Green Balls Research Articles

Doughty-electronegative heteroatom-induced defective MoS2 for the hydrogen evolution reaction.

Producing hydrogen through water electrolysis is one of the most promising green energy storage and conversion technologies for the long-term development of energy-related hydrogen technologies. MoS2 is a very promising electrocatalyst which may replace precious metal catalysts for the hydrogen evolution reaction (HER). In this work, doughty-electronegative heteroatom defects (halogen atoms such as chlorine, fluorine, and nitrogen) were successfully introduced in MoS2 by using a large-scale, green, and simple ball milling strategy to alter its electronic structure. The physicochemical properties (morphology, crystallization, chemical composition, and electronic structure) of the doughty-electronegative heteroatom-induced defective MoS2 (N/Cl-MoS2) were identified using SEM, TEM, Raman, XRD, and XPS. Furthermore, compared with bulk pristine MoS2, the HER activity of N/Cl-MoS2 significantly increased from 442mV to 280mV at a current of 10mA cm-2. Ball milling not only effectively reduced the size of the catalyst material, but also exposed more active sites. More importantly, the introduced doughty-electronegative heteroatom optimized the electronic structure of the catalyst. Therefore, the doughty-electronegative heteroatom induced by mechanical ball milling provides a useful reference for the large-scale production of green, efficient, and low-cost catalyst materials.

Effective adsorption of Congo red dye by magnetic chitosan prepared by solvent-free ball milling

Chitosan and Fe3O4 were used as raw materials to successfully synthesize chitosan@Fe3O4 by a simple, green and friendly solvent-free ball milling method. The surface morphology, phase composition, structure and magnetic properties of the chitosan@Fe3O4 material were characterized using SEM, FT-IR, PXRD, VSM methods. The prepared material was used as an adsorbent to remove the target congo red dye. The effect of experimental factors such as solution pH and contact time on the adsorption performance were studied and optimized. The adsorption behavior of chitosan@Fe3O4 material for congo red dye was investigated, and the adsorption mechanism, recycling performance of the materials were discussed.

Recovery of Lignins with Potent Antioxidant Properties from Shells of Edible Nuts by a Green Ball Milling/Deep Eutectic Solvent (DES)-Based Protocol.

Lignins are phenolic polymers endowed with potent antioxidant properties that are finding increasing applications in a variety of fields. Consequently, there is a growing need for easily available and sustainable sources, as well as for green extraction methodologies of these compounds. Herein, a ball milling/deep eutectic solvent (DES)-based treatment is reported as an efficient strategy for the recovery of antioxidant lignins from the shells of edible nuts, namely chestnuts, hazelnuts, peanuts, pecan nuts, and pistachios. In particular, preliminarily ball-milled shells were treated with 1:2 mol/mol choline chloride:lactic acid at 120 °C for 24 h, and the extracted material was recovered in 19–27% w/w yields after precipitation by the addition of 0.01 M HCl. Extensive spectroscopic and chromatographic analysis allowed for confirmation that the main phenolic constituents present in the shell extracts were lignins, accompanied by small amounts (0.9% w/w) of ellagic acid, in the case of chestnut shells. The recovered samples exhibited very promising antioxidant properties, particularly in the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay (EC50 values ranging from 0.03 to 0.19 mg/mL). These results open new perspectives for the valorization of nut shells as green sources of lignins for applications as antioxidants, e.g., in the biomedical, food, and/or cosmetic sector.

Parametric Optimization of Ball-Milled Bimetallic Nanoadsorbents for the Effective Removal of Arsenic Species

Arsenic (As) removal from portable water bodies using the nanotechnology-based adsorption technique offers a unique method to lower the As contamination below the World Health Organization’s (WHO) maximum contaminant level (MCL). This work promotes a systematic methodological-based adsorption study by optimizing the different parameters that affect As removal using TiO2/γ-Fe2O3 nanocomposites (T/M NCs) prepared with the green, facile, and cost-effective ball milling method. The studies using X-ray Diffraction (XRD) illustrate the structural modifications with variations in the constituting T/M ratios, with high-resolution transmission electron microscopy (HRTEM) being used for the NC morphological studies. The optical characterization studies showed that bandgap tuning between 2–2.8 eV reduced the maghemite (γ-Fe2O3) content in the NCs and the elemental analysis confirmed the desired stoichiometry of the NCs. The magnetic measurements showed that the magnetic interaction among the particles tends towards exchange coupling behavior as the weight ratio of γ-Fe2O3 content decreases in the NCs. The adsorption studies using the most efficient NCs with an optimized condition (NC dose (8 g/L), contact time (15 min), As concentration (2 ppm), and pH (4)) resulted in a more than 99% removal of As species, suggesting the excellent behavior of the synthesized nanomaterial for water treatment and making it more economical than other competing adsorption techniques and materials.

Ball milling synthesis of robust sandwich-structured C/Si@SnO2 anode with porous silicon buffer layer for fast charging lithium-ion battery

Aiming at enhancing cyclic stability and fast charging performance of lithium-ion batteries (LIBs), a sandwich structured composite with a buffer layer of porous silicon (Si) between the carbon layer and SnO2 layer (C/Si@SnO2) was developed by using ball milling. The results showed that the Si layer with plenty of mesoporous and cracks was coated successfully and the introduction of Si increased the disordered structure of SnO2, including the expansion of interlayer spacing, the emergence of Sn and SiOx indicated the reaction between Si and SnO2 occurred during the ball milling process, while the generation of Si-O-Sn and Si-O-C bonds formed by Si integration connected the three components with intimate interfaces. Used as an anode for LIBs, the C/Si@SnO2 electrode performed a favorable discharge capacity (919.21 mAh·g−1 at 0.1 A·g−1), the ultra-long cyclability after 1000 and 2000 cycles, impressive rate performance (269.87 mAh·g−1 at 5 A·g−1), and fast charging capability accompanying discharge capacity of 805.57 mAh·g−1 at 0.2 A·g−1 and charge capacity of 400.55 mAh·g−1 at 2 A·g−1. In addition, the electrochemical impedance spectroscopy analysis showed that the graphitic carbon layer and porous Si layer improved the rapid Li+ diffusion and transportation, which was beneficial to fast charging in LIBs. Our work provided a facile and green ball milling method to construct porous sandwich structured metal oxide/C composites with the introduction of Si, which can effectively increase the disordered structure of composite and also open up a new scheme of Si materials as an anode in the field of fast charging for LIBs.

Incorporating pristine biochar into metal-organic frameworks: Facile green synthesis, characterization, and wastewater remediation

Modification of pristine biochar (PBC) with metal-organic frameworks (MOFs) is essential for the enhancement of biochar properties for heavy metals cleanup from wastewater. The green solvent-free ball milling method was employed for the incorporation of PBC and MOFs. The incorporation was done at different mixing percentages of MOFs to biochar; 15 %, 25 %, and 50 %. The ball-milled PBC/MOFs were then characterized by BET, SEM-EDS, FTIR, XPS, and TGA-DSC analysis. The engineered PBC/MOF was tested for heavy metals (Cd, Ni, and Pb) remediation from wastewater. The ball milling process enhanced the ball-milled biochar/MOFs nanocomposites' crystallinity, surface morphology, textural properties, and thermal stability. The removal percentage for influent and effluent were between 94.40 % – 95.48 % and 95.73 % – 96.87 % respectively, while the removal percentage was between 96.89 % – 98.22 % obtained for the spiked solution with deionized water. From the characterization and wastewater application results obtained, ball-milled biochar/MOFs nanocomposites could be applied for remediation of wastewater.

Amino acid functionalized boron nitride nanosheets towards enhanced thermal and mechanical performance of epoxy composite

HypothesisThe practical applications of boron nitride nanosheet (BNNS) are dramatically limited by the harsh exfoliation and surface functionalization conditions due to the hydrophobic and chemically inert nature. This issue can be improved by selecting efficient modifiers with hydrophilic groups. ExperimentsA green and scalable amino acid-assisted ball milling method is presented to exfoliate and functionalize BNNS simultaneously. The different interactions between BNNS and four amino acids (tryptophan (Trp), phenylalanine (Phe), arginine (Arg), lysine (Lys)) are thoroughly investigated to rationalize the thermal and mechanical properties of their corresponding epoxy (EP) composites. FindingTrp and Phe display higher functionalization degree and dispersibility of BNNS than Arg and Lys thanks to the additional π-π interactions between the aromatic groups and BNNS. Moreover, both BNNS-Trp/EP and BNNS-Phe/EP exhibit higher cross-plane thermal conductivity of 2.1 and 1.96 W m−1 K−1 at 30 wt% filler loading. In addition, the mechanical strengths of all these amino acids functionalized BNNS filled epoxy composites are significantly enhanced due to stronger interfacial interactions between fillers and epoxy matrix. Thus, this work paves the way for the facile mass production of functionalized BNNS and expedites their applications in thermal interface materials of electronic components.

Effects of mirror and coloured balls as environmental enrichment tools on performance, welfare and meat quality traits of commercial broiler.

This study evaluated the effect of environmental enrichment on the performance, behaviour and welfare aspects; blood biochemistry; carcass and meat quality traits of broiler chickens. A total of 450 straight run broiler chicks (Ross-308) were divided into 5 treatment groups having 6 replicates of 15 birds each under a completely randomised design. Treatments were environmental enrichment (EE) tools and consisted of C = control group; R = red ball for EE; G = green ball for EE; B = blue ball for EE and M = mirror for EE. These environmental enrichment tools were provided throughout the experimental period (0 to 35days). Mean feed intake per bird was higher in all treatment groups except the blue balls group; weight gain and feed conversion ratio were better in the green and blue ball groups. Broiler chickens reared under different environmental enrichment were more active and they exhibited maintenance behaviour (preening, dust bathing and wing stretching, or scratching) more frequently. Regarding welfare traits, lower incidence of toe damage, footpad dermatitis and hock burn was observed in birds having different environmental enrichment tools as compared to the control group. The birds reared with red balls as environmental enrichment showed the lowest values for glucose, cholesterol, total protein, albumin and globulin amongst all the treatment groups. Birds reared with green balls had the highest body weight at slaughter, dressed weight, carcass yield and liver weight. Breast meat of environmentally enriched treated groups was lighter and had lower ultimate pH. It was concluded that the addition of environmental enrichment tools (visual, structural and plastic) motivates the birds for physical activities and improves the performance of broiler chickens.

Isoquercitrin isolated from newly bred Green ball apple peel in lipopolysaccharide-stimulated macrophage regulates NF-κB inflammatory pathways and cytokines.

Apple peel has several bioactive properties. The fruit is grown worldwide, and its ingredients are used medicinally. However, its anti-inflammatory activities are poorly characterized. In this study, isoquercitrin isolated from newly bred Green ball apple peel from Korea showed anti-inflammatory effects. To confirm its anti-inflammatory effects, isoquercitrin was treated with lipopolysaccharide, which induces proinflammatory factors in Raw 264.7 macrophage cells. Proinflammatory effects were measured by real-time polymerase chain reaction and Western blotting as well as enzyme-linked immunosorbent assay. Cell viability was measured using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay to define the isoquercitrin concentration nontoxic to cells. Nitric oxide (NO) production, prostaglandin E2, inducible NO synthase, cyclooxygenase-2 (COX-2), and nuclear factor-κB p65 protein expression decreased in a concentration-dependent manner by isoquercitrin. mRNA expression of tumor necrosis factor-α, interleukin (IL)-1β, IL-6, monocyte chemoattractant protein-1, and prostaglandin E synthase 2 (PTGES2) as proinflammatory factors significantly decreased. PTGES2, which was stimulated by COX-2 and involved in PGE2 expression, was inhibited. Therefore, this study rendered isoquercitrin isolated from the newly bred Green ball apple peel as a potential pharmacological alternative to treat inflammation-related diseases.

Slow Phase Transition-Induced Scan Rate Dependence of Spin Crossover in a Two-Dimensional Supramolecular Fe(III) Complex

Slow Phase Transition-Induced Scan Rate Dependence of Spin Crossover in a Two-Dimensional Supramolecular Fe(III) Complex

Heterogenously‐expressed chitosanase combining a green ball milling method for enzymatic degradation

AbstractChitooligosaccharides (COSs) and d‐glucosamine (GlcN), the most valuable biomolecules due to their various physiological functions, can be available inexpensively from chitosan by bio‐enzymatic degradation, in which chitosanases play a key role. On the other hand, pretreatment of chitosan is the necessary procedure in the bioproduction by enzymatic hydrolysis. Therefore, the green and efficient pretreatment strategy as well as superior enzyme activity are the most critical aspects in scaled up production. This study investigated environmentally friendly and efficient enzymatic hydrolysis of powdery chitosan (PC) pretreated by ball‐milling. First, heterologous expression yielded OUC‐CsnPT, a glycoside hydrolase family 46 chitosanase with a predominant specific activity of 5346.56 U/mg at pH 6.0°C and 45°C. The endo‐type chitosanase OUC‐CsnPT hydrolyzed chitosan to produce GlcN and chitobiose [(GlcN)2]. Then, ball‐milling was employed to pretreat PC to promote chitosanase OUC‐CsnPT hydrolysis, and the effectiveness was characterized by scanning electron microscope, X‐ray diffraction, and FTIR‐attenuated total reflection. Through the development of the novel route, the yield of COSs and GlcN for ball‐milling powdery chitosan increased by 10.8‐folds with a concentration of 14.5 μmol/ml. Hence, this technique presents a promising strategy suited to be a straightforward and environmentally friendly option for oligosaccharides production, broadening the theoretical basis for PC biodegradation.

Fluorous Metal–Organic Frameworks with Unique Cage-in-Cage Structures Featuring Fluorophilic Pore Surfaces for Efficient C 2 H 2 /CO 2 Separation

Fluorous Metal–Organic Frameworks with Unique Cage-in-Cage Structures Featuring Fluorophilic Pore Surfaces for Efficient C ₂ H ₂ /CO ₂ Separation

Facilitating the emergence of intraverbal tacts in children with autism spectrum disorder: A preliminary analysis.

Intraverbal tacts are an example of multiply controlled verbal behavior. More specifically, they are verbal responses under control of both a nonverbal (visual) stimulus (e.g., a green ball) and a verbal (auditory) stimulus (e.g., "What color?" vs. "What shape?"). Studies have shown that verbal behavior training can be arranged in a way that would lead to the emergence of other verbal operants, including multiply controlled (convergent) intraverbals. Our study sought to evaluate the relevance of a specific set of component skills on the emergence of intraverbal tacts in children with an autism spectrum disorder. Intraverbal tacts were observed only when all component skills were mastered, suggesting that this set of skills was sufficient to produce emergent verbal performance. Preliminary data were obtained on the necessity of 4 of the 6 component skills and tentatively suggest that they may be necessary to produce emergent intraverbal tacts, at least under some conditions.

A new genus of soil green microalgae Edaphochloris gen. nov. (Chlorellaceae, Trebouxiophyceae)

The problem of studying the species diversity of small single-celled green coccoid microalgae (Chlorophyta) is still relevant, since their simple and uniform cellular morphology makes it extremely difficult to correctly identify them. It is now generally accepted that the best approach for creating a new, more natural classification of “little green balls” is an approach that combines morphological, ecological, physiological and molecular phylogenetic methods. Strains ACSSI 104 and ACSSI 144 were isolated from solonetz and chestnut soil (Volgograd region, Russia). Their cells have a typical Nannochloris-like morphology: single spherical or subspherical cells, chloroplast single, parietal, cup-shaped, without pyrenoid, but with starch grains in it. Old cells accumulate numerous oil droplets in cytoplasm. Reproduction by 2−4 autospores. Autospores of both strains are equal size and exhibit liberation by rupture of sporangium cell wall. Zoospores and sexual reproduction not observed. Both strains are part of independent cluster closely related to genera Marvania, Pumiliosphaera, Nannochloris and Gloeotila. A comparative analysis of morphological (cell size, chloroplast type) and ultrastructural characteristics (structure of cell wall and lamellar system), features of reproduction (asexual reproduction by autospores only) and habitat (soil) with other members of the Nannochloris-clade, as well as results of analysis of 18S rRNA gene and ITS2 secondary structure of the studied strains, allowed us to propose a new genus – Edaphochloris with the type species – E. andreyevae. The report was prepared based on the materials of the V All-Russian Scientific Conference with international participation "Algae: problems of systematics, ecology and use in monitoring", 2021.

The first finding of aegagropilious, or algal balls, in the oldest freshwater Lake Baikal

Abstract. Free-floating algal aggregations, or aegagropilious, are a rare phenomenon known from some freshwater or marine environments worldwide. In September 2014, unusual green algal balls were washed ashore in Ludar Bay on the west coast of the northern basin of Lake Baikal. The paper describes these algal aggregations and characterizes their composition. The Baikal algal balls mainly consisted of green filamentous algae of the family Cladophoraceae, such as Cladophora glomerata, Rhizoclonium sp., and Chaetomorpha sp. Other prominent components of the balls were numerous filaments of Spirogyra and Oedogonium. These taxa are known for their rapid growth in response to nutrients increase. As the result of the hyperproduction of filamentous benthic algae in the coastal zone of Lake Baikal, new living forms such as aegagropilious-like aggregations have been occurring. The algal balls signify the adaptive capacities of the Lake Baikal algal communities and might retain their functioning in the natural ecosystem s self-purification processes.

Evaluation of Zucchini (Cucurbita pepo L.) Genotypes for Spring Season Production in the Mid–Hills of Nepal

Zucchini (Cucurbita pepo L.) is one of the most popular and demanded vegetable in Nepal. Seedlings of seven genotypes of squash gourd; Super Squash Ball, Squash Long, Squash Light, Squash Green Ball, Squash Green House Sondo V (check) and Grey Zucchini (check) were transplanted on second week of March in two consecutive years; 2016 and 2017 in field condition at Khumaltar with a spacing of 90 x 90 cm in four replications. The standard recommended dose of fertilizers (240:180:60 NPK kg/ha + 15 ton FYM/ha) and minimum pesticide and fungicide was applied. The main objective of this experiment was to find out suitable high yielding and insect pest and disease tolerant hybrid Zucchini cultivars for commercial production in mid-hills of Nepal. Crops were evaluated for their vegetative, insect pest and disease, and yield attributing parameters. Among the tested genotypes; Squash Long was found highly uniform, vigorous, least virus and insect damage, significantly higher number of fruits(8.6), and yield (3894 g) per plant and yield (46.89 t/ha) followed by Super Squash Ball having highly uniform, less insect and powdery mildew damage, significantly higher number of fruits (8.5) and yield (2565 g) per plant and yield (29.28 t/ha) as compared to check Sondo V and Grey Zucchini where Sondo V had yield (22.50 t/ha and 1703 g/plant), number of fruits (5.6), per plant respectively. Squash Long and Super Squash Ball have been selected and recommended for cultivation during spring season in mid-hills of Nepal.

Green synthesis of manganese–cobalt–tungsten composite oxides for degradation of doxycycline via efficient activation of peroxymonosulfate

The advanced oxidation process of peroxymonosulfate activated by solid catalyst is one of the main technologies to solve the pollution of antibiotics in water environment.In this work, a series of composites (MCW) containing Mn, Co, and W were synthesized using green ball milling, which does not produce the three wastes (waste gas, waste water and industrial residue). It shows a unique and high catalytic activity for peroxymonosulfate-based degradation of doxycycline (DC) under the pH condition between 4 and 9, and it can be reused five times. MCW composites remove DC using singlet oxygen and superoxide free radicals, as well as a large number of oxygen vacancies for electron storage. The formation rate of free radicals is determined by the conversion rates of Mn3+/Mn2+ and Co3+/Co2+. In addition, there are three ways to degrade DC to form 18 kinds of intermediates, and the toxicity of all the intermediates were predicted by ECOSAR program. The highly active catalysts obtained using a green synthetic route for the activation of peroxymonosulfate show a great potential for decontamination of antibiotics wastewater.

Front Cover: Breathing‐Assisted Selective Adsorption of C8 Alkyl Aromatics in Zn‐Based Metal‐Organic Frameworks (Chem. Eur. J. 60/2021)

A key point of our work is selective adsorption of a C8 isomer with the assistance of metal–organic framework (MOF) breathing, which can be further applied to C8 isomer separation. When a C8 isomer mixture (colored balls) is applied to the MOF from an inlet bottle, the MOF starts to preferentially adsorb a single isomer (green balls) in the pores of MOF by breathing, as depicted by the expanding of the empty cages (MOFs) by incorporating the balls. As a result, the single C8 isomer is selectively isolated from the mixture, which is collected in the other bottle. More information can be found in the Full Paper by P. C. Rao, M. Yoon et al. (DOI: 10.1002/chem.202102640).

Boosting the Rate Performance of Li–S Batteries via Highly Dispersed Cobalt Nanoparticles Embedded into Nitrogen-Doped Hierarchical Porous Carbon

Boosting the Rate Performance of Li–S Batteries via Highly Dispersed Cobalt Nanoparticles Embedded into Nitrogen-Doped Hierarchical Porous Carbon

Confined-space strategy for anchoring catalytic nanoparticles on Si-OH by ball milling for enhanced O3/PMS oxidation of ciprofloxacin

Design and preparation of effective catalysts for advanced oxidation processes (AOPs) remain challenging, especially concerning the creation of strong interactions between catalytic sites and the support, which is essential for effective charge transfer and generation of reactive oxygen species (ROSs). In the present work, a pore-confinement approach based on a green ball milling method is proposed to anchor Co-Ce nanoparticles on a mesoporous silica support, and its chemical features and advantages are addressed. Remarkably, such a catalyst exhibited high activity due to the enhanced interface-mediated electron transfer, giving superior total organic carbon (TOC) removal (>70%) of ciprofloxacin (CIP) after only 10 min of treatment with O3/peroxymonosulfate (O3/PMS), which was much higher than for a catalyst synthesized by a traditional non-confined space process in previous reported literature. This confinement effect could stretch Co–Co bonds in a tetrahedral coordination and promote the growth of highly dispersed nanosized particles due to the Si-OH anchoring according to the results of X-ray absorption fine structure (XAFS). Furthermore, theoretical analysis revealed that Co3O4 {111} as main active sites significantly raised the adsorption of PMS, CIP and O3 than other phase, thereby favoring catalyst–reactant interaction and boosting electron transfer in this system.