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In this study, we report the optoelectric and thermoelectric properties of famatinite Cu3SbS4 that was mechanochemically synthesized in a planetary mill from powder elements for 120 min in an inert atmosphere. The tetragonal famatinite Cu3SbS4 was nanocrystalline with a crystallite size of 14 nm, as endorsed by Rietveld refinement. High-resolution transmission electron microscopy showed several crystallites in the range of 20–50 nm. Raman spectroscopy proved the purity of the synthesized famatinite Cu3SbS4 and chemical-state characterization performed by X-ray photoelectron spectroscopy confirmed that the prepared sample was pure. The Cu1+, Sb5+, and S2− oxidation states in Cu3SbS4 sample were approved. The morphology characterization showed homogeneity of the prepared sample. The photoresponse of Cu3SbS4 was confirmed from I–V measurements in the dark and under illumination. The photocurrent increase reached 20% compared to the current in the dark at a voltage of 5 V. The achieved results confirm that synthesized famatinite Cu3SbS4 can be applied as a suitable absorbent material in solar cells. The performed thermoelectric measurements revealed a figure of merit ZT of 0.05 at 600 K.

The Fe3O4@SiO2@ZnO composite was synthesized via the simultaneous deposition of SiO2 and ZnO onto pre-prepared Fe3O4 nanoparticles. Physicochemical methods (TEM, EDXS, XRD, SEM, FTIR, PL, zeta potential measurements, and low-temperature nitrogen adsorption/desorption) revealed that the simultaneous deposition onto magnetite surfaces, up to 18 nm in size, results in the formation of an amorphous shell composed of a mixture of zinc and silicon oxides. This composite underwent modification to form Fe3O4@SiO2@ZnO*, achieved by activation with H2O2. The modified composite retained its structural integrity, but its surface groups underwent significant changes, exhibiting pronounced catalytic activity in the photodegradation of methyl orange under UV irradiation. It was capable of degrading 96% of this azo dye in 240 min, compared to the initial Fe3O4@SiO2@ZnO composite, which could remove only 11% under identical conditions. Fe3O4@SiO2@ZnO* demonstrated robust stability after three cycles of use in dye photodegradation. Furthermore, Fe3O4@SiO2@ZnO* exhibited decreased PL intensity, indicating an enhanced efficiency in electron-hole pair separation and a reduced recombination rate in the modified composite. The activation process diminishes the electron-hole (e−)/(h+) recombination and generates the potent oxidizing species, hydroxyl radicals (OH˙), on the photocatalyst surface, thereby playing a crucial role in the enhanced photodegradation efficiency of methyl orange with Fe3O4@SiO2@ZnO*.

In this paper, ZnS nanoparticles were bioconjugated with bovine serum albumin and prepared in a form of nanosuspension using a wet circulation grinding. The stable nanosuspension with monomodal particle size distribution (d50 = 137 nm) and negative zeta potential (−18.3 mV) was obtained. The sorption kinetics and isotherm were determined. Interactions between ZnS and albumin were studied using the fluorescence techniques. The quenching mechanism, describing both static and dynamic interactions, was investigated. Various parameters were calculated, including the quenching rate constant, binding constant, stoichiometry of the binding process, and accessibility of fluorophore to the quencher. It has been found that tryptophan, in comparison to tyrosine, can be closer to the binding site established by analyzing the synchronous fluorescence spectra. The cellular mechanism in multiple myeloma cells treated with nanosuspension was evaluated by fluorescence assays for quantification of apoptosis, assessment of mitochondrial membrane potential and evaluation of cell cycle changes. The preliminary results confirm that the nontoxic nature of ZnS nanoparticles is potentially applicable in drug delivery systems. Additionally, slight changes in the secondary structure of albumin, accompanied by a decrease in α-helix content, were investigated using the FTIR method after analyzing the deconvoluted Amide I band spectra of ZnS nanoparticles conjugated with albumin. Thermogravimetric analysis and long-term stability studies were also performed to obtain a complete picture about the studied system.

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.

The biocompatible nanosuspension of CuS nanoparticles (NPs) using bovine serum albumin (BSA) as a capping agent was prepared using a two-stage mechanochemical approach. CuS NPs were firstly synthetized by a high-energy planetary ball milling in 15 min by milling elemental precursors. The stability of nanoparticles in the simulated body fluids was studied, revealing zero copper concentration in the leachates, except simulated lung fluid (SLF, 0.015%) and simulated gastric fluid (SGF, 0.078%). Albumin sorption on CuS NPs was studied in static and dynamic modes showing a higher kinetic rate for the dynamic mode. The equilibrium state of adsorption was reached after 90 min with an adsorption capacity of 86 mg/g compared to the static mode when the capacity 59 mg/g was reached after 2 h. Then, a wet stirred media milling in a solution of BSA was introduced to yield the CuS-BSA nanosuspension, being stable for more than 10 months, as confirmed by photon cross-correlation spectroscopy. The fluorescent properties of the nanosuspension were confirmed by photoluminescence spectroscopy, which also showed that tryptophan present in the BSA could be closer to the binding site of CuS than the tyrosine residue. The biological activity was determined by in vitro tests on selected cancer and non-tumor cell lines. The results have shown that the CuS-BSA nanosuspension inhibits the metabolic activity of the cells as well as decreases their viability upon photothermal ablation.

Ternary wittichenite Cu3BiS3 nanocrystals were prepared mechanochemically using a planetary ball mill from elemental copper, bismuth and sulfur in a stoichiometric ratio in only 5 min. The orthorhombic wittichenite Cu3BiS3 was nanocrystalline with an approximate crystallite size of 38 nm ± 9 nm, as confirmed by Rietveld refinement. The nanocrystalline character of orthorhombic Cu3BiS3 was also proven by transmission electron microscopy. The measured Raman spectrum confirmed the formation of pure wittichenite Cu3BiS3. The morphology characterization demonstrated the homogeneity of the sample. The value of the specific surface area for pure mechanochemically prepared Cu3BiS3 after 5 min was 2.7 m2g−1. The optical properties were investigated using UV–Vis absorption and micro-photoluminescence spectroscopy. From the absorption UV–Vis spectrum, the value of the bandgap energy was determined to be 1.52 eV, which creates an assumption for the use of wittichenite Cu3BiS3 in photovoltaic applications. The optoelectrical properties of the prepared Cu3BiS3 nanocrystals were verified by current–voltage measurements in the dark and under white light illumination. The photocurrent increased by 26% compared to the current in the dark at a voltage of 1 V. The achieved results confirmed a very fast and efficient way of synthesizing a ternary wittichenite Cu3BiS3, which can be used for applications in solar cells.

Copper, antimony and sulfur in elemental form were applied for one-pot solid-state mechanochemical synthesis of skinnerite (Cu3SbS3) in a laboratory mill and an industrial mill. This synthesis was completed after 30 min of milling in the laboratory mill and 120 min in the industrial mill, as corroborated by X-ray diffraction. XRD analysis confirmed the presence of pure monoclinic skinnerite prepared in the laboratory mill and around 76% monoclinic skinnerite, with the secondary phases famatinite (Cu3SbS4; 15%), and tetrahedrite (Cu11.4Sb4S13; 8%), synthesized in the industrial mill. The nanocrystals were agglomerated into micrometer-sized grains in both cases. Both samples were nanocrystalline, as was confirmed with HRTEM. The optical band gap of the Cu3SbS3 prepared in the laboratory mill was determined to be 1.7 eV with UV–Vis spectroscopy. Photocurrent responses verified with I–V measurements under dark and light illumination and Cu3SbS3 nanocrystals showed ~45% enhancement of the photoresponsive current at a forward voltage of 0.6 V. The optical and optoelectrical properties of the skinnerite (Cu3SbS3) prepared via laboratory milling are interesting for photovoltaic applications.

Nickel mono- (NiSe) and diselenide (NiSe2) were produced from stoichiometric mixtures of powdered Ni and Se precursors by the one-step, undemanding mechanochemical reactions. The process was carried out by high-energy milling for 30 and 120 min in a planetary ball mill. The kinetics of the reactions were documented, and the products were studied in terms of their crystal structure, morphology, electrical, and optical properties. X-ray powder diffraction confirmed that NiSe has hexagonal and NiSe2 cubic crystal structure with an average crystallite size of 10.5 nm for NiSe and 13.3 nm for NiSe2. Their physical properties were characterized by the specific surface area measurements and particle size distribution analysis. Transmission electron microscopy showed that the prepared materials contain nanoparticles of irregular shape, which are agglomerated into clusters of about 1–2 μm in diameter. The first original values of electrical conductivity, resistivity, and sheet resistance of nickel selenides synthesized by milling were measured. The obtained bandgap energy values determined using UV–Vis spectroscopy confirmed their potential use in photovoltaics. Photoluminescence spectroscopy revealed weak luminescence activity of the materials. Such synthesis of nickel selenides can easily be carried out on a large scale by milling in an industrial mill, as was verified earlier for copper selenide synthesis.

CdS nanoparticles were successfully synthesized using cadmium acetate and sodium sulfide as Cd and S precursors, respectively. The effect of using sodium thiosulfate as an additional sulfur precursor was also investigated (combined milling). The samples were characterized by XRD, Raman spectroscopy, XPS, UV-Vis spectroscopy, PL spectroscopy, DLS, and TEM. Photocatalytic activities of both CdS samples were compared. The photocatalytic activity of CdS, which is produced by combined milling, was superior to that of CdS, and was obtained by an acetate route in the degradation of Orange II under visible light irradiation. Better results for CdS prepared using a combined approach were also evidenced in photocatalytic experiments on hydrogen generation. The antibacterial potential of mechanochemically prepared CdS nanocrystals was also tested on reference strains of E. coli and S. aureus. Susceptibility tests included a 24-h toxicity test, a disk diffusion assay, and respiration monitoring. Bacterial growth was not completely inhibited by the presence of neither nanomaterial in the growth environment. However, the experiments have confirmed that the nanoparticles have some capability to inhibit bacterial growth during the logarithmic growth phase, with a more substantial effect coming from CdS nanoparticles prepared in the absence of sodium thiosulfate. The present research demonstrated the solvent-free, facile, and sustainable character of mechanochemical synthesis to produce semiconductor nanocrystals with multidisciplinary application.

Abstract The ZnS nanocrystals were prepared in chitosan solution (0.1 wt.%) using a wet ultra-fine milling. The obtained suspension was stable and reached high value of zeta potential (+57 mV). The changes in FTIR spectrum confirmed the successful surface coating of ZnS nanoparticles by chitosan. The prepared ZnS nanocrystals possessed interesting optical properties verified in vitro. Four cancer cells were selected (CaCo-2, HCT116, HeLa, and MCF-7), and after their treatment with the nanosuspension, the distribution of ZnS in the cells was studied using a fluorescence microscope. The particles were clearly seen; they passed through the cell membrane and accumulated in cytosol. The biological activity of the cells was not influenced by nanoparticles, they did not cause cell death, and only the granularity of cells was increased as a consequence of cellular uptake. These results confirm the potential of ZnS nanocrystals using in bio-imaging applications.

Abstract In this study, we demonstrate a one-pot mechanochemical synthesis of the nanocomposite composed of stannite Cu2FeSnS4 and rhodostannite Cu2FeSn3S8 nanocrystals using a planetary ball mill and elemental precursors (Cu, Fe, Sn, S). By this approach, unique nanostructures with interesting properties can be obtained. Methods of XRD, Raman spectroscopy, UV-Vis, nitrogen adsorption, SEM, EDX, HRTEM, STEM, and SQUID magnetometry were applied. Quaternary tetragonal phases of stannite and rhodostannite with crystallite sizes 18–19 nm were obtained. The dominant Raman peaks corresponding to the tetragonal stannite structure corresponding to A-symmetry optical modes were identified in the spectra. The bandgap 1.25 eV calculated from UV-Vis absorption spectrum is very well-acceptable value for the application of the synthesized material. The SEM micrographs illustrate the clusters of particles in micron and submicron range. The formation of agglomerates is also illustrated on the TEM micrographs. Weak ferromagnetic properties of the synthesized nanocrystals were documented.

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.

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 μm. Transmission electron microscopy proved the nanocrystalline character of the CuSe particles. The optical properties were studied using UV–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.

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.

In this study, CuInS2/ZnS nanocrystals were synthesized by a two-step mechanochemical synthesis for the first time. In the first step, tetragonal CuInS2 was prepared from copper, indium and sulphur precursors. The obtained CuInS2 was further co-milled with zinc acetate dihydrate and sodium sulphide nonahydrate as precursors for cubic ZnS. Structural characterization of the CuInS2/ZnS nanocrystals was performed by X-ray diffraction analysis, Raman spectroscopy and transmission electron microscopy. Specific surface area of the product (86 m2/g) was measured by low-temperature nitrogen adsorption method and zeta potential of the particles dispersed in water was calculated from measurements of their electrophoretic mobility. Optical properties of the nanocrystals were determined using photoluminescence emission spectroscopy.

In this work mechanical activation of realgar As4S4 was studied. The addition of sodium chloride NaCl as a solid diluent intothe milling process substantially improved solid state properties of the obtained fines. However, the polymorphous transformationof

In this study we demonstrate the synthesis of quaternary semiconductor nanocrystals of stannite Cu2FeSnS4/rhodostannite Cu2FeSn3S8 (CFTS) via mechanochemical route using Cu, Fe, Sn and S elements as precursors in one-pot experiments. Methods of X-ray diffraction (XRD), nitrogen adsorption, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) were applied to characterize properties of the unique nanostructures. Mechanochemical route of synthesis induced new phenomena like explosive character of reaction, where three stages could be identified and the formation of nanostructures 5–10 nm in size. By using XPS method, Cu(I), Fe(II), Sn(IV) and S(-II) species were identified on the surface of CFTS. The value of optical band gap 1.27 eV is optimal for semiconductors applicable as absorbers in solar cells. The significant photocatalytic activity of the CFTS nanocrystals was also evidenced. The obtained results confirm the excellent properties of the quaternary semiconductor nanocrystals synthesized from earth-abundant elements.

In this work, a nanocomposite consisting of ternary chalcogenide CuInS2 and TiO2 was prepared and its optical and optoelectrical properties were investigated. The CuInS2/TiO2 nanocomposite was produced via one-step mechanochemical synthesis and characterized from the crystal structure, microstructural, morphology, surface, optical, and optoelectrical properties viewpoints. X-ray diffraction confirmed the presence of both components, CuInS2 and TiO2, in the nanocomposite and revealed a partial transformation of anatase to rutile. The presence of both components in the samples was also proven by Raman spectroscopy. HRTEM confirmed the nanocrystalline character of the samples as crystallites ranging from around 10 nm and up to a few tens of nanometers were found. The presence of the agglomerated nanoparticles into larger grains was proven by SEM. The measured optical properties of CuInS2, TiO2, and CuInS2/TiO2 nanocomposites demonstrate optical bandgaps of ~1.62 eV for CuInS2 and 3.26 eV for TiO2. The measurement of the optoelectrical properties showed that the presence of TiO2 in the CuInS2/TiO2 nanocomposite increased its conductivity and modified the photosensitivity depending on the ratio of the components. This study has demonstrated the possibility of preparing a CuInS2/TiO2 nanocomposite material with promising applications in optoelectronics in the visible region in an eco-friendly manner.

Abstract Nanoparticles in medicine can integrate actively targeted imaging agents and drug delivery vehicles, and combining multiple types of therapeutics in a single particle has numerous advantages, especially in multiple myeloma. MM is an incurable hematological disorder characterized by clonal proliferation of plasma cells in the bone marrow. In this study, we evaluated the anti-myeloma activity of 3 nanocomposites (3NPs): As4S4/ZnS/Fe3O4 (1:4:1), As4S4/ZnS/Fe3O4 with folic acid (FA), and As4S4/ZnS/Fe3O4 with FA and albumin with reduced survival MM cell lines and primary MM samples by each of 3NP. Cytotoxic effects of 3NPs were associated with caspase- and mitochondria-dependent apoptosis induction and reduced c-Myc expression. Modulation of cell cycle regulators, such as p-ATM/ATM and p-ATR/ATR, and increases in p-Chk2, cyclin B1, and histones were accompanied by G2/M arrest triggered by 3NPs. In addition, 3NPs activated several myeloma-related signaling, including JNK1/2/3, ERK1/2 and mTOR. To overcome BM microenvironment-mediated drug resistance, nanocomposites retained its anti-MM activity in the presence of stroma. 3NPs significantly decreased the stem cell-like side population in MM cells, even in the context of stroma. We observed strong synergistic effects of 3NPs combined with lenalidomide, pomalidomide, or melphalan, suggesting the potential of these combinations for future clinical studies.

Abstract 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.