Search

Carbamazepine is a crucial medication used to treat nervous system disorders, and its low level of absorption in the human body suggests that a significant amount of it may be present in sewage water. Consequently, this pioneering research deals with the synthesis and application of a luminescent sensor based on rhodamine 6 G-modified bifunctional silica particles for the determination of carbamazepine. The sensing material was fabricated in one step by the sol–gel technique and the dye was adsorbed onto the surface from an alcohol solution. The composition, morphology and size of functionalized silica particles were determined by physico-chemical methods. The material’s features provide the possibility of its application as a sensing material for carbamazepine determination at a variety of concentrations. The sensor possesses a linear response towards carbamazepine in the concentration range of 0.8–200.0 μM with a limit of detection (LOD) of 17.9 μM and a limit of quantification (LOQ) of 59.7 μM and has demonstrated reliable quantification over a wide range of concentrations, from therapeutic to high fatal concentrations. Additionally, the sensing mechanism has been proposed, which involves the formation of hydrogen bonding between carbamazepine and Rhodamine 6G immobilized bifunctional silica particles.

Copper, antimony and sulfur in elemental form were applied for one-pot solid-state mechanochemical synthesis of skinnerite (Cu

An effort to prepare different non-stoichiometric Cu

In this work, the very rapid one-step mechanochemical synthesis of nanocrystalline ternary chalcogenide chalcostibite CuSbS2 prepared from copper, antimony, and sulfur precursors by high-energy milling for only 30 min in a planetary mill is reported. XRD confirmed the orthorhombic crystal structure of CuSbS2. The crystallite size of CuSbS2 calculated by LeBail refinement of the X-ray powder diffraction data was 25 nm. The nanocrystalline chalcostibite CuSbS2 was also confirmed by transmission electron microscopy. The purity of CuSbS2 was verified by Raman spectroscopy. The synthesized chalcostibite exhibits the specific surface area value of 2.4 m2g−1. UV–Vis spectroscopy showed the optical bandgap of CuSbS2 as 1.54 eV with wide range of absorption in visible region. Photoresponse of CuSbS2 was confirmed by I–V measurements under dark and light illumination. The proposed mechanochemical synthesis provides an alternative approach to prepare also other ternary semiconductor nanomaterials. CuSbS2 semiconductor nanocrystals have the potential to be used as light absorbers in photovoltaics.

Chalcopyrite CuFeS2, a semiconductor with applications in chemical sector and energy conversion engineering, was synthetized in a planetary mill from elemental precursors. The synthesis is environmentally friendly, waste‐free and inexpensive. The synthesized nano‐powders were characterized by XRD, SEM, EDX, BET and UV/Vis techniques, tests of chemical reactivity and, namely, thermoelectric performance of sintered ceramics followed. The crystallite size of ∼13 nm and the strain of ∼17 were calculated for CuFeS2 powders milled for 60, 120, 180 and 240 min, respectively. The evolution of characteristic band gaps, Eg, and the rate constant of leaching, k, of nano‐powders are corroborated by the universal evolution of the parameter SBET/X (SBET‐specific surface area, X‐crystallinity) introduced for complex characterization of mechanochemically activated solids in various fields such as chemical engineering and/or energy conversion. The focus on non‐doped semiconducting CuFeS2 enabled to assess the role of impurities, which critically and often negatively influence the thermoelectric properties.

This study demonstrates scalable mechanochemical synthesis of rhodostannite Cu2FeSn3S8 nanocrystals. On the contrary to the previous reports focused on the synthesis of stannite Cu2FeSnS4 reporting the rhodostannite impurity, we succeeded in preparing stannite-free product after milling. Pure elements were used for a solvent-free production in a batch of 100 g using an eccentric vibratory mill. The progress of the synthesis was monitored by X-ray diffraction and magnetometry, which both confirmed a successful reaction progress until 6 h of milling. However, further treatment (until 10 h) did not result in an improvement, as quite a high saturation magnetization (7.8 emu/g) and clearly evident diffraction at around 44° in the XRD pattern of the product due to the presence of ferromagnetic un-reacted iron with content slightly above 5% was evidenced. The product is sulfur- and tin-deficient, with crystallite size of around 12 nm. In-depth SEM/EDS analysis has shown the inhomogeneity of Fe distribution due to unfinished reaction. The bandgap of the produced material was 1.29 eV. The spark plasma sintering treatment resulted in complete consumption of non-reacted iron, but partial decomposition to stannite Cu2FeSnS4 was observed. The product is an intrinsic semiconductor with high electrical resistivity, and is therefore unsuitable for thermoelectric application. However, its thermal conductivity is low, thus it could be used as an electrically and thermally insulating material.

Copper(I) selenide-nanocrystalline semiconductor was synthesized via one-step mechanochemical synthesis after 5 min milling in a planetary ball mill. The kinetics of synthesis was followed by X-ray powder diffraction analysis and specific surface area measurements of milled 2Cu/Se mixtures. The X-ray diffraction confirmed the orthorhombic crystal structure of Cu2Se with the crystallite size ∼25 nm. The surface chemical structure was studied by X-ray photoelectron spectroscopy, whereby the binding energy of the Cu 2p and Se 3d signals corresponded to Cu+ and Se2− oxidation states. Transmission electron microscopy revealed agglomerated nanocrystals and confirmed their orthorhombic structure, as well. The optical properties were studied utilizing ultraviolet-visible spectroscopy and photoluminescence spectroscopy. The direct bandgap energy 3.7 eV indicated a blue-shift phenomenon due to the quantum size effect. This type of Cu2Se synthesis can be easily adapted to production dimensions using an industrial vibratory mill. The advantages of mechanochemical synthesis represent the potential for inexpensive, environmentally-friendly, and waste-free manufacturing of Cu2Se.

Twelve Cu-based ternary (Cu-Me

The difficult and predominantly toxic processing of sulphide concentrates with a low gold content has prompted the finding of a more efficient and environmentally friendly method of obtaining this noble metal. This work was therefore focused on the recovery of gold from the concentrate of refractory sulphide complex (Banská Hodruša, Slovakia) using a non-cyanide mechanochemico-biological process. Gold in this complex concentrate is physically located in the intercrystalline space of sulfide minerals and fills in structural defects in sulfides. The precipitation of gold from the complex mineral matrices of the concentrate can be achieved using a mechanochemico-biological process. This innovative process makes it possible to recover gold by applying a thiourea solution, which is a preferred alternative to toxic a cyanidation. The use of a biological process with the application of algae has shown that algae with siliceous structures make it possible to obtain gold from a complex concentrate (Banská Hodruša, Slovakia) with dimensions of the nano. Limnetic algae (diatoms, golden algae) are part of aquatic ecosystems and form the largest of biomass of all plants on Earth. Mechanochemicobiological process is a method that allows to obtain 100 nm gold nanoparticles from refractory sulphide concentrate (Banská Hodruša, Slovakia).

Mechanochemistry is a multidisciplinary branch of science and has significantly developed within the last few years. In the Department of Mechanochemistry at the Institute of Geotechnics of Slovak Academy of Sciences in Kosice, Slovakia, the mechanochemical synthesis of advanced nanomaterials, namely chalcogenides and oxides, applicable in energy industry is performed. Furthermore, the treatment of waste, synthesis of antibacterially active nanoparticles, and performing organic reactions using mechanochemistry have been in the spotlight. The possibility to up-scale these processes using vibratory ball mill in collaboration with TU Clausthal in Germany has been successfully applied. These advancements are briefly reviewed in this paper.

Nanostructured semiconductor, copper sulphide, CuS prepared by a mechanochemical synthesis in a large-scale operation industrial mill was modified by surfactant-assisted milling in a planetary mill...

Novel drug delivery systems containing advanced materials are currently the focus of many scientists, particularly in the field of medicine. Nowadays, these materials can play an important role when the authors talk about human health and especially the need to develop personalized treatment. In this work, multiparticulate As4S4/ZnS/Fe3O4 nanocomposite based on components possessing promising therapeutic, photoluminescent, and magnetic functionality was prepared by the milling. Subsequently, it was covered with the bio-compatible polymer Poloxamer 407 and/or folic acid for the functionalization of inorganic material. The samples were studied from the structural (X-ray powder diffraction analysis), magnetic, and optical (UV–Vis and photoluminescence spectroscopies) point of view. Particle size distribution and zeta potential measurements were performed to determine long-term stability of these nanosuspensions. Fourier transform infrared spectroscopy was used to identify bonding between organic and inorganic entities. Prominent optical fluorescence properties were found in a sample containing folic acid.

The CuInSe2/ZnS multiparticulate nanocomposites were first synthesized employing two-step mechanochemical synthesis. In the first step, tetragonal CuInSe2 crystals prepared from copper, indium and selenium precursors were co-milled with zinc acetate dihydrate and sodium sulfide nonahydrate as precursors for ZnS in different molar ratios by mechanochemical route in a planetary mill. In the second step, the prepared CuInSe2/ZnS nanocrystals were further milled in a circulation mill in sodium dodecyl sulphate (SDS) solution (0.5 wt.%) to stabilize the synthesized nanoparticles. The sodium dodecyl sulphate capped CuInSe2/ZnS 5:0-SDS nanosuspension was shown to be stable for 20 weeks, whereas the CuInSe2/ZnS 4:1-SDS one was stable for about 11 weeks. After sodium dodecyl sulphate capping, unimodal particle size distribution was obtained with particle size medians approaching, respectively, 123 nm and 188 nm for CuInSe2/ZnS 5:0-SDS and CuInSe2/ZnS 4:1-SDS nanocomposites. Successful stabilization of the prepared nanosuspensions due to sodium dodecyl sulphate covering the surface of the nanocomposite particles was confirmed by zeta potential measurements. The prepared CuInSe2/ZnS 5:0-SDS and CuInSe2/ZnS 4:1-SDS nanosuspensions possessed anti-myeloma sensitizing potential assessed by significantly reduced viability of multiple myeloma cell lines, with efficient fluorescence inside viable cells and higher cytotoxic efficacy in CuInSe2/ZnS 4:1-SDS nanosuspension.

In the present study, a quick and environmentally friendly approach has been developed for the synthesis of CuS nanocrystals of different shape with antibacterial activity. The process is completed...

Out of many functionalities of zinc oxide, its magnetic properties are only sparsely explored. Herein we report on the evolution of ferromagnetism of undoped ZnO nanoparticles, depending on the zinc source used for the synthesis. We started from mechanochemical synthesis of phase pure nanocrystalline hydrozincite, Zn5(CO3)2(OH)6 (ZnHC) by milling a mixture comprising either Zn(NO3)2·6H2O or ZnCl2, and Na2CO3 for 10 min. Zinc oxide nanoparticles with specific surface over 70 m2/g were obtained by subsequent heating of ZnHC up to 300 °C. Ferromagnetism was observed only for ZnO nanoparticles derived from Zn(NO3)2, while those from ZnCl2 were conventionally diamagnetic. X-ray photoelectron, Raman, as well as electron paramagnetic resonance spectrograms consistently showed significantly higher concentration of oxygen vacancies in the Zn(NO3)2-derived ZnO. We also referred to the difference in the charging states of oxygen vacancies by detailed observation of EPR spectra. Since the formation of ZnO from ZnHC is topotactic, the difference in the lattice imperfection was discussed in terms of the hydration energy of the coexisting NO3− or Cl− anion. The present simple mechanochemical – thermal procedure offers a facile method for obtaining well-dispersed active ZnO nanoparticles. More importantly, the new synthesis method offers possibility of controlling their magnetic properties by choosing anionic species of the starting zinc source.

Chalcopyrite CuFeS2, a semiconductor with applications in chemical sector and energy conversion engineering, was synthetized in a planetary mill from elemental precursors. The synthesis is environmentally friendly, waste‐free and inexpensive. The synthesized nano‐powders were characterized by XRD, SEM, EDX, BET and UV/Vis techniques, tests of chemical reactivity and, namely, thermoelectric performance of sintered ceramics followed. The crystallite size of ∼13 nm and the strain of ∼17 were calculated for CuFeS2 powders milled for 60, 120, 180 and 240 min, respectively. The evolution of characteristic band gaps, Eg, and the rate constant of leaching, k, of nano‐powders are corroborated by the universal evolution of the parameter SBET/X (SBET ‐specific surface area, X‐crystallinity) introduced for complex characterization of mechanochemically activated solids in various fields such as chemical engineering and/or energy conversion. The focus on non‐doped semiconducting CuFeS2 enabled to assess the role of impurities, which critically and often negatively influence the thermoelectric properties., Energy materials: The parameter SBET /X (SBET – specific surface area, X – crystallinity degree) was applied to characterize surface and bulk changes in the mechanochemically synthesized chalcopyrite CuFeS2. The dependence of the rate constant of chemical leaching k as well as the optical band gap Eg on this parameter illustrates its general character applicable in such diverse fields like chemical engineering and semiconductor science.

The CuInSe2/ZnS multiparticulate nanocomposites were first synthesized employing two-step mechanochemical synthesis. In the first step, tetragonal CuInSe2 crystals prepared from copper, indium and selenium precursors were co-milled with zinc acetate dihydrate and sodium sulfide nonahydrate as precursors for ZnS in different molar ratios by mechanochemical route in a planetary mill. In the second step, the prepared CuInSe2/ZnS nanocrystals were further milled in a circulation mill in sodium dodecyl sulphate (SDS) solution (0.5 wt.%) to stabilize the synthesized nanoparticles. The sodium dodecyl sulphate capped CuInSe2/ZnS 5:0-SDS nanosuspension was shown to be stable for 20 weeks, whereas the CuInSe2/ZnS 4:1-SDS one was stable for about 11 weeks. After sodium dodecyl sulphate capping, unimodal particle size distribution was obtained with particle size medians approaching, respectively, 123 nm and 188 nm for CuInSe2/ZnS 5:0-SDS and CuInSe2/ZnS 4:1-SDS nanocomposites. Successful stabilization of the prepared nanosuspensions due to sodium dodecyl sulphate covering the surface of the nanocomposite particles was confirmed by zeta potential measurements. The prepared CuInSe2/ZnS 5:0-SDS and CuInSe2/ZnS 4:1-SDS nanosuspensions possessed anti-myeloma sensitizing potential assessed by significantly reduced viability of multiple myeloma cell lines, with efficient fluorescence inside viable cells and higher cytotoxic efficacy in CuInSe2/ZnS 4:1-SDS nanosuspension.

A combination of solid-state mechanochemical and green approaches for the synthesis of silver nanoparticles (AgNPs) is explored in this study. Thymus serpyllum L. (SER), Sambucus nigra L. (SAM) and Thymus vulgaris L. (TYM) plants were successfully applied to reduce AgNO3 to AgNPs, as confirmed by X-ray diffraction analysis, with SER being the best reducing agent, and TYM being the worst. The experiments were performed via a one-step planetary milling process, where various AgNO3:plant mass ratios (1:1, 1:10, 1:50 and 1:100) were investigated. Atomic absorption spectrometry indicated that the stability of the mechanochemically produced AgNPs increased markedly when a sufficiently large quantity of the reducing plant was used. Furthermore, when larger quantities of plant material were employed, the crystallite size of the AgNPs decreased. TEM analysis revealed that all AgNPs produced from both AgNO3:plant ratios 1:1 and 1:10 exhibit the bimodal size distribution with the larger fraction with size in tens of nm and the smaller one below 10 nm in size. The antibacterial activity of the produced AgNPs was observed only for AgNO3:plant ratio 1:1, with the AgNPs prepared using SER showing the greatest antibacterial properties.

Copper(II) selenide, CuSe was prepared from Cu and Se powders in a stoichiometric ratio by a rapid, and convenient one-step mechanochemical synthesis, after 5 and 10 min of milling in a planetary, and an industrial vibratory, mill. The kinetics of the synthesis, and the structural, morphological, optical, and electrical properties of CuSe products prepared in the two types of mill were studied. Their crystal structure, physical properties, and morphology were characterized by X-ray diffraction, specific surface area measurements, particle size distribution, scanning, and transmission electron microscopy. The products crystallized in a hexagonal crystal structure. However, a small amount of orthorhombic phase was also identified. The scanning electron microscopy revealed that both products consist of agglomerated particles of irregular shape, forming clusters with a size ~50 mm. Transmission electron microscopy proved the nanocrystalline character of the CuSe particles. The optical properties were studied using UV&ndash, Vis and photoluminescence spectroscopy. The determined band gap energies of 1.6 and 1.8 eV for the planetary- and vibratory-milled product, respectively, were blue-shifted relative to the bulk CuSe. CuSe prepared in the vibratory mill had lower resistivity and higher conductivity, which corresponds to its larger crystallite size in comparison with CuSe prepared in the planetary mill.

Chalcopyrite CuFeS2 was shown to be a promising thermoelectric material. Considering thermoelectric efficiency, its relatively high and temperature weakly dependent power factor, economic affordability and ecological benignity is counterbalanced by a high lattice thermal conductivity. Thus it is highly desirable to lower the thermal conductivity of chalcopyrite thermoelectric material without deterioration of other thermoelectric characteristics. In our study, we demonstrate that mechanosynthesis followed by appropriate sintering enables to prepare such nanostructured ceramics with a favourable thermoelectric response. Our study shows that mechanosynthesis is a low-cost technological route for the production of thermoelectric chalcopyrite ceramics. Chalkopyrit CuFeS2 se ukázal jako slibný termoelektrický materiál. Vzhledem k termoelektrické účinnosti je její relativně vysoký a teplotně slabě závislý účiník, ekonomická dostupnost a ekologická neškodnost vyvážena vysokou tepelnou vodivostí mřížky. Proto je velmi žádoucí snížit tepelnou vodivost termoelektrického materiálu chalkopyritu bez zhoršení dalších termoelektrických vlastností. V naší studii dokazujeme, že mechanosyntéza následovaná vhodným slinováním umožňuje připravit takovou nanostrukturovanou keramiku s příznivou termoelektrickou odezvou. Naše studie ukazuje, že mechanosyntéza je levnou technologickou cestou pro výrobu termoelektrické keramiky z chalkopyritu.

Copper, iron, and sulphur in elemental form were applied for mechanochemical synthesis of chalcopyrite CuFeS2. Products of synthesis were characterized by XRD method and evaluated by Rietveld analysis. A mixture of cubic (JCPDS 75-6866) and tetragonal (JCPDS 37-0471) phases of chalcopyrite with almost identical diffractograms were identified. Both phases are nanocrystalline with sizes 13 nm and 7 nm for laboratory and industrial milling, respectively. For determination of iron consumption during the synthesis, method of magnetometry has been applied. Based on magnetization data reflecting time dependent incorporation of elemental iron into chalcopyrite nanostructure, the kinetics of the synthesis was evaluated. From kinetic data the rate constant of reaction k, as well as the conversion degree R were determined. High conversion degree of mechanochemical synthesis performed in a laboratory mill (R = 100%), as well as in an industrial mill (R = 96%) offer the possibility to scale-up the process of synthesis in preparation of this perspective magnetic semiconductor. The method of magnetometry was proved to be an effective tool for following the processes of synthesis where iron particles are incorporated. Měď, železo a síra v elementární formě byly použity pro mechanochemickou syntézu chalkopyritu CuFeS2. Produkty syntézy byly charakterizovány metodou XRD a hodnoceny analýzou společnosti Rietveld. Byla zjištěna směs krychlových (JCPDS 75-6866) a tetragonálních (JCPDS 37-0471) fází chalkopyritu s téměř totožnými difraktogramy. Obě fáze jsou nanokrystalické s velikostí 13 nm pro laboratorní a 7 nm pro průmyslové mletí. Pro stanovení spotřeby železa během syntézy byla použita metoda magnetometrie. Na základě magnetizačních dat odrážejících na čase závislou inkorporaci elementárního železa do chalkopyritové nanostruktury byla vyhodnocena kinetika syntézy. Z kinetických údajů byla stanovena rychlostní konstanta reakce k a také konverzní stupeň R. Vysoký stupeň konverze mechanochemické syntézy prováděné v laboratorní válcovně (R = 100 %), jakož i v průmyslové válcovně (R = 96 %) nabízí možnost rozšířit proces syntézy při přípravě tohoto perspektivního magnetického polovodiče. Ukázalo se, že metoda magnetometrie je účinným nástrojem pro sledování procesů syntézy, při nichž jsou obsaženy částice železa.

The rapid mechanochemical synthesis of nanocrystalline CuFeS particles prepared by high-energy milling for 60 min in a planetary mill from copper, iron and sulphur elements is reported. The CuFeS nanoparticles crystallize in tetragonal structure with mean crystallite size of about 38 ± 1 nm determined by XRD analysis. HRTEM study also revealed the presence of nanocrystals with the size of 5–30 nm with the tendency to form agglomerates. The Raman spectrum confirms the chalcopyrite structure. Low temperature magnetic data for CuFeS support the coexistence of antiferromagnetic and paramagnetic spin structure. Moreover, the hysteresis loops taken at temperatures from 5 K to 300 K revealed a presence of very small amount of ferromagnetic phase, which seems to be associated with the non-consumed elemental Fe in as-prepared nanoparticles. The optical band gap of CuFeS nanoparticles has been detected to be 1.05 eV, larger than band gap of the bulk material. The wider gap possibly resulted from the nano-size effect. Photoresponses of CuFeS nanoparticles were confirmed by I-V measurements under dark and light illumination. It was demonstrated that mechanochemical synthesis can be successfully employed in the one step preparation of nanocrystalline CuFeS with good structural, magnetic, optical and electrooptical properties., This work was promoted by the Slovak Research and Development Agency under the contract No. APVV-14-0103. The support through the Slovak Grant Agency VEGA (projects 2/0027/14, 1/0739/16 and 2/0065/18) is also thankfully acknowledged. The authors also appreciate the help of the European Regional Development Fund- project NANOCEXMAT 2 (ITMS 26220120035) and European Union through the CT-2011-1-REGPOT285895 AL-NANOFUN project (Advanced Laboratory for the Nano-Analysis of novel Functional materials), for the microscopy facilities sited in Seville.

Rapid solvent-free mechanochemical synthesis of CTS nanocrystals from elemental precursors is reported herein. The process is completed in 15 min, proceeding through immediate formation of CuS in a self-sustaining manner and its subsequent reaction with Sn and residual sulfur. The reaction progress was monitored by pressure and temperature changes in the milling vessel, X-ray diffraction, Soxhlet analysis, grain size analysis and electric resistivity measurements. The relationship between the consumption of metallic precursors, grain size and electrical resistivity is provided. The final product was nanocrystalline with crystallite size below 10 nm, as confirmed by both X-ray diffraction and transmission electron microscopy. The nanocrystals are agglomerated into micrometer-sized grains. It exhibits poor porous properties with the specific surface area value of 2.5 m2/g. The X-ray photoelectron spectroscopy has shown that the surface is significantly oxidized, due to milling in air. The optical properties of the prepared CTS nanocrystals are interesting for photovoltaic applications.

In this study, the mechanochemical synthesis of Co9S8 nanoparticles from cobalt and sulphur by high-energy milling in a planetary mill in an argon atmosphere is reported. Structural characterization of the synthesized nanoparticles by XRD was performed. Co9S8 nanoparticles crystallize in the cubic structure with the crystallite size of about 16 nm. The microstructure of the Co9S8 nanoparticles was further studied using TEM, HRTEM and EDS-HAADF-STEM techniques. Co9S8 nanoparticles consist of nanocrystals exhibiting size in the range of 10–30 nm that are densely aggregated into spherical-like objects. The highest specific surface area value observed was 4 m2g-1 and the pore properties of this sample are quite poor. The magnetic properties of mechanochemically synthesized nanoparticles were investigated using SQUID magnetometer. The room temperature magnetic data supported the paramagnetic spin structure of Co9S8 nanoparticles. The transition from paramagnetic to weak ferromagnetic or ferrimagnetic behaviour was indicated from temperature dependence of magnetization at cryogenic temperatures. It is demonstrated that mechanochemical synthesis can be successfully employed in the one-step solid-state preparation of Co9S8 nanoparticles.

In the present study, the mechanochemically prepared covellite, CuS and chalcocite, Cu2S nanocrystals are compared in detail. Concretely, the SEM, EDS, N2 adsorption, UV–Vis, PL, FTIR, ZP measurement, PCCS, XPS and DTA/TG were used. SEM, EDS and elemental mapping have shown that the agglomerates containing nanoparticles of the corresponding phases were formed as a result of milling. The nitrogen adsorption method has documented richer surface properties in the case of CuS sample. The specific surface area values were 2.7 m2 g−1 and 1.4 m2 g−1 for CuS and Cu2S, respectively. UV–Vis and PL measurements have shown that these materials might be suitable for optoelectronic applications, as the optical bandgaps were 1.92 eV and 3 eV for CuS and Cu2S, respectively. FTIR spectrum of CuS exhibited a peak at 621 cm−1, which is characteristic for this material. ZP values were more negative in the case of CuS and PCCS has confirmed the finer character of this sample (x50 values were 680 nm and 617 nm for Cu2S and CuS, respectively). XPS method documented the surface oxidation of the prepared Cu2S. The thermal stability measurement up to 550 °C has shown that Cu2S does not undergo significant changes (only 1.4% weight loss was observed), whereas CuS is losing sulfur and is transformed into digenite and chalcocite (14.3% weight loss was observed). The mechanochemically synthesized copper sulfides show high activities in photodecolorization of Methyl Orange dye under visible light irradiation, as Cu2S was able to completely decompose the dye in 150 min and CuS caused 80% decomposition after the same time of treatment.

Stannite Cu2FeSnS4 and kesterite Cu2ZnSnS4 were synthesized by an eco-friendly ball-milling method in an industrial mill. Both synthesized sulfides represent perspective materials in solar cell technology. Several characterization methods have been applied to determine the course of solid state mechanochemical reactions leading to the synthesis of potential chalcogenide solar cell absorbers. The phase and surface composition, solid state kinetics, and surface morphology of these quaternary sulfides were elucidated by the methods of X-ray diffractometry, X-ray photoelectron spectroscopy, Soxhlet analysis, and scanning electron microscopy. The application of eccentric vibration mills for these syntheses constitutes the big challenge for researchers in the field of photovoltaics in their permanent effort in scaling up new materials and processes.

Multiple myeloma (MM), a B cell malignancy characterized by clonal proliferation of plasma cells in the bone marrow, remains incurable despite the use of novel and conventional therapies. In this study, we demonstrated MM cell cytotoxicity triggered by realgar (REA; As4S4) nanoparticles (NREA) versus Arsenic trioxide (ATO) against MM cell lines and patient cells. Both NREA and ATO showed in vivo anti-MM activity, resulting in significantly decreased tumour burden. The anti-MM activity of NREA and ATO is associated with apoptosis, evidenced by DNA fragmentation, depletion of mitochondrial membrane potential, cleavage of caspases and anti-apoptotic proteins. NREA induced G2/M cell cycle arrest and modulation of cyclin B1, p53 (TP53), p21 (CDKN1A), Puma (BBC3) and Wee-1 (WEE1). Moreover, NREA induced modulation of key regulatory molecules in MM pathogenesis including JNK activation, c-Myc (MYC), BRD4, and histones. Importantly, NREA, but not ATO, significantly depleted the proportion and clonogenicity of the MM stem-like side population, even in the context of the bone marrow stromal cells. Finally, our study showed that both NREA and ATO triggered synergistic anti-MM activity when combined with lenalidomide or melphalan. Taken together, the anti-MM activity of NREA was more potent compared to ATO, providing the preclinical framework for clinical trials to improve patient outcome in MM.

In this work, we demonstrate the use of elemental precursors (Cu, Sb, S) to synthesize famatinite Cu3SbS4 using a laboratory planetary ball milling and an industrial eccentric vibratory milling. Cu3SbS4 was prepared for 120 min and 180 min in laboratory and industrial mill, respectively, with the utilization of protective atmosphere. The Cu3SbS4 prepared in the laboratory and industrial mill with crystallite size 14 nm and 10 nm, respectively, was confirmed by both LeBail refinement of the X-ray powder diffraction data and transmission electron microscopy. The determined band gap energy 1.31 eV and 1.24 eV is blue-shifted relative to the bulk Cu3SbS4. The synthesis of Cu3SbS4 by a scalable milling process represents a prospective route for mass production of material with potential photovoltaic properties.