Search Results (120)

Inorganic nanoparticles (NPs) have been synthesised via mixing and coalescence of droplets containing precursors and entrained by gaseous streams. The droplets have been generated by ultrasonic aerosolisation of two different liquid phases, each containing the respective reagent. The as-produced NPs are trapped by mixing with a liquid phase in a Venturi nozzle, acting simultaneously as a collector and concentrator of the solid nanosized phase produced. Commercial electrically powered ultrasonic aerosolising devices have been adapted to atomise salt solutions characterised by high electrical conductivity. This process allowed the synthesis of calcium carbonate NPs with an average diameter in the range of (34–52) nm, according to the concentration of precursors in the aerosolised phases. This closed-loop method of synthesis, where neither capping agents were used nor demanding operating conditions were adopted, can represent a safe and viable eco-friendly technique for NP production free of undesirable compounds, as required for pharmaceutical preparations and theranostic uses. Full article

A 3D-printed device was designed and printed by a stereolithographic technique (SLA) and coated with a highly selective solid phase extraction resin for on-site diclofenac extraction from wastewater, avoiding the transport and treatment of large volumes of samples in the laboratory. The best results in terms of chemical and mechanical resistance were obtained with Rigid 10K resin. The “stick-and-cure” impregnation technique was used to coat the 3D-printed device with Oasis^® HLB resin. The coated 3D-printed device can be reused up to eight times without losing extraction efficiency. The eluent and derivatization reagent volumes were optimized by a multivariate design. The proposed method allowed for the extraction and determination of diclofenac by PTV-GC-MS, achieving methodological detection and quantification limits of 0.019 and 0.055 μg L⁻¹, respectively, with a preconcentration factor of 46. The analysis time was 23 min per sample. To validate the proposed methodology, addition/recovery tests were carried out in different wastewater samples, obtaining recoveries above 90%. The methodology was applied at the wastewater treatment plant (WWTP) of Calvià (Mallorca, Spain), finding diclofenac in concentrations of 15.39 ± 0.07 μg L⁻¹ at the input of the primary decantation process, 4.48 ± 0.03 μg L⁻¹ at the output of the secondary decantation, and 0.099 ± 0.001 μg L⁻¹ at the output of the tertiary treatment, demonstrating the feasibility of the on-site extraction method in monitoring diclofenac over a wide concentration range. Finally, a greenness index of 0.58 for the proposed on-site sample preparation was achieved according to the AGREEprep metrics, making it an eco-friendly alternative for diclofenac monitoring. Full article

This study compares gold leaching using sodium cyanide (NaCN) with alternative YX500 and Jinchan reagents. The research object was a gold–sulfide polymetallic ore (Republic of Kazakhstan) with a gold content of 0.38 g/t. The closed flotation beneficiation experiment resulted in a concentrate with an 81.40% recovery and a 5.3 g/t gold grade. The resulting concentrate was subjected to oxidizing roasting to completely oxidize the sulfides and mineral grains of arsenopyrite, pyrite, and carbon. A comparative evaluation of leaching showed that the gold recovery from the roasted concentrate using alternative YX500 and Jinchan reagent solutions was comparable to that using NaCN, with the recoveries at approximately the same level of 86.5%. The differential analysis of the obtained multiplicative multifactor Protodyakonov–Malyshev model made it possible to determine the apparent activation energy of the process using the Arrhenius equation, which eliminates the widely used graphical model. In the proposed method of kinetic experiment planning, the time differentiation of the Kolmogorov–Erofeev equation is mandatory, determining it as a partial dependence on the duration and multiplicative equation for all transformations to determine the activation energy of the process at any given conversion value and other operative factors. The variation range of the apparent value of the activation energy of the gold leaching process, from 0.718 to 78.0 kJ/mol, indicates that the limiting stage of this process is the solid-phase diffusion of CN ions from the outside to the center of the grain material. Full article

The safety-catch concept involves a protecting group that remains stable under a range of chemical conditions and subsequently becomes labile under one of those conditions upon a chemical modification of the protecting group. The safety-catch approach introduces flexibility into the scheme, enabling the use of the same reagent in two distinct steps of the chemical process. For example, it facilitates α-amino deprotection and final cleavage in a solid-phase peptide synthesis scheme. Herein, we developed a safety-catch linker based on sulfinyl designed to enable peptide elongation via fluorenylmethoxycarbonyl (Fmoc) chemistry. Subsequently, upon chemical modification (oxidation of the sulfinyl group into the corresponding sulfone), the peptide is released using a secondary amine via a β-elimination reaction, which also serves to remove the Fmoc group in each step. The optimization of both key reactions, oxidation of the linker, and peptide release were achieved using a multi-detachable system, which allows specific control of both reactions. The use of this linker opens the possibility of cleaving peptides from the solid support without trifluoroacetic acid. Full article

The growing demand for metal production promotes the search for alternative sources and novel modalities in metallurgy. Flotation tailings are an important secondary mineral resource; however, they might pose a potential environmental threat due to containing toxic metals. Therefore, proper leaching reagent selection is required. Ozone is an alternative oxidizing agent for metal leaching, as its use prevents contaminating product generation while increasing the noble metal extraction efficiency in the presence of complexing agents. In this study, the feasibility and efficiency of combining the use of thiosulfate and ozone for gold and silver extraction have been investigated as an eco-friendly alternative for recovery from flotation tailings. Two sets of samples from old flotation tailings of Copper Mine Bor (Serbia) were prepared and physico-chemically characterized, then treated in two experimental leaching procedures, followed by thorough XRD and SEM/EDS analyses of the products. It showed that after 1 h of leaching in a water medium at room temperature and a solid-to-liquid phase ratio of 1:4, 88.8% of Cu was obtained, while a high efficiency of Au extraction from solid residue (after Cu leaching) was attained (83.4%). The results suggest that ozone-assisted leaching mediated by Ca-thiosulfate can be an effective eco-friendly treatment for noble metals recovery from sulfide-oxide ores. Full article

The solid phase composition in oily sludge (OS) is a key factor affecting the oil–solid separation of OS. In this paper, the effects and mechanisms of solid-phase particle factors on the oil content of residue phase were investigated in order to improve the oil–solid separation efficiency. Flotation experiments were carried out on single-size sand and mixed-size sand OS consisting of three particle sizes at room temperature without adding flotation reagents. The effects of different-size particles as solid phase composition of OS and flotation parameter settings such as flotation temperature (Tp), flotation time (Tt), impeller speed (Rs) and liquid-solid ratio (L/OS) on the oil–solid separation efficiency were investigated. The experimental results showed that the oil content of residue phase decreased with the increasing of solid-phase particle size for single-size sand OS, and the optimal flotation conditions were Tp of 50 °C, Tt of 25 min, Rs of 1450 r/min and L/OS of 12:1. The oil–solid separation was more pronounced for mixed-size sand OS with a complex particle composition, while different particle compositions of the solid phase in OS promoted oil–solid separation. Scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FT-IR) characterisation of OS before and after flotation confirmed the relative advantage of coarse particle OS in the oil–solid separation process. The classical first-order model was well fitted to the flotation kinetic process of single-size sand and mixed-size sand OS. The response surface methodology (RSM) method was used to determine the Rs as the main control factor of the flotation process, and the oil content of residue phase in mixed-size sand OS was optimised to 2.63%. This study provides important process parameters and theoretical basis for the efficient treatment of OS. Full article

Polyphenolic compounds are considered one as the most important plant-originated species with antioxidant properties. This paper focuses on exploring the structure and antiradical properties of supramolecular complexes derived from the selected polyphenolic (caffeic and protocatechuic) acids and isomers of pyridinecarboxamide. The chemical interactions between polyphenolic acids and carboxamides were analyzed using FT–IR spectroscopy. The thermal behavior of the solid phases was tested with the help of thermal analysis via thermogravimetry (TG) coupled with differential scanning calorimetry (DSC). The antiradical activity was determined by using the ABTS method (2,2′-azino-bis(3-ehylbenzothiazoline-6-sulfonic acid). The obtained results indicate that the solutions prepared by dissolving the solid materials exhibited better antiradical activity than the binary mixtures prepared by mixing the stock reagents’ solutions. These studies confirmed that supramolecular complexes derived from polyphenolic compounds and N-heterocyclic entities may constitute a quite interesting material for future research. Full article

One of the priority goals of sustainable socio-economic development for the period up to 2030 is providing food for the planet’s population. This entails an increase in the output of mineral fertilizers and, consequently, an increase in the quantities of solid industrial waste. Phosphogypsum, a by-product of phosphate fertilizer production from apatite ore, is one example of such waste. The problem of solid industrial waste recycling is urgent. The present study examines the process of converting calcium sulfate, in the form of a reagent, and phosphogypsum into a composite material of calcium sulfate/sulfide. An environmentally friendly material, sucrose, is used as a reducing agent. Reduced phosphogypsum (as well as calcium sulfate) luminescence is suggested to be associated with the formation of a CaS/CaSO₄ composite material. The synthesized materials are characterized by X-ray phase analysis, X-ray photoelectron spectroscopy, elemental analysis, and calcium sulfide qualitative and quantitative content in the samples. It is shown that in the reduction process at the phase contact point, crystal grids are formed with a significant number of defects, which contributes to the convergence of some of the energy levels of the calcium cation and sulfide anion, facilitating the transitions of electrons from the valence zone to the core zone and the formation of luminescence centers (cross-luminescence). Both samples of reduced phosphogypsum and alkaline earth metal sulfates are found to exhibit luminescence properties under ultraviolet radiation. The data obtained open up broad prospects for the use of solid industrial waste for the synthesis of new materials. Full article

Methyl ethyl ketone (MEK) is among the most extensively utilized solvents in various industrial applications. In this study, we present a highly efficient synthesis route for MEK via the decarboxylation of biomass-derived levulinic acid, using potassium persulfate (K₂S₂O₈) and silver nitrate (AgNO₃) as key reagents. The specific roles of AgNO₃ and K₂S₂O₈ were thoroughly investigated. Additional silver species, such as Ag₂O and AgO, were also detected during the reaction. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses provided evidence of the evolution of solid phases throughout the reaction. Based on these findings, we propose a radical decarboxylation mechanism initiated by the generation of sulfate radicals (SO₄•⁻) through the catalytic breakdown of K₂S₂O₈ by AgNO₃. This mechanistic understanding, combined with a parametric study, enabled us to achieve an unprecedented level of levulinic acid conversion (97.9%) and MEK yield (86.6%) with this system, surpassing all previously reported results in the literature. Full article

Background: Affibody molecules represent a class of highly specific binders of particular interest for the development of highly affine target-specific radiopharmaceuticals. Their chemical synthesis is, however, intricate due to their considerable length of 58 amino acids; thus, approaches to optimize their preparation are constantly being sought. Methods: As ultrasound assistance has recently been shown to increase the efficiency of amino acid conjugation during solid-phase peptide synthesis (SPPS), the influence of ultrasonication on the outcome of the SPPS-based preparation of the EGFR-specific affibody Z_EGFR:1907 was compared to a common protocol relying on mechanical shaking. Results: After the identification of a suitable solid support for the study, the execution of the systematic comparison of both approaches showed that conventional and ultrasound-assisted syntheses yielded equivalent results with analogous composition of the raw products. Further, both approaches produced the affibody in good isolated yields of >20% when applying the same optimal reagent excesses and coupling times for the conjugation of each amino acid. This indicates that, under optimal reaction conditions, the choice of solid support used has a much stronger influence on the outcome of the preparation of Z_EGFR:1907 than the application of ultrasound, which did not further improve the synthesis results. Conclusions: Therefore, for the chemical synthesis of affibodies, great attention should be paid to the choice of a suitable solid support, enabling this highly interesting class of biomolecules to be obtained in good yields and to bring them more into the focus of radiopharmaceutical research. Full article

Trace concentrations of dyes are often present in textile wastewater streams and present a serious environmental problem. Thus, these dyes must be removed from wastewater either by degradation or sequestration prior to discharge of the wastewater into the environment. Existing processes to remove these wastewater contaminants include the use of solid sorbents to sequester dyes or the use of biochemical or chemical methods of dye degradation. However, these processes typically generate their own waste products, are not necessarily rapid because of the low dye concentration, and often use expensive or non-recyclable sequestrants or reagents. This paper describes a simple, recyclable, liquid–liquid extraction scheme where ionic dyes can be sequestered into poly(α-olefin) (PAO) solvent systems. The partitioning of anionic and cationic dyes from water into PAOs is facilitated by ionic PAO-phase anchored sequestering agents that are readily prepared from commercially available vinyl-terminated polyisobutylene (PIB). This is accomplished by a sequence of reactions involving hydroboration/oxidation, conversion of an alcohol into an iodide, and conversion of the resulting primary alkyl iodide into a cationic nitrogen derivative. The products of this synthetic sequence are cationic nitrogen iodide salts which serve as anionic sequestrants that are soluble in PAO. These studies showed that the resulting series of cationic PIB-bound cationic sequestering agents facilitated efficient extraction of anionic, azo, phthalein, and sulfonephthalein dyes from water into a hydrocarbon PAO phase. Since the hydrocarbon PAO phase is completely immiscible with water and the PIB derivatives are also insoluble in water, neither the sequestration solvent nor the sequestrants contaminate wastewater. The effectiveness and efficiency of these sequestrations were assayed by UV–visible spectroscopy. These spectroscopic studies showed that extraction efficiencies were in most cases >99%. These studies also involved procedures that allowed for the regeneration and recycling of these PAO sequestration systems. This allowed us to recycle the PAO solvent system for at least 10 sequential batch extractions where we sequestered sodium salts of methyl red and 4′,5′-dichlorofluorescein dyes from water with extraction efficiencies of >99%. These studies also showed that a PIB-bound derivative of the sodium salt of 1,1,1-trifluoromethylpentane-2,4-dione could be prepared from a PIB-bound carboxylic acid ester by a Claisen-like reaction and that the sodium salt of this β-diketone could be used to sequester cationic dyes from water. This PIB-bound anion rapidly and efficiently extracted >99% of methylene blue, malachite green, and safranine O from water based on UV–visible and ¹H NMR spectroscopic assays. Full article

A common issue in studies on liquid-phase chemical processes is that the natural solid nanoimpurities present in reagent-grade chemicals are ignored. Little is known about these impurities’ nature, sizes, concentrations, and behavior, yet they significantly affect the efficiency of antiscalants in municipal and laboratory solutions. Recent research has focused on: (i) estimating nanoimpurity concentrations in in-house deionized water and semiconductor-grade isopropanol using “light sheet” optical ultramicroscopy, and (ii) visualizing antiscalant sorption on these impurities. Using a fluorescent-tagged antiscalant aminobis(methylenephosphonic acid) (ADMP-F), we tracked its affinity to particulate matter in deionized water and reagent-grade KCl solutions. Our study showed that the total concentration of nanoparticles with a size larger than 20 nm is about 10⁶ units/mL in deionized water and 10⁵ units/mL in isopropanol. Extrapolation of these values to a size ≥1 nm resulted in concentrations of 10¹¹ and 10⁸ units/mL. The addition of KCl or ADMP-F significantly increased foreign nanoparticle populations. ADMP-F is selectively adsorbed by only some impurities, while most antiscalant molecules remain as true solution. To our knowledge, this is the first instance of fluorescently labeled aminoalkylphosphonates being able to differentiate particulate matter traces in reagent-grade purity solutions. Therefore, the role of nanoparticles as crystallization centers should be seriously reconsidered, especially in their important application in scale inhibition. Full article

In this paper, we present the characteristics of photoluminescent YBO₃ successfully synthesized through a solid-state reaction and a microwave-assisted method. We used yttrium oxide and boric acid in excess as the starting reagents. The synthesis conditions were reflected in the fluorescent characteristics and the structure. Excess boric acid caused structural changes, as observed by the FTIR spectroscopy analysis. Powder X-ray diffraction (XRD) analysis confirmed the crystalline phases and purity of the samples. We observed improved photoluminescence properties in the samples synthesized by the microwave-assisted method. These findings enhance the understanding of the material’s properties and indicate potential applications in illumination, displays, and narrow-band fluorescent smartphone-readable markers. Full article

The use of mixtures of thiol collectors has been reported to benefit the flotation of Cu-Ni-PGM ores. However, the increasing reliance on recycled water in mineral processing may alter the performance of flotation reagents. This necessitates a deeper understanding of flotation reagents into their behaviour in different components or constituents of process water. This is crucial for better decision-making when determining the quality of process water that optimises reagent performance for specific ores. Ca²⁺ and Na⁺ are common cations in process water and are known to exert various effects in both the pulp and froth phases, making them frequent subjects of recent investigations into water quality. In contrast, NO₃⁻ anions have received less research attention compared to other common ions in process water, such as Cl⁻, SO₄²⁻, and S₂O₃²⁻, despite being present in significant concentrations. NO₃⁻ ions are understood to originate from blasting chemicals used during mining, leaching into solution during milling, and thus can be considered key players in the interactions occurring in the pulp phase. Their interactions in the pulp phase and their role in flotation are therefore important to consider. This work presents results from bench-scale batch flotation tests conducted on a Cu-Ni-PGM ore from the Merensky Reef, using mixtures of thiol collectors, namely sodium isobutyl xanthate and sodium diethyl dithiophosphate, in solutions containing Ca(NO₃)₂ and NaNO₃. NaNO₃ solutions showed higher solids recoveries for all thiol collector mixtures compared to Ca(NO₃)₂ solutions, this was attributed to increased gangue entrainment in Na⁺ compared to Ca²⁺. Higher Cu and Ni recoveries were observed in NaNO₃ solutions across all thiol collector mixtures; however, higher Cu and Ni grades were achieved in Ca(NO₃)₂ solutions compared to NaNO₃. Full article

Solid-phase peptide synthesis (SPPS) is the preferred strategy for synthesizing most peptides for research purposes and on a multi-kilogram scale. One key to the success of SPPS is the continual evolution and improvement of the original method proposed by Merrifield. Over the years, this approach has been enhanced with the introduction of new solid supports, protecting groups for amino acids, coupling reagents, and other tools. One of these improvements is the use of the so-called “safety-catch” linkers/resins. The linker is understood as the moiety that links the peptide to the solid support and protects the C-terminal carboxylic group. The “safety-catch” concept relies on linkers that are totally stable under the conditions needed for both α-amino and side-chain deprotection that, at the end of synthesis, can be made labile to one of those conditions by a simple chemical reaction (e.g., an alkylation). This unique characteristic enables the simultaneous use of two primary protecting strategies: tert-butoxycarbonyl (Boc) and fluorenylmethoxycarbonyl (Fmoc). Ultimately, at the end of synthesis, either acids (which are incompatible with Boc) or bases (which are incompatible with Fmoc) can be employed to cleave the peptide from the resin. This review focuses on the most significant “safety-catch” linkers. Full article