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Mechanochemical reactions by ball milling have opened new avenues in chemical synthesis. Particularly, mechanochemistry has facilitated the reaction of insoluble materials to simplify stablished synthetic protocols and develop new ones. One notable application involves the use of calcium carbide (CaC2) as a C2-synthon through mechanochemistry, which has offered a more practical alternative to incorporate C2-units compared to the conventional use of highly flammable gaseous acetylene. For example, by ball milling, the acetylenic anions [C2]2- found in CaC2 have been harnessed for the synthesis of diverse functional carbon materials as well as discrete organic molecules. This Concept aims to contribute to the conceptualization of this innovative approach while highlighting both its advantages and the challenges inherent in the use of CaC2.

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High Energy Ball-Milling (HEBM) modifies starchs' granule morphology, physicochemical properties, and chemical structure. However, understanding how the HEBM changes the starch chemical structure is necessary to control these modifications. Therefore, this study aimed to investigate the changes in potato starch's long- and short-range molecular order during HEBM at different environmental conditions such as oxygen (Air) and humidity content. Due to the correlation between the starch modification and the energy supplied (Esupp) by the HEBM, Burgio's equation was used to calculate this energy. The starch transformation was followed by X-ray diffraction, Fourier Transform-Infrared Spectroscopy, and Raman spectroscopy. A Principal Component Analysis (PCA) was conducted to reduce the HEBM variables. PAC analysis demonstrated that the different oxygen-humidity conditions do not affect the HEBM of potato starch. Based on the starch chemical structure transformation correlated with Esupp during HEBM, four stages were observed: orientation, modification, mechanolysis, and over-destruction. It was identified for the first time that at low milling energy (<1.5 kJ/g, orientation stage), the glycosidic rings change their orientation, and starch-water interaction increases while the starch's organization reduces. Ergo, the potato starch could be more susceptible to chemical modifications during the first two stages.

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Mechanochemical reactions offer methodological and environmental advantages for chemical synthesis, constantly attracting attention within the scientific community. Besides unmistakable sustainability advantages, the conditions under which mechanochemical reactions occur, namely solventless conditions, sometimes facilitate the isolation of otherwise labile or inaccessible products. Despite these advantages, limited knowledge exists regarding the mechanisms of these reactions and the types of intermediates involved. Nevertheless, in an expanding number of cases, ex situ and in situ monitoring techniques have allowed for the observation, characterization, and isolation of reaction intermediates in mechanochemical transformations. In this Minireview, we present a series of examples in which reactive intermediates have been detected in mechanochemical reactions spanning organic, organometallic, inorganic, and materials chemistry. Many of these intermediates were stabilized by non-covalent interactions, which played a pivotal role in guiding the chemical transformations. We believe that by uncovering and understanding such instances, the growing mechanochemistry community could find novel opportunities in catalysis and discover new mechanochemical reactions while achieving simplification in chemical reaction design.

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To prevent neural tube defects and other cardiovascular diseases in newborns, folic acid (FA) is recommended in pregnant women. A daily dose of 600 µg FA consumption is widely prescribed for women during pregnancy and 400 µg for women with childbearing potential. FA is a class IV compound according to the Biopharmaceutics Classification System (BCS) due to its low permeability (1.7 × 10-6 cm/s) and low solubility (1.6 mg/L); therefore, it must be administered via a formulation that enhances its solubility. Studies reported in the literature have proved that co-amorphization and salt formation of a poorly soluble drug with amino acids (AA) can significantly increase its solubility. Although arginine has been used with FA as a supplement, there is no information on the effect of basic AA (arginine and lysine) on the physical and chemical properties of FA-AA binary formulations. The present study implemented a conductimetric titration methodology to find the effective molar ratio to maximize FA solubility. The results showed that a 1:2.5 FA:AA molar ratio maximized solubility for arginine and lysine. Binary formulations were prepared using different methods, which led to an amorphous system confirmed by the presence of a glass transition, broad FTIR bands, and the absence of an X-ray diffraction pattern. Results of FA:AA (1:2.5) solubility increased in the range of 5500-6000 times compared with pure FA. In addition to solubility enhancement, the binary systems presented morphological properties that depend on the preparation method and whose consideration could be strategic for scaling purposes.

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Starch's crystalline structure and gelatinization temperature might facilitate or hinder its use. Ball milling has frequently been mentioned in the literature as a method for reducing starch size and as a more environmentally friendly way to change starch, such as by increasing surface area and reactivity, which has an impact on other starch properties. In this study, starch samples were milled for varying durations (1, 5, 10, 20, and 30 h) and at different starch-to-ball mass ratios (1:6 and 1:20). Microscopy and XRD revealed that prolonged milling resulted in effective fragmentation and a decrease in crystallinity of the starch granules. Increasing milling times resulted in an increase in amylose content. Rheology and thermal studies revealed that gelatinization temperatures dropped with milling duration and that viscosity and thixotropy were directly influenced. The samples milled for 10, 20, and 30 h at a ratio of 1:20 were the most fragmented and upon drying formed a transparent film at ambient temperature, because of the lower gelatinization temperature. Starch ball milling could lead to the use of this material in thermosensitive systems.

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The occurrence of crystalline intermediates in mechanochemical reactions might be more widespread than previously assumed. For example, a recent study involving the acetate-assisted C-H activation of N-Heterocycles with [Cp*RhCl2 ]2 by ball milling revealed the formation of transient cocrystals between the reagents prior to the C-H activation step. However, such crystalline intermediates were only observed through stepwise intervallic ex-situ analysis, and their exact role in the C-H activation process remained unclear. In this study, we monitored the formation of discrete, stoichiometric cocrystals between benzo[h]quinoline and [Cp*RhCl2 ]2 by ball milling using in-situ synchrotron X-ray powder diffraction. This continuous analysis revealed an initial cocrystal that transformed into a second crystalline form. Computational studies showed that differences in noncovalent interactions made the [Cp*RhCl2 ]2 unit in the later-appearing cocrystal more reactive towards NaOAc. This demonstrated the advantage of cocrystal formation before the acetate-assisted metalation-deprotonation step, and how the net cooperative action of weak interactions between the reagents in mechanochemical experiments can lead to stable supramolecular assemblies, which can enhance substrate activation under ball-milling conditions. This could explain the superiority of some mechanochemical reactions, such as acetate-assisted C-H activation, compared to their solution-based counterparts.

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This review aims to expose mechanical milling as an alternative method for generating copper-based particles (copper particles (CuP) and copper composites (CuC)); more specifically, via a top-down or bottom-up approach, on a lab-scale. This work will also highlight the different parameters that can affect the size distribution, the type, and the morphology of the obtained CuP or CuC, such as the type of mechanical mill, ball-to-powder ratios (BPR), the milling speed, milling time, and the milling environment, among others. This review analyzes various papers based on the Cu-based particle generation route, which begins with a pretreatment step, then mechanical milling, its approach (top-down or bottom-up), and the post-treatment. Finally, the characterization methods of the resulting CuP and CuC through mechanical milling are also discussed.

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Hydrogen storage in Mg/MgH2 materials is still an active research topic. In this work, a mixture of Mg-15wt.% VCl3 was produced by cryogenic ball milling and tested for hydrogen storage. Short milling time (1 h), liquid N2 cooling, and the use of VCl3 as an additive produced micro-flaked particles approximately 2.5-5.0 µm thick. The Mg-15wt.% VCl3 mixture demonstrated hydrogen uptake even at near room-temperature (50 °C). Mg-15wt.% VCl3 achieved ~5 wt.% hydrogen in 1 min at 300 °C/26 bar. The fast hydriding kinetics is attributed to a reduction of the activation energy of the hydriding reaction (Ea hydriding = 63.8 ± 5.6 kJ/mol). The dehydriding reaction occurred at high temperatures (300-350 °C) and 0.8-1 bar hydrogen pressure. The activation energy of the dehydriding reaction is 123.11 ± 0.6 kJ/mol. Cryomilling and VCl3 drastically improved the hydriding/dehydriding of Mg/MgH2.

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Heterojunctions based on metal halide perovskites (MHPs) are promising systems for the photocatalytic hydrogen evolution reaction (HER). In this work, we coupled Cs3Bi2Br9 nanocrystals (NCs), obtained by wet ball milling synthesis, with g-C3N4 nanosheets (NSs), produced by thermal oxidation of bulk g-C3N4, in air. These methods are reproducible, inexpensive and easy to scale up. Heterojunctions with different loadings of Cs3Bi2Br9 NCs were fully characterised and tested for the HER. A relevant improvement of H2 production with respect to pristine carbon nitride was achieved at low NCs levels reaching values up to about 4600 µmol g-1 h-1. This work aims to provide insights into the synthesis of inexpensive and high-performing heterojunctions using MHP for photocatalytic applications.

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The formation and scission of chemical bonds facilitated by mechanical force (mechanochemistry) can be accomplished through various experimental strategies. Among them, ultrasonication of polymeric matrices and ball milling of reaction partners have become the two leading approaches to carry out polymer and small molecule mechanochemistry, respectively. Often, the methodological differences between these practical strategies seem to have created two seemingly distinct lines of thought within the field of mechanochemistry. However, in this Perspective article, the reader will encounter a series of studies in which some aspects believed to be inherently related to either polymer or small molecule mechanochemistry sometimes overlap, evidencing the connection between both approaches.

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Silver-gold nanoalloys were prepared from their metal salts precursors through bottom-up mechanochemical synthesis, using one-pot or galvanic replacement reaction strategies. The nanostructures were prepared over amorphous SiO2 as an inert supporting material, facilitating their stabilization without the use of any stabilizing agent. The nanomaterials were extensively characterized, confirming the formation of the bimetallic nanostructures. The nanoalloys were tested as catalysts in the hydrogenation of 2-nitroaniline and exhibited up to 4-fold the rate constant and up to 37% increased conversion compared to the respective single metal nanoparticles. Our approach is advantageous to produce nanoparticles with clean surfaces with available catalytic sites, directly in the solid-state and in an environmentally friendly manner.

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Pure potato starch has been modified by high-energy-ball-milling as a function of energy supplied, aiming to obtain products for different possibilities of industrial application. Burgios's equation has been used to calculate the energy supplied. The effect of the milling has been followed by a characterization of the starch morphology, crystallinity, solubility, swelling, retrogradation, viscosity, apparent viscosity, functional groups, and reducing sugar concentration. The high-energy-ball-milling not only changes the physical properties but also induces the mechanolysis of potato starch, breaking the glycosidic linkages of the starch molecules. A representation of the possible mechanism of starch mechanolysis is proposed. Three stages of the transformation of potato starch through high-energy ball-milling can be identified. Each of these stages generates starch with properties that can be used in different industrial applications.

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Tthe present work studied the cationic substitution of Y3+ by Bi3+ on the crystal structure of orthorhombic YFeO3 and its effect over magnetic, dielectric and electric properties of multiferroic yttrium orthoferrite. Stoichiometric mixtures of Y2O3, Fe2O3 and Bi2O3 were mixed and milled for 5 h using a ball to powder weight ratio of 10:1 by high-energy ball milling. The obtained powders were pressed at 1500 MPa and sintered at 700 °C for 2 h. The test samples were characterized at room temperature by X-ray diffraction (XRD), vibrating sample magnetometer (VSM), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS) and impedance spectroscopy (IS). The X-ray diffraction patterns disclosed a maximum solubility of 30 % mol. of Bi3+ into the orthorhombic YFeO3. For higher concentrations, a transformation from orthorhombic to garnet structure was produced, obtaining partially Y3Fe5O12 phase. The substitution of Bi3+ in Y3+ sites promoted a distortion into the orthorhombic structure and modified Fe-O-Fe angles and octahedral tilt. In addition, it promoted a ferromagnetic (FM) order, which was attributed to both the crystal distortion and Dzyaloshinskii-Moriya interaction. For doped samples, an increase in real permittivity values was observed, and reduced with the increase of frequency. This in good agreement with the Maxwell-Wagner effect.

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Soybean meal has been intensively used as a substrate in culture media for several microorganisms. However, the fermentable sugar containing the soybean needs to be released from the solid matrix through different processes. Against this backdrop, the present study explores the use of high-energy ball milling as a one-step treatment method for expedited production of fermentable sugars of textured soybean. The best result is observed after only 5 min of milling, obtaining 34.1 times more fermentable sugars than untreated textured soybean, and 2.5 times more than commercially used soybean meal. Notably, the textured soybean ball-milled has been used as a substrate for Bacillus thuringiensis var. kurstaki HD-73 fermentation. The cell and spore production is also compared with a standard Rowe media. The maximum cell concentration obtained in the entire fermentation process using ball-milled textured soybean media is found to be higher than the concentration obtained using the standard Rowe media. In addition, it is observed that there is a direct correlation between maximum cell production and reducing sugar concentration generated by the high-energy ball milling treatment. No fermentation inhibitors or by-products are generated during the physical treatment.

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The use of colorimetric methods for protein quantification in microalgae is hindered by their elevated amounts of membrane-embedded intracellular proteins. In this work, the protein content of three species of microalgae was determined by the Lowry method after the cells were dried, ball-milled, and treated with the detergent sodium dodecyl sulfate (SDS). Results demonstrated that the association of milling and SDS treatment resulted in a 3- to 7-fold increase in protein quantification. Milling promoted microalgal disaggregation and cell wall disruption enabling access of the SDS detergent to the microalgal intracellular membrane proteins and their efficient solubilization and quantification.

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[This corrects the article DOI: 10.3762/bjoc.13.167.].

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The use of mechanochemistry to carry out enantioselective reactions has been explored in the last ten years with excellent results. Several chiral organocatalysts and even enzymes have proved to be resistant to milling conditions, which allows for rather efficient enantioselective transformations under ball-milling conditions. The present article reports the first example of a liquid-assisted grinding (LAG) mechanochemical enzymatic resolution of racemic ß3-amino esters employing Candida antarctica lipase B (CALB) to afford highly valuable enantioenriched N-benzylated-ß3-amino acids in good yields. Furthermore the present protocol is readily scalable.

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In this work, industrial grade multi-walled carbon nanotubes (MWCNT) were coated with humic acid (HA) for the first time by means of a milling process, which can be considered an eco-friendly mechanochemical method to prepare materials and composites. The HA-MWCNT hybrid material was characterized by atomic force microscopy (AFM), scanning electron microscopies (SEM and STEM), X-ray photoelectron spectroscopy (XPS), termogravimetric analysis (TGA), and Raman spectroscopy. STEM and AFM images demonstrated that the MWCNTs were efficiently coated by the humic acid, thus leading to an increase of 20% in the oxygen content at the nanotube surface as observed by the XPS data. After the milling process, the carbon nanotubes were shortened as unveiled by SEM images and the values of ID/IG intensity ratio increased due to shortening of the nanotubes and increasing in the number defects at the graphitic structure of carbon nanotubes walls. The analysis of TGA data showed that the quantity of the organic matter of HA on the nanotube surface was 25%. The HA coating was responsible to favor the dispersion of MWCNTs in ultrapure water (i.e. -42mV, zeta-potential value) and to improve their capacity for copper removal. HA-MWCNTs hybrid material adsorbed 2.5 times more Cu(II) ions than oxidized MWCNTs with HNO3, thus evidencing that it is a very efficient adsorbent material for removing copper ions from reconstituted water. The HA-MWCNTs hybrid material did not show acute ecotoxicity to the tested aquatic model organisms (Hydra attenuata, Daphnia magna, and Danio rerio embryos) up to the highest concentration evaluated (10mgL-1). The results allowed concluding that the mechanochemical method is effective to coat carbon nanotubes with humic acid, thus generating a functional hybrid material with low aquatic toxicity and great potential to be applied in environmental nanotechnologies such as the removal of heavy metal ions from water.

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Pearled amaranth grains obtained by abrasive milling were processed by planetary ball milling to produce amaranth flours. The influence of milling energy on rheological and thermal behavior of amaranth flour dispersions and stability during 24 h storage at 4 °C were investigated based on a factorial design. The rheological behavior of flour dispersions (4 % and 8 % w/v) was determined using a rotational viscometer, while gelatinization degree was determined by differential scanning calorimetry as a measure of structural changes.The power law model was found to be suitable in expressing the relationship between shear stress and shear rate. Flour dispersions showed a pseudoplastic behavior. However this character decreased with the storage being dependent on flour concentration and milling energy. A decrease of the consistency index and an increase of the flow behavior index were observed as a result of the increasing milling energy. Gelatinization enthalpy decrease showed the loss of crystalline structure due to ball milling. Amaranth flour dispersions presented increasing stability during storage. It was observed, that the stability changed with the concentration of amaranth flours.Thus, more stable dispersions were obtained as the flour concentration increased. The highly milled sample was the most stable sample during the storage.

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Acyclovir, an analog of 2'-deoxyguanosine, is one of the most important drugs in the current approved antiviral treatment. However, it's biopharmaceutical properties, contribute to acyclovir's poor oral bioavailability, which restricts the clinical use of the drug. In this view, the aim of this work was to improve the dissolution rate and intestinal permeability of acyclovir through the development of ball milling solid dispersions with the hydrophilic carriers Pluronic F68®, hydroxypropylmethyl cellulose K100M® and chitosan. Solid dispersions were obtained and completely characterized through different solid state techniques. The solid state data demonstrated a decrease in the crystallinity (amorphous phase and defects) and the presence of hydrogen bonds for SD HPMC and SD CTS. The enhancement of dissolution rates was observed for all SDs developed. In addition, no detrimental effects over the in vitro antiviral activity were detected. The solid dispersions with Pluronic F68® significantly improved the intestinal permeability of acyclovir across Caco-2 cells. In summary, the SDs developed in this study could be considered as potential systems for solid dosage forms containing acyclovir with superior biopharmaceutical properties.

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