Search Results (16)

Silicon content plays an important role in determining the operational efficiency of blast furnaces (BFs) and their downstream processes in integrated steelmaking; however, existing sampling methods and first-principles models are somewhat limited in their capability and flexibility. Current data-based prediction models primarily rely on a limited set of manually selected furnace parameters. Additionally, different BFs present a diverse set of operating parameters and state variables that are known to directly influence the hot metal’s silicon content, such as fuel injection, blast temperature, and raw material charge composition, among other process variables that have their own impacts. The expansiveness of the parameter set adds complexity to parameter selection and processing. This highlights the need for a comprehensive methodology to integrate and select from all relevant parameters for accurate silicon content prediction. Providing accurate silicon content predictions would enable operators to adjust furnace conditions dynamically, improving safety and reducing economic risk. To address these issues, a two-stage approach is proposed. First, a generalized data processing scheme is proposed to accommodate diverse furnace parameters. Second, a robust modeling pipeline is used to establish a machine learning (ML) model capable of predicting hot metal silicon content with reasonable accuracy. The method employed herein predicted the average Si content of the upcoming furnace cast with an accuracy of 91% among 200 target predictions for a specific furnace provisioned by the XGBoost model. This prediction is achieved using only the past shift’s operating conditions, which should be available in real time. This performance provides a strong baseline for the modeling approach with potential for further improvement through provision of real-time features. Full article

Metallodrugs represent a critical area of medicinal chemistry with the potential to address a wide range of diseases. Their design requires a multidisciplinary approach, combining principles of inorganic chemistry, pharmacology, and molecular biology to create effective and safe therapeutic agents. Vanadium, the element of the fifth group of the first transition series (3d metals), has been already detected as a crucial species in the biological action of some enzymes, e.g., nitrogenases and chloroperoxidase; furthermore, vanadium-based compounds have recently been described as physiologically stable with therapeutic behavior, e.g., having anticancer, antidiabetic (insulin-mimicking), antiprotozoal, antibacterial, antiviral, and inhibition of neurodegenerative disease properties. Since the binding of metallodrugs to serum albumin influences the distribution, stability, toxicity (intended and off-target interactions), and overall pharmacological properties, the biophysical characterization between serum albumin and vanadium-based compounds is one of the hot topics in pharmacology. Overall, since vanadium complexes offer new possibilities for the design of novel metallodrugs, this review summarized some up-to-date biological and medicinal aspects, highlighting proteins as the main targets for the inorganic complexes based on this transition metal. Full article

Aluminum (Al) placed in hot water (HW) at 90 °C is roughened due to its reaction with water, forming Al hydroxide and Al oxide, as well as releasing hydrogen gas. The roughened surface is thus hydrophilic and possesses a hugely increased surface area, which can be useful in applications requiring hydrophilicity and increased surface area, such as atmospheric moisture harvesting. On the other hand, when using HW to roughen specified areas of an Al substrate, ways to protect the other areas from HW attacks are necessary. We demonstrated that self-assembled monolayers (SAMs) of a fluorinated phosphonic acid (FPA, CF₃(CF₂)₁₃(CH₂)₂P(=O)(OH)₂) derivatized on the native oxide of an Al film protected the underneath metal substrate from HW attack. The intact wettability and surface morphology of FPA-derivatized Al subjected to HW treatment were examined using contact angle measurement, and scanning electron microscopy and atomic force microscopy, respectively. Moreover, the surface and interface chemistry of FPA-derivatized Al before and after HW treatment were investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS), verifying that the FPA SAMs were intact upon HW treatment. The ToF-SIMS results therefore explained, on the molecular level, why HW treatment did not affect the underneath Al at all. FPA derivatization is thus expected to be developed as a patterning method for the formation of hydrophilic and hydrophobic areas on Al when combined with HW treatment. Full article

Reservoirs are human-made ecosystems with diverse purposes that benefit humans both directly and indirectly. They however cause changes in geomorphological processes such as sediment cycling and influence the composition and structure of aquatic biota. This study aimed to identify water and sediment quality parameters as drivers of macroinvertebrates and fish communities during the cool-dry and hot-wet seasons in the littoral zones of three subtropical reservoirs (Albasini, Thathe and Nandoni). Macroinvertebrates and fish were collected from three sites (n = 3 from each site) in each reservoir. A total of 501 and 359 macroinvertebrates and fish individuals were collected throughout the sampling period, respectively. The present study employed a two-way ANOVA in conjunction with redundancy analysis (RDA) to assess the relationships that exist between water and sediment variables, macroinvertebrates diversity and species abundances across seasons. Based on the two-way ANOVA model, significant differences were observed across reservoirs for evenness, Simpson’s diversity, and total abundance, while seasonal differences were observed for most metrics, with exception for evenness. The RDA results identified four water variables (i.e., water temperature, oxidation–reduction potential, pH and conductivity) and one sediment metal (Mg) as the most important parameters in driving the fish community structure. Field observations and metal results attest that the Nandoni reservoir shows high concentrations of metals in sediments as compared to other reservoirs, suggesting that anthropogenic activities such as car washing, brick making, recreation, fishing, wastewater treatment work and landfill site may be the major contributor of metals to the Nandoni reservoir, which accumulate in the littoral zones. Findings of this study highlight the need to analyze reservoir ecological conditions at several scales. The study of macroinvertebrates and fish, water, and sediment chemistry in the littoral zone laid the groundwork for proposing measures for conserving aquatic ecosystems. Full article

The Ediacaran peralkaline granites, which were emplaced during the post-collisional tectonic extensional stage, have a limited occurrence in the northern tip of the Nubian Shield. In this contribution, we present new mineralogical and geochemical data of Mount El-Sibai granites from the Central Eastern Desert of Egypt. The aim is to discuss their crystallization condition, tectonic setting, and petrogenesis as well as the magmatic evolution of their associated mineralization. Mount El-Sibai consists of alkali-feldspar granites (AFGs) as a main rock unit with scattered and small occurrences of alkali-amphibole granites (AAGs) at the periphery. The AAG contain columbite, nioboaeschynite, zircon and thorite as important rare metal-bearing minerals. Geochemically, both of AFG and AAG exhibit a highly evolved nature with a typical peralkaline composition (A/CNK = 0.82–0.97) and formed in within-plate anorogenic setting associated with crustal extension and/or rifting. They are enriched in some LILEs (Rb, K, and Th) and HFSEs (Ta, Pb, Zr, and Y), but strongly depleted in Ba, Sr, P and Ti with pronounced negative Eu anomalies (Eu/Eu* = 0.07–0.34), consistent with an A-type granite geochemical signature. The calculated T_Zrn (774–878 °C) temperatures indicate that the magma was significantly hot, promoting the saturation of zircon. The texture and chemistry of minerals suggest that they were crystallized directly from a granitic magma and were later subject to late- to post-magmatic fluids. Both granitic types were most likely generated through partial melting of a juvenile crustal source followed by magmatic fractionation. The lithospheric delamination is the main mechanism which causes uplifting of the asthenospheric melts and hence provides enough heat for crustal melting. The produced parent magma was subjected to prolonged fractional crystallization to produce the different types of Mount El-Sibai granites at different shallow crustal levels. During magma fractionation, the post-magmatic fluids (especially fluorine) contribute significantly to the formation of rare metal mineralization within Mount El-Sibai granites. Full article

The development of metal salts-based nanocomposites is highly desired for the Fenton or Fenton-like reaction-based chemodynamic therapy of cancer. Manganese sulfate (MnSO₄)-dispersed nanoparticles (NPs) were fabricated with a hot-melt extrusion (HME) system for the chemodynamic therapy of colorectal cancer in this study. MnSO₄ was homogeneously distributed in polyethylene glycol (PEG) 6000 (as a hydrophilic polymer) with the aid of surfactants (Span 80 and Tween 80) by HME processing. Nano-size distribution was achieved after dispersing the pulverized extrudate of MnSO₄-based composite in the aqueous media. The distribution of MnSO₄ in HME extrudate and the interactions between MnSO₄ and pharmaceutical additives were elucidated by Fourier-transform infrared, X-ray diffractometry, X-ray photoelectron spectroscopy, and scanning electron microscopy analyses. Hydroxyl radical generation efficiency by the Fenton-like chemistry capability of Mn²⁺ ion was also confirmed by catalytic assays. By using the intrinsic H₂O₂ in cancer cells, MnSO₄ NPs provided an elevated cellular reactive oxygen species level, apoptosis induction capability, and antiproliferation efficiency. The designed HME-processed MnSO₄ formulation can be efficiently used for the chemodynamic therapy of colorectal cancer. Full article

A bibliometric analysis, using the Scopus database as a source, was carried out in order to study the scientific documents published up to 2021 regarding the use of electrodialysis, membrane distillation, and forward osmosis for the removal of heavy metals from wastewater. A total of 362 documents that fulfilled the search criteria were found, and the results from the corresponding analysis revealed that the number of documents greatly increased after the year 2010, although the first document was published in 1956. The exponential evolution of the scientific production related to these innovative membrane technologies confirmed an increasing interest from the scientific community. The most prolific country was Denmark, which contributed 19.3% of the published documents, followed by the two main current scientific superpowers: China and the USA (with 17.4% and 7.5% contributions, respectively). Environmental Science was the most common subject (55.0% of contributions), followed by Chemical Engineering (37.3% of contributions) and Chemistry (36.5% of contribution). The prevalence of electrodialysis over the other two technologies was clear in terms of relative frequency of the keywords. An analysis of the main hot topics identified the main advantages and drawbacks of each technology, and revealed that examples of their successful implementation beyond the lab scale are still scarce. Therefore, complete techno-economic evaluation of the treatment of wastewater polluted with heavy metals via these innovative membrane technologies must be encouraged. Full article

N-Heterocyclic carbenes (NHCs) are nowadays one of the most widely employed ligands in organometallic chemistry and homogeneous catalysis due to the inherent stability of the metal-carbene bond and the ease of modification of the backbone as well as the N-wingtips substituents of these ligands. The functionalization of NHCs with hydrophilic groups offers the possibility of using NHC-metal complexes in aqueous catalysis, a hot topic within the Green Chemistry context due to the positive implications associated with the use of water as a reaction medium. In line with the enormous interest aroused by gold complexes in catalysis, significant efforts have been directed in the last years to the design and application of hydrophilic NHC-gold catalysts. This review is aimed to summarize the research in this area. The catalytic applications of water-soluble gold nanoparticles stabilized by hydrophilic NHCs are also covered. Full article

The Middle Devonian Marcellus Formation of North America is the most prolific hydrocarbon play in the Appalachian basin, the second largest producer of natural gas in the United States, and one of the most productive gas fields in the world. Regional differences in Marcellus fluid chemistry reflect variations in thermal maturity, migration, and hydrocarbon alteration. These differences define specific wet gas/condensate and dry gas production in the basin. Marcellus gases co-produced with condensate in southwest Pennsylvania and northwest West Virginia are mixtures of residual primary-associated gases generated in the late oil window and postmature secondary hydrocarbons generated from oil cracking in the wet gas window. Correlation of API gravity and C₇ expulsion temperatures, high heptane and isoheptane ratios, and the gas geochemical data confirm that the Marcellus condensates formed through oil cracking. Respective low toluene/nC₇ and high nC₇/methylcyclohexane ratios indicate selective depletion of low-boiling point aromatics and cyclic light saturates in all samples, suggesting that water washing and gas stripping altered the fluids. These alterations may be related to deep migration of hot basinal brines. Dry Marcellus gases produced in northeast Pennsylvania and northcentral West Virginia are mixtures of overmature methane largely cracked from refractory kerogen and ethane and propane cracked from light oil and wet gas. Carbon and hydrogen isotope distributions are interpreted to indicate (1) mixing of hydrocarbons of different thermal maturities, (2) high temperature Rayleigh fractionation of wet gas during redox reactions with transition metals and formation water, (3) isotope exchange between methane and water, and, possibly, (4) thermodynamic equilibrium conditions within the reservoirs. Evidence for thermodynamic equilibrium in the dry gases includes measured molecular proportions (C₁/(C₁ − C₅) = 0.96 to 0.985) and δ¹³C₁ values significantly greater than δ¹³C_KEROGEN. Noble gas systematics support the interpretation of hydrocarbon–formation water interactions, constrain the high thermal maturity of the hydrocarbon fluids, and provide a method of quantifying gas retention versus expulsion in the reservoirs. Full article

Hydrophobicity on steel-based metallic surfaces provides an advantage in limiting corrosion and debris buildup on the surface, thereby, improving the substrate performance. An experimental investigation was conducted on the development of zinc stearate and silicon dioxide coatings on the surface of hot-dipped galvanised zinc-coated steel substrates, which could be used to induce superhydrophobicity. Under optimal formulation and processing conditions, a contact angle of 146° could be produced within a 120-min processing window. This represents a reduction in processing time of 67% over previous literature using similar chemistry. In addition, we proved that costly nano silicon dioxide can be replaced by lower cost micro silicon dioxide without decreasing the performance of the coating contact angle. Under standard accelerated exposure tests, the coating was shown to reduce oxide build up by a factor of 3 compared to uncoated galvanized steel. Full article

We discuss the evolution of stars through the asymptotic giant branch, focusing on the physical mechanisms potentially able to alter the surface chemical composition and on how changes in the chemistry of the external regions affect the physical properties of the star and the duration of this evolutionary phase. We focus on the differences between the evolution of low-mass stars, driven by the growth of the core mass and by the surface carbon enrichment, and that of their higher mass counterparts, which experience hot bottom burning. In the latter sources, the variation of the surface chemical composition reflects the equilibria of the proton capture nucleosynthesis experienced at the base of the convective envelope. The pollution expected from this class of stars is discussed, outlining the role of mass and metallicity on the chemical composition of the ejecta. To this aim, we considered evolutionary models of 0.7–8 ${\mathrm{M}}_{\odot }$ stars in a wide range of metallicities, extending from the ultra-metal-poor domain to super-solar chemistries. Full article

Gold (Au) and silver (Ag) nanostructures have widespread utilization from biomedicine to materials science. Therefore, their synthesis with control of their morphology and surface chemistry have been among the hot topics over the last decades. Here, we introduce a new approach relying on sugar derivatives that work as reducing, stabilizing, and capping agents in the synthesis of Au and Ag nanostructures. These sugar derivatives are utilized alone and as mixture, resulting in spherical, spheroid, trigonal, polygonic, and star-like morphologies. The synthesis approach was further tested in the presence of acetate and dimethylamine as size- and shape-directing agents. With the use of transmission electron microscopy (TEM), selected area electron diffraction (SAED), x-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet-visible (UV-vis) absorption spectroscopy techniques, the particle size, shape, assembly, aggregation, and film formation characteristics were evaluated. NPs’ attributes were shown to be tunable by manipulating the sugar ligand selection and sugar ligand/metal-ion ratio. For instance, with an imine side group and changing the sugar moiety from cellobiose to lactose, the morphology of the Ag nanoparticles (NPs) transformed from well dispersed cubic to rough and aggregated. The introduction of acetate and dimethylamine further extended the growth pattern and morphological properties of these NPs. As examples, L5 AS, G5AS, and S5AS ligands formed spherical or sheet-like structures when used alone, which upon the use of these additives transformed into larger multicore and rough NPs, revealing their significant effect on the NP morphology. Selected samples were tested for their stability against protein corona formation and ionic strength, where a high chemical stability and resistance to protein coating were observed. The findings show a promising, benign approach for the synthesis of shape- and size-directed Au and Ag nanostructures, along with a selection of the chemistry of carbohydrate-derivatives that can open new windows for their applications. Full article

Even 155 years after their first synthesis, Schiff bases continue to surprise inorganic chemists. Schiff-base ligands have played a major role in the development of modern coordination chemistry because of their relevance to a number of interdisciplinary research fields. The chemistry, properties and applications of transition metal and lanthanoid complexes with Schiff-base ligands are now quite mature. On the contrary, the coordination chemistry of Schiff bases with actinoid (5f-metal) ions is an emerging area, and impressive research discoveries have appeared in the last 10 years or so. The chemistry of actinoid ions continues to attract the intense interest of many inorganic groups around the world. Important scientific challenges are the understanding the basic chemistry associated with handling and recycling of nuclear materials; investigating the redox properties of these elements and the formation of complexes with unusual metal oxidation states; discovering materials for the recovery of trans-{U^VIO₂}²⁺ from the oceans; elucidating and manipulating actinoid-element multiple bonds; discovering methods to carry out multi-electron reactions; and improving the 5f-metal ions’ potential for activation of small molecules. The study of 5f-metal complexes with Schiff-base ligands is a currently “hot” topic for a variety of reasons, including issues of synthetic inorganic chemistry, metalosupramolecular chemistry, homogeneous catalysis, separation strategies for nuclear fuel processing and nuclear waste management, bioinorganic and environmental chemistry, materials chemistry and theoretical chemistry. This almost-comprehensive review, covers aspects of synthetic chemistry, reactivity and the properties of dinuclear and oligonuclear actinoid complexes based on Schiff-base ligands. Our work focuses on the significant advances that have occurred since 2000, with special attention on recent developments. The review is divided into eight sections (chapters). After an introductory section describing the organization of the scientific information, Sections 2 and 3 deal with general information about Schiff bases and their coordination chemistry, and the chemistry of actinoids, respectively. Section 4 highlights the relevance of Schiff bases to actinoid chemistry. Sections 5–7 are the “main menu” of the scientific meal of this review. The discussion is arranged according the actinoid (only for Np, Th and U are Schiff-base complexes known). Sections 5 and 7 are further arranged into parts according to the oxidation states of Np and U, respectively, because the coordination chemistry of these metals is very much dependent on their oxidation state. In Section 8, some concluding comments are presented and a brief prognosis for the future is attempted. Full article

Native iron has been identified in an active thermogenic travertine deposit, located at Ilia area (Euboea Island, Greece). The deposit is forming around a hot spring, which is part of a large active metallogenetic hydrothermal system depositing ore-bearing travertines. The native iron occurs in two shapes: nodules with diameter 0.4 and 0.45 cm, and angular grains with length up to tens of μm. The travertine laminae around the spherical/ovoid nodules grow smoothly, and the angular grains are trapped inside the pores of the travertine. Their mineral-chemistry is ultra-pure, containing, other than Fe, only Mn (0.34–0.38 wt.%) and Ni (≤0.05 wt.%). After evaluating all the possible environments where native iron has been reported up until today and taking under consideration all the available data concerning the study area, we propose two possible scenarios: (i) Ilia’s native iron has a magmatic/hydrothermal origin i.e., it is a deep product near the magmatic chamber or a peripheral cooling igneous body that was transferred during the early stages of the geothermal field evolution, from high temperature, reduced gas-rich fluids and deposited along with other metals in permeable structural zones, at shallow levels. Later on, it was remobilized and mechanically transferred and precipitated at the Ilia’s thermogenic travertine by the active lower temperatures geothermal fluids; (ii) the native iron at Ilia is remobilized from deep seated ophiolitic rocks, originated initially from reduced fluids during serpentinization processes; however, its mechanical transport seems less probable. The native iron mineral-chemistry, morphology and the presence of the other mineral phases in the same thermogenic travertine support both hypotheses. Full article

Due to their small size, extremely fast response, and low cost, refractory metallic thin film thermocouples (TFTCs) are well suited for the surface temperature measurement of hot components. In this study, PtRh films with different amounts of Rhodium (10% and 13%) were deposited with direct current magnetron sputtering and annealed at different temperatures in air. The chemistry, microstructure, and resistivity of the films were investigated. Type S (Pt10%Rh-Pt) and type R (Pt13%Rh-Pt) TFTC were fabricated on alumina substrates. Rhodium segregation at the surface of PtRh film was observed, and the variation of the thermoelectric properties of TFTCs was discussed based on the chemistry and microstructure of PtRh films. Full article