ophiolite chromitebearing complexes, and the Khudolaz differentiated mafic-ultramafic complex with sulfide Cu-Ni mineralization. The ophiolite chromite-bearing complexes include fragments of the upper mantle and lower crust of the Paleouralian Ocean, which were induced by collision onto the edge of the East European platform. The origin of the Khudolaz complex is related a mantle plume activity. Here, we review and compare the main features of platinum-metal mineralization (PMM) in these two formations.The article presents the results of mineralogical and geochemical studies of PMM associated with chromite and sulfide Cu-Ni ores. In association with chromitites, two types of PMM are distinguished: (1) predominating refractory platinoids in chromitites of the mantle unit of the section, and (2) predominating platinum and palladium in chromitites of the transitional wehrlite-clinopyroxenite complex. Compositions of platinum group minerals (PGM) and relations between their elements and host minerals suggest that the minerals of the ophiolite chromite-bearing complexes are of a restite origin, while the Khudolaz complex results from a combination of magmatic processes and solid-phase redistribution of material. Palladium (michenerite, froodite, merenskyite, borovskite, sudburyite) and platinum (sperrylite, moncheite) minerals are found in magmatic sulfide ores of the Khudolaz complex, which were subjected to hydrothermal metasomatization. Texture observations using electron microscope and optical (reflected light) images, as well as LA ICP MS analyses of sulfides suggest late- and post-magmatic crystallization of PMM in three phases: (1) immiscible metalloid or highly fractionated residual sulfide melts trapped in sulfides; (2) segregation of isomorphic impurities of platinum group elements (PGE) and chalcogenide elements from sulfide solid solutions; and (3) interaction of hydrothermal fluids with soluble sulfides.Prospective for PMM are extended bodies of disseminated chromitites in marginal dunites of the Kraka and Nurali massifs, and wehrlite-clinopyroxenite complexes of the same massifs containing PGE (above 500 ppb). In the Khudolaz complex, promising PMM bodies are low-metasomatized parts of sulfide ore bodies (1 ppm of ΣPGE and above) located in the largest massifs, Severny Buskun and Zapadny Karasaz. Exocontact zones of these intrusions are also promising for PMM.

Reconciling metal–silicate partitioning and late accretion in the Earth

Highly siderophile elements (HSE), including platinum, provide powerful geochemical tools for studying planet formation. Late accretion of chondritic components to Earth after core formation has been invoked as the main source of mantle HSE. However, core formation could also have contributed to the mantle’s HSE content. Here we present measurements of platinum metal-silicate partitioning coefficients, obtained from laser-heated diamond anvil cell experiments, which demonstrate that platinum partitioning into metal is lower at high pressures and temperatures. Consequently, the mantle was likely enriched in platinum immediately following core-mantle differentiation. Core formation models that incorporate these results and simultaneously account for collateral geochemical constraints, lead to excess platinum in the mantle. A subsequent process such as iron exsolution or sulfide segregation is therefore required to remove excess platinum and to explain the mantle’s modern HSE signature. A vestige of this platinum-enriched mantle can potentially account for 186Os-enriched ocean island basalt lavas.

Platinum-group minerals from alluvial placers of the Kitoy river (south-east part of East Sayan, Russia)

<p>The studied area is in the southeastern region of Eastern Sayan. Several tectonically dissected ophiolite complexes were exposed along the margin of the Gargan block and tectonically thrust over this block. Placer nuggets of PGE alloys from the Kitoy river were examined using a scanning electron microscope. Platinum-group minerals (PGM's) in placer deposits provide vital information about the types of their primary source rocks and ores as well as the conditions of formation and alteration. The primary PGM's are Os-Ir-Ru alloys, (Os, Ru)S<sub>2</sub>, and (Os, Ir, Ru)AsS. (Os, Ru)S<sub>2</sub> form overgrowth around the Os-Ir-Ru alloys. The secondary, remobilized PGM's are native osmium, (Ir-Ru) alloys, garutite (Ir, Ni, Fe), zaccarinite (RhNiAs), selenides, tellurides (Os, Ir, Ru), and non-stoichiometric (Pd, Pt, Fe, Te, Bi) phases (Fig.1). Secondary PGM's (garutite and RhNiAs) form rims around Os-Ir-Ru alloys, intergrowth with them, or form polyphase aggregates. Such PGM's (identical in composition and microstructure) are also found in chromitites from Neoproterozoic ophiolite massifs of Eastern Sayan (Kiseleva et al., 2014; 2020). Platinum-metal minerals, exotic for ophiolites, are found among secondary PGM's such as selenides and tellurides (Os, Ir, Ru), (Pt, Pd)<sub>3</sub>Fe, Pd<sub>3</sub>(Te, Bi), (Au, Ag), and non-stoichiometric (Pd, Pt, Fe, Te, Bi) phases. They occur as inclusions in the Os-Ir-Ru alloys or fill cracks in crushed grains of primary PGM's. PGM's in placer deposits of the Kitoy river are similar to the mineral composition of PGE in chromitites of the Ospa-Kitoy ophiolitic massif, which contain Pt-Pd minerals and Pt impurities in Os-Ir-Ru alloys (Kiseleva et al., 2014). Selenides (Os-Ir-Ru) are rare within PGM's from ophiolite chromitites (Barkov et al., 2017; Airiyants et al., 2020) and also occur in chromitites of the Dunzhugur ophiolite massif (Kiseleva et al., 2016). Features of selenides and tellurides (Os, Ir, Ru) indicate their late formation as a result of the influence of magmatic and metamorphic fluids on primary PGE alloys. The filling of cracks in crushed (Os-Ir-Ru) alloys indicates that selenides and tellurides formed during tectonic deformation processes. The source of platinum-group minerals from the Kitoy river placer is the Ospa-Kitoy ophiolite massif, and primarily chromitites.</p><p><img src="https://contentmanager.copernicus.org/fileStorageProxy.php?f=gepj.eb9553e3c70065361211161/sdaolpUECMynit/12UGE&app=m&a=0&c=f3ccc1c7cf7d06094d2afaa34fe9d9a1&ct=x&pn=gepj.elif&d=1" alt=""></p><p>Figure 1. BSE microphotographs of PGM from from alluvial placers of the Kitoy river</p><p>Mineral chemistry was determined at the Analytical Centre for multi-elemental and isotope research SB RAS. This work supported by RFBR grants: No. 16-05-00737a,  19-05-00764а, 19-05-00464a and the Russian Ministry of Education and Science</p><p>References</p><p>Airiyants E.V., Belyanin D.K., Zhmodik S.M., Agafonov L.V., Romashkin P.A.  // Ore Geology Reviews. 2020. V. 120. P.  103453</p><p>Barkov A.Y., Nikiforov A.A., Tolstykh N.D., Shvedov G.I., Korolyuk V.N. // European J. Mineralogy. 2017. V.29(9). P.613-621.</p><p>Kiseleva O.N., Zhmodik S.M., Damdinov B.B., Agafonov L.V., Belyanin D.K. // Russian Geology and Geophysics. <strong>2014</strong>. V. 55. P. 259-272.</p><p>Kiseleva O.N., Airiyants E.V., Belyanin D.K., Zhmodik S.M., Ashchepkov I.V., Kovalev S.A. // Minerals. 2020. V. 10. N 141. P. 1-30.</p><p>Kiseleva O.N., Airiyants E.V., Zhmodik S.M., Belyanin D.K / Russian and international conference proceedings “The problems of geology and exploitation of platinum metal deposits” – St.Petersburg: Publishing house of St.Petersburg State University. 2016. 184 P.</p>

Synthesis and Application of Nanolayered and Nanoporous Materials

Nanoscale materials are currently an attractive research subject because their properties are in contrast to their macroscopic counterparts. An inert material, such as bulk platinum metal for example, is known to exhibit a catalytic properties when its size is reduced into nanoscale. A stable material can become flammable or combustible, such as aluminum, and isolator material can become a conductor. Many attractive quantum phenomena also arise from reducing a material size into nanoscale dimensions. This review article discusses the concept, synthesis, and characterization of organic and inorganic nanolayered and nanoporous materials; and their application to catalysis and adsorption processes. Past achievements and future perspectives in the field of nanomaterial researches will be discussed as well. Furthermore, in the era of green chemistry, nanomaterials with all their derivatives are also required to have sustainable characteristics, such as biodegradable and renewable; which emphasizes that the development of nanomaterials in the framework of green chemistry should always be a priority. Through the synthesis of novel and functional nanomaterials using natural and local-based materials around us that are environmentally friendly and relatively easy to be obtained, our goal toward the inheritance of a greener world for the future generations is not an impossible dream.