Search

Abstract This paper is devoted to the investigation of the plasmonic effect of metal nanoparticles (NPs) formed on the surface of the YAG: Bi, Ce, Yb phosphors in a temperature range between 4 and 300 K. Combination of a thin conversion layer with silver plasmonic nanostructures leads to increase of sensitizer absorption and emission efficiency. Enhancement of Bi3+ luminescence in YAG epitaxial films with Ag NPs was observed upon cooling the samples below 200 K. High enhancement factors were associated with closely matching the maximum of plasmon extinction and Bi3+ emission bands. The maximum value of enhancement factor near 170% at 4 K was obtained. It is shown that temperature decrease causes an increase in the EM field intensity around the NPs, the probability of spontaneous recombination, the penetration depth of the localized surface plasmon resonances (LSPR) into the substrate, and the adjustment of the position of the LSPR. Simultaneous action of all these factors leads to Bi3+ emission intensity enhancement. Comparative analysis of the Finite-Difference Time-Domain (FDTD) simulation data vs. experimental results of the temperature behavior of plasmon absorption spectra, luminescence spectra of Bi3+ ions, and their decay kinetics confirms the correctness of the proposed mechanisms.

K-feldspar represents an important natural resource of potassium and aluminum. Within the framework of this study, the K-feldspar was mechanically activated in a planetary ball mill under different conditions planned according to 43 Taguchi orthogonal array experimental design. As outputs, specific surface area (SBET), median particle size (d50), amorphization degree of mineral phases , and Al recovery were used. It was found that the initial d50 value of 293 μm could be reduced to 6.7 μm and the SBET value of 4.7 m2/g could be increased up to 32.5 m2/g upon milling. Both microcline KAl3SiO8, and albite NaAl3SiO8 could be almost completely amorphized, whereas quartz SiO2 still maintained some crystallinity even under the most intensive conditions. Increasing SBET and decreasing the d50 values did not lead to a significant improvement in Al leach recovery, whereas a clear relationship between the amorphization of microcline and the recovered aluminum was found. Analysis of Variance (ANOVA) showed that increasing ball-to-powder ratio is the most beneficial for the improvement in Al recovery. In situ powder X-ray diffraction monitoring performed in an oscillation ball mill under synchrotron irradiation has shown very rapid amorphization of microcline phase at the beginning. However, amorphization of microcline was only partial after two hours of the treatment in this mill, apart from almost complete process in the planetary ball mill. In the end, regressions for the calculation of Al recovery by knowing the values of input parameters were calculated. In general, by just using mechanical activation without the subsequent roasting process that is commonly used to boost metal recoveries, it was possible to quantitatively recover aluminum from K-feldspar.

Abstract In this study, we explore the mechanical treatment of two metal–organic frameworks (MOFs), HKUST-1 and MOF-76, applying various milling methods to assess their impact on stability, porosity, and CO2 adsorption capacity. The effects of different mechanical grinding techniques, such as high-energy ball milling and hand grinding, on these MOFs were compared. The impact of milling time, milling speed and ball size during high-energy ball milling was assessed via the Design of Experiments methodology, namely using a 33 Taguchi orthogonal array. The results highlight a marked improvement in CO2 adsorption capacity for HKUST-1 through hand milling, increasing from an initial 25.70 wt.% (5.84 mmol g-1) to 41.37 wt.% (9.40 mmol g-1), marking a significant 38% increase. In contrast, high-energy ball milling seems to worsen this property, diminishing the CO2 adsorption abilities of the materials. Notably, MOF-76 shows resistance to hand grinding, closely resembling the original sample’s performance. Hand grinding also proved to be well reproducible. These findings clarify the complex effects of mechanical milling on MOF materials, emphasising the necessity of choosing the proper processing techniques to enhance their stability, texture, and performance in CO2 capture and storage applications.

In the original publication [...]

Molybdenum is a refractory metal regarded as a promising basis for producing high-temperature components. However, the potential of manufacturing molybdenum-based structures by direct ink writing (DIW) has not been explored. In this study, three-dimensional porous molybdenum (Mo) and molybdenum-silicon (Mo–Si) composite lattices were fabricated using DIW with non-milled and milled powders. The effects of Mo powder morphology (resulting from milling) and chemical composition (alloying Mo with 3 and 10 wt% of Si) on the microstructure, phase composition, and static and cyclic compression properties at room temperature were investigated. Lattices fabricated from commercial spherical Mo powder exhibited the highest intra-filament porosity. Conversely, lattices fabricated from milled Mo powder were denser and had higher compressive strength, offset stress, and quasi-elastic gradient. Alloying Mo with Si during sintering resulted in composite lattices with Mo + Mo3Si microstructure. A low content of Mo3Si slightly decreased monotonic compression properties but did not affect the cyclic compression response compared to Mo lattices made from milled powder. In contrast, a high content of Mo3Si produced quasi-brittle lattices with reduced compressive strength and increased damage accumulation during cyclic loading. The cyclic behavior of all lattices was characterized by a ratcheting-dominated stress-strain response. Lattices fabricated from milled Mo and milled Mo-3 wt.%Si powders demonstrated superior performance compared to those fabricated from commercial spherical Mo and milled Mo-10 wt%Si powders. The results suggest that using milled powders can enhance the mechanical reliability and promote the use of DIW as preferred additive manufacturing technology for the fabrication of Mo–Si composite lattices.

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.

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.

An efficient eco-friendly one-step mechanochemical synthesis of indole hybrid chalcones via the Claisen–Schmidt condensation of 1-methylindole-3-carboxaldehyde with various substituted acetophenones is described using liquid assisted grinding in a high-energy ball mill. The notable advantages of the present method are small organic solvent required (100 μL ethanol) and mainly shorter reaction time (15–60 min) as compared to the conventional method. Antiproliferative activity of synthesized chalcones was studied on several human cancer cell lines (MCF-7, HeLa, A549, MDA-MB-231, HCT116) and non-cancer lines (Cos-7 or BJ-5ta). 3,4,5-Trimethoxyphenyl 3g, 2,5-dimethoxyphenyl 3h, and 2,4,5-trimethylphenyl 3j chalcones showed considerable cytotoxicity, particularly, chalcones 3h and 3j were identified as the most potent and selective anticancer agents with IC50 values 7.9 and 6.6 μM, respectively, against the colon cancer HCT116 cell line.

Herein, the room-temperature sulfuric acid leaching of copper smelter slag powder in the presence of potassium dichromate was investigated, resulting in the selective extraction of copper with its separation from zinc and iron. To enhance the extraction of copper, mechanical activation in the planetary ball mill and attritor was used. The Taguchi method was applied to determine the optimal conditions for both mechanical activation and leaching. For mechanical activation in the attritor, a rotation speed of 1200 rpm, ball-to-powder ratio of 40 and milling time of 75 min were ideal. Under these conditions, the specific surface area (SBET) could be increased from 1.7 m2/g, for the starting slag, to 59.4 m2/g. According to ANOVA, the most important factor is the rotation speed. For comparison, the slag was subjected also to planetary ball milling using the same conditions and a specific surface area of 116 m2/g was obtained. Leaching conditions that maximize copper recovery and, independently, copper selectivity, were also found. The maximum copper recovery was 87.3%, while the maximum copper selectivity was 97.9%. The most influential parameters in leaching were the concentration of K2Cr2O7 and the liquid-to-solid ratio. The copper selectivity is attributed to better solubility of chalcopyrite (CuFeS2) in comparison with zinc ferrite (ZnFe2O4) and fayalite (FeSiO4) containing the other metals. This study provides a statistical approach for planning the experiments of pretreatment and leaching to efficiently recover valuable metals from secondary raw resources in an environmentally interesting fashion by using low concentrations of leaching agents and mechanical pretreatment.

Strontium ferromolybdate, Sr2FeMoO6, is an important member of the family of double perovskites with the possible technological applications in the field of spintronics and solid oxide fuel cells. Its preparation via a multi-step ceramic route or various wet chemistry-based routes is notoriously difficult. The present work demonstrates that Sr2FeMoO6 can be mechanosynthesized at ambient temperature in air directly from its precursors (SrO, α-Fe, MoO3) in the form of nanostructured powders, without the need for solvents and/or calcination under controlled oxygen fugacity. The mechanically induced evolution of the Sr2FeMoO6 phase and the far-from-equilibrium structural state of the reaction product are systematically monitored with XRD and a variety of spectroscopic techniques including Raman spectroscopy, 57Fe Mössbauer spectroscopy, and X-ray photoelectron spectroscopy. The unique extensive oxidation of iron species (Fe0 → Fe3+) with simultaneous reduction of Mo cations (Mo6+ → Mo5+), occuring during the mechanosynthesis of Sr2FeMoO6, is attributed to the mechanically triggered formation of tiny metallic iron nanoparticles in superparamagnetic state with a large reaction surface and a high oxidation affinity, whose steady presence in the reaction mixture of the milled educts initiates/promotes the swift redox reaction. High-resolution transmission electron microscopy observations reveal that the mechanosynthesized Sr2FeMoO6, even after its moderate thermal treatment at 923 K for 30 min in air, exhibits the nanostructured nature with the average particle size of 21(4) nm. At the short-range scale, the nanostructure of the as-prepared Sr2FeMoO6 is characterized by both, the strongly distorted geometry of the constituent FeO6 octahedra and the extraordinarily high degree of anti-site disorder. The degree of anti-site disorder ASD = 0.5, derived independently from the present experimental XRD, Mössbauer, and SQUID magnetization data, corresponds to the completely random distribution of Fe3+ and Mo5+ cations over the sites of octahedral coordination provided by the double perovskite structure. Moreover, the fully anti-site disordered Sr2FeMoO6 nanoparticles exhibit superparamagnetism with the blocking temperature TB = 240 K and the deteriorated effective magnetic moment μ = 0.055 μB per formula unit.

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.

Eggshell waste is among the most abundant waste materials coming from food processing technologies. Despite the unique properties that both its components (eggshell, ES, and eggshell membrane, ESM) possess, it is very often discarded without further use. This review article aims to summarize the recent reports utilizing eggshell waste for very diverse purposes, stressing the need to use a mechanochemical approach to broaden its applications. The most studied field with regards to the potential use of eggshell waste is catalysis. Upon proper treatment, it can be used for turning waste oils into biodiesel and moreover, the catalytic effect of eggshell-based material in organic synthesis is also very beneficial. In inorganic chemistry, the eggshell membrane is very often used as a templating agent for nanoparticles production. Such composites are suitable for application in photocatalysis. These bionanocomposites are also capable of heavy metal ions reduction and can be also used for the ozonation process. The eggshell and its membrane are applicable in electrochemistry as well. Due to the high protein content and the presence of functional groups on the surface, ESM can be easily converted to a high-performance electrode material. Finally, both ES and ESM are suitable for medical applications, as the former can be used as an inexpensive Ca2+ source for the development of medications, particles for drug delivery, organic matrix/mineral nanocomposites as potential tissue scaffolds, food supplements and the latter for the treatment of joint diseases, in reparative medicine and vascular graft producing. For the majority of the above-mentioned applications, the pretreatment of the eggshell waste is necessary. Among other options, the mechanochemical pretreatment has found an inevitable place. Since the publication of the last review paper devoted to the mechanochemical treatment of eggshell waste, a few new works have appeared, which are reviewed here to underline the sustainable character of the proposed methodology. The mechanochemical treatment of eggshell is capable of producing the nanoscale material which can be further used for bioceramics synthesis, dehalogenation processes, wastewater treatment, preparation of hydrophobic filters, lithium-ion batteries, dental materials, and in the building industry as cement.

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.

Lichens are symbiotic organisms with an extraordinary capability to colonise areas of extreme climate and heavily contaminated sites, such as metal-rich habitats. Lichens have developed several mechanisms to overcome the toxicity of metals, including the ability to bind metal cations to extracellular sites of symbiotic partners and to subsequently form oxalates. Calcium is an essential alkaline earth element that is important in various cell processes. Calcium can serve as a metal ligand but can be toxic at elevated concentrations. This study investigated calcium-rich and calcium-poor sites and the lichen species that inhabit them (Cladonia sp.). The calcium content of these lichen species were analyzed, along with localized calcium oxalate formed in thalli collected from each site. The highest concentration of calcium was found in the lichen squamules, which can serve as a final deposit for detoxification. Interestingly, the highest content of calcium in Cladonia furcata was localized to the upper part of the thallus, which is the youngest. The produced calcium oxalates were species-specific. Whewellite (CaC2O4∙H2O) was formed in the case of C. furcata and weddellite (CaC2O4∙2H2O) was identified in C. foliacea.

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.

In this study, we demonstrate the feasibility of Bi-doped tetrahedrite Cu12Sb4−xBixS13 (x = 0.02–0.20) synthesis in an industrial eccentric vibratory mill using Cu, Sb, Bi and S elemental precursors. High-energy milling was followed by spark plasma sintering. In all the samples, the prevailing content of tetrahedrite Cu12Sb4S13 (71–87%) and famatinite Cu3SbS4 (13–21%), together with small amounts of skinnerite Cu3SbS3, have been detected. The occurrence of the individual Cu-Sb-S phases and oxidation states of bismuth identified as Bi0 and Bi3+ are correlated. The most prominent effect of the simultaneous milling and doping on the thermoelectric properties is a decrease in the total thermal conductivity (κ) with increasing Bi content, in relation with the increasing amount of famatinite and skinnerite contents. The lowest value of κ was achieved for x = 0.2 (1.1 W m−1 K−1 at 675 K). However, this sample also manifests the lowest electrical conductivity σ, combined with relatively unchanged values for the Seebeck coefficient (S) compared with the un-doped sample. Overall, the lowered electrical performances outweigh the benefits from the decrease in thermal conductivity and the resulting figure-of-merit values illustrate a degradation effect of Bi doping on the thermoelectric properties of tetrahedrite in these synthesis conditions.

A green synthetic route for the production of silver nanoparticles (AgNPs) using five different aqueous plant extracts, namely, Berberis vulgaris, Brassica nigra, Capsella bursa-pastoris, Lavandula angustifolia and Origanum vulgare, was investigated in this study. The present work demonstrates the influence of plant extract composition (antioxidant and total phenolic content) on the size and morphology of the produced AgNPs. The biosynthetic procedure was rapid and simple and was easily monitored via colour changes and ultraviolet and visible (UV-Vis) spectroscopy. Subsequently, measurement of zeta potential (ZP), photon cross-correlation spectroscopy (PCCS), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) analysis were employed to characterise the as-synthesised nanoparticles. The XRD investigation confirmed the presence of Ag0 in the nanoparticles, and interactions between the bioactive compounds of the plants and the produced AgNPs were evident in the FTIR spectra. TEM indicated that the nanoparticles exhibited a bimodal size distribution, with the smaller particles being spherical and the larger having a truncated octahedron shape. In addition, the antimicrobial activity of the AgNPs was tested against five bacterial strains. All synthesised nanoparticles exhibited enhanced antimicrobial activity at a precursor concentration of 5 mM compared to the control substance, gentamicin sulphate, with the best results observed for AgNPs prepared with B. nigra and L. angustifolia extracts.

This study shows mechanochemical synthesis as an alternative method to the traditional green synthesis of silver nanoparticles in a comparative manner by comparing the products obtained using both methodologies and different characterization methods. As a silver precursor, the most commonly used silver nitrate was applied and the easily accessible lavender (Lavandula angustofolia L.) plant was used as a reducing agent. Both syntheses were performed using 7 different lavender:AgNO3 mass ratios. The synthesis time was limited to 8 and 15 min in the case of green and mechanochemical synthesis, respectively, although a significant amount of unreacted silver nitrate was detected in both crude reaction mixtures at low lavender:AgNO3 ratios. This finding is of particular interest mainly for green synthesis, as the potential presence of silver nitrate in the produced nanosuspension is often overlooked. Unreacted AgNO3 has been removed from the mechanochemically synthesized samples by washing. The nanocrystalline character of the products has been confirmed by both X-ray diffraction (Rietveld refinement) and transmission electron microscopy. The latter has shown bimodal size distribution with larger particles in tens of nanometers and the smaller ones below 10 nm in size. In the case of green synthesis, the used lavender:AgNO3 ratio was found to have a decisive role on the crystallite size. Silver chloride has been detected as a side-product, mainly at high lavender:AgNO3 ratios. Both products have shown a strong antibacterial activity, being higher in the case of green synthesis, but this can be ascribed to the presence of unreacted AgNO3. Thus, one-step mechanochemical synthesis (without the need to prepare extract and performing the synthesis as separate steps) can be applied as a sustainable alternative to the traditional green synthesis of Ag nanoparticles using plants.

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.

Our objective in this review article is to find out relevant information about methods of determination of antioxidant activity of silver nanoparticles. There are many studies dealing with mentioned problem and herein we summarize the knowledge about methods evaluating the antioxidant activity of silver nanoparticles reported so far. Many authors declare better antioxidant activity of silver nanoparticles compared to the extract used for synthesis of them. In this review, we focused on methods of antioxidant activity determination in detail to find out novel and perspective techniques to solve the general problems associated with the determination of antioxidant activity of silver nanoparticles.

Nanomaterials, including zinc oxide nanoparticles (ZnO NPs), have a great application potential in many fields, such as medicine, the textile industry, electronics, and cosmetics. Their impact on the environment must be carefully investigated and specified due to their wide range of application. However, the amount of data on possible negative effects of ZnO NPs on plants at the cellular level are still insufficient. Thus, we focused on the effect of ZnO NPs on tobacco BY-2 cells, i.e., a widely accepted plant cell model. Adverse effects of ZnO NPs on both growth and biochemical parameters were observed. In addition, reactive oxygen and nitrogen species visualizations confirmed that ZnO NPs may induce oxidative stress. All these changes were associated with the lipid peroxidation and changes in the plasma membrane integrity, which together with endoplasmatic reticulum and mitochondrial dysfunction led to autophagy and programmed cell death. The present study demonstrates that the phytotoxic effect of ZnO NPs on the BY-2 cells is very complex and needs further investigation.

The effects of high-temperature (90°C) sulphuric acid dissolution on the physical and chemical properties of a commercial vermiculite sample, in natural and heated forms, were investigated using chemical, X-ray diffraction, Fourier transform infrared spectroscopy and thermal analyses, and specific surface area measurements. The X-ray diffraction analyses showed that vermiculite and mixed-layer micavermiculite structures in the natural sample were completely destroyed following dissolution in 4 N H2SO4, whereas the basal peak related to mica, which exist in minor amounts in the natural sample, was observed in the X-ray diffraction patterns even after the dissolution in 8 N H2SO4. As a result of the destruction of main clay structures in both samples by acid dissolution, hydrous amorphous silica phases were formed. The maximum specific surface area values were obtained after dissolution in 4 N H2SO4 solution, where the increases in surface area values were approximately 150 (from 3.3 up to 494.6 m2/g) and 24 (from 14.0 up to 335.2 m2/g) times in the natural and heated samples, respectively. The results of all experiments indicated that the heated sample had higher resistance to acid dissolution than the natural sample, probably due to its dehydrated and collapsed mica-like layer content, which was formed by the heating process at 900°C applied before the dissolution experiments. Besides, in this study, the changes in some of the magnetic properties of the heated sample, before and after dissolution, were also determined.

Performing solution-phase oximation reactions with hydroxylamine hydrochloride (NH2OH·HCl) carries significant risk, especially in aqueous solutions. In the present study, four N-substituted indole-3-carboxaldehyde oximes were prepared from the corresponding aldehydes by solvent-free reaction with NH2OH·HCl and a base (NaOH or Na2CO3) using a mechanochemical approach, thus minimizing the possible risk. In all cases, the conversion to oximes was almost complete. The focus of this work is on 1-methoxyindole-3-carboxaldehyde oxime, a key intermediate in the production of indole phytoalexins with useful antimicrobial properties. Under optimized conditions, it was possible to reach almost 95% yield after 20 min of milling. Moreover, for the products containing electron-donating substituents (-CH3, -OCH3), the isomerization from the oxime anti to syn isomer under acidic conditions was discovered. For the 1-methoxy analog, the acidic isomerization of pure isomers in solution resulted in the formation of anti isomer, whereas the prevalence of syn isomer was observed in solid state. From NMR data the syn and anti structures of produced oximes were elucidated. This work shows an interesting and possibly scalable alternative to classical synthesis and underlines environmentally friendly and sustainable character of mechanochemistry.

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.

Iron-based substrates with polyethylene glycol coating were prepared as possible materials for biodegradable orthopedic implants. Biodegradable materials that provide mechanical support of the diseased tissue at the time of implanting and then disappear gradually during the healing process are sometimes favored instead of permanent implants. The implant degradation rate should match the time of the tissue regrowth. In this work, the degradation behavior of iron-based foams was studied electrochemically during immersion tests in Hanks’ solution. The corrosion rate of the polyethylene glycol-coated samples increased and the corrosion potential shifted to more negative values. This indicates an enhanced degradation rate as compared to the uncoated material, fulfilling the goal of being able to tune the degradation rate. It is the interfacial interaction between the hydrophilic polymer layer and the iron surface that is responsible for the enhanced oxidation rate of iron.

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.