Particle Size Reduction Research Articles

Rapid preparation of AlFeO3/ZnO bulk heterojunctions through jet milling for photoelectrochemical water splitting

The investigation of photocatalytic behavior of compounds consisting of earth-abundant elements is vital for discovering cheap photocatalysts/photoelectrocatalysts. AlFeO3 is an attractive material in this context because all its constituent elements are earth-abundant. In this work, bulk heterojunctions (heterojunctions distributed throughout the volume of powder) of AlFeO3 and ZnO were prepared using the technique of jet milling and subsequently used for photoelectrochemical water splitting. Jet milling achieved two objectives – reduction of particle size and formation of heterojunctions. Jet milling of AlFeO3 and ZnO particles was performed under a nitrogen atmosphere to produce AlFeO3/ZnO heterojunctions. Making heterojunctions by using jet milling is extremely rapid, a single jet milling operation taking only five to ten minutes. The heterojunction powder sample exhibited a current density of 34.25 mA/cm2 under illumination (at 1.5 V vs. Ag/AgCl) when it was used as the working electrode in a three-electrode electrochemical cell for Oxygen Evolution Reaction (OER). In contrast, ZnO nanoparticles prepared by jet milling (under nitrogen atmosphere) exhibited a current density of 18.54 mA/cm2 under illumination (at 1.5 V vs. Ag/AgCl). Thus, AlFeO3/ZnO bulk heterojunctions showed a superior photoelectrochemical (PEC) performance as compared to ZnO nanoparticles.

Effect of 2-acrylamide-2-methylpropane sulfonic acid on the early strength enhancement of calcium silicate hydrate seed

Nanomaterials are becoming widely used in cement to enhance the properties of cement-based materials. Artificially synthesized nano-C-S-H serves as a nucleation site for the hydration product C–S–H gel, facilitating its formation. This is deemed as an early strength agent to effectively promote cement hydration. Introducing comb-like polycarboxylate ether (PCE) during the synthesis of C–S–H can effectively reduce the size of C–S–H, resulting in better early strength effects. In this study, the acid-ether ratio of PCE is set at 6:1, and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) substitutes acrylic acid (AA) at varying molar ratios to obtain modified PCE. Calcium silicate hydrate seed-polycarboxylate ether (C-S-Hs-PCE) is synthesized using co-precipitation technique. This study investigated impacts of AMPS on the particle size of C-S-Hs-PCE and the early strength of cement-based materials using dynamic light scattering analysis, total organic carbon analyzer, X-ray diffraction analysis, low-field nuclear magnetic resonance, scanning electronic microscopy, isothermal calorimeter, and compressive strength testing. The results show that the C-S-Hs-PCE, synthesized at an AMPS to AA molar ratio of 5:95, turns out to possess a reduced particle size compared to use of PCE without AMPS. This is pivotal in promoting the hydration of the silicate phase and the formation of calcium hydroxide and C–S–H gel in the paste, and thereby reducing the total porosity while improving the early mechanical strength of the mortar, especially within first 24 h.

Enhancement of Anaerobic Digestion from Food Waste via Ultrafine Wet Milling Pretreatment: Simulation, Performance, and Mechanisms

Particle size reduction is a commonly used pretreatment technique to promote methane production from anaerobic digestion (AD) of food waste (FW). However, limited research has focused on the effect of micron-sized particles on AD of FW. This research presented an ultrafine wet milling (UFWM) pretreatment method to reduce the particle size of FW particles. After four hours of milling, D90 was reduced to 73 μm and cumulative methane production boosted from 307.98 mL/g vs. to 406.75 mL/g vs. without ammonia inhibition. We evaluated the performance of the AD systems and explored their facilitation mechanisms. Kinetic analysis showed that the modified Gompertz model predicted experimental values most accurately. UFWM pretreatment increased the maximum methane production rate by 44.4% and reduced the lag time by 0.65 days. The mechanical stress and collisions of milling resulted in a scaly surface of the particles, which greatly increased the voids and surface area. A rise in the XPS peak area of the C–N and C=O bonds proved the promotion of the liberation of carbohydrates and fats. Further microbial community analysis revealed that the relative abundance of Bacteroidota and Methanosarcina were enriched by UFWM. Meanwhile, methane metabolism pathway analysis confirmed that module M00567, module M00357, and related enzymes were stimulated. This study provided a theoretical basis for UFWM pretreatment applications and improvements in AD of FW.

Aspergillus niger as an eco-friendly agent for potassium release from K- bearing minerals: Isolation, screening and culture medium optimization using Plackett-Burman design and response surface methodology

The potential of Aspergillus niger, to enhance non-exchangeable potassium (K+) release from mineral structures were investigated as a cost-effective and environmentally friendly alternative to traditional chemical fertilizers. Optimizing the culture medium for maximum K+ release, alongside identifying potential mechanisms of action of the A. niger including the production of various organic acids and pH reduction in the minerals feldspar and phlogopite, were among the primary objectives of the present study. K+ dissolution from feldspar and phlogopite in the presence of Aspergillus niger were examined through a two-step experiment; impact of different carbon sources (glucose, sucrose, and fructose) on K+ release using the Plackett-Burman design (PBD) with 12 experimental runs and effect of other independent variables including pH (ranging from 5 to 10), carbon concentration (3–12.3 g l−1), and incubation time (5–18 days) on K+ release using the central composite design (CCD). Our results indicated that the PBD demonstrated a strong predictive capacity (RMSE = 0.012–0.018 g l−1 and R2 = 0.85–0.89) for K+ release. According to the CCD model, pH exerted a significant positive influence on increasing soluble K+ release (P < 0.001). The highest levels of K+ release (157.8 and 175.3 mg l−1 in feldspar and phlogopite, respectively) were observed at the central levels (0) of time and carbon source, and at the +α level (+1.68) of pH. Furthermore, based on the CCD model, the optimal conditions for achieving high K+ release from feldspar and phlogopite in a medium were pHs of 10.36 and 10.31, sucrose concentrations of 11.23 and 11.32 g l−1, and incubation times of 15 and 18 days, respectively. The determination coefficients of the CCD model indicated that 89.5% and 92.6% of the changes in soluble K+ for feldspar and phlogopite, could be explained by this model, respectively. In the current study, the production of organic acids and the resulting pH reduction, along with the reduction in mineral particle size in feldspar and phlogopite, were identified as potential mechanisms influencing the enhancement of potassium solubility. The predominant acids in both feldspar and phlogopite were lactic acid (70.9 and 69.15 mg l−1) and citric acid (40.48 and 22.93 mg l−1), although the production levels of organic acids differed in the two minerals. Overall, our findings highlight the potential of A. niger to proficiently release non-exchangeable potassium from mineral matrices, indicating its promising potential in agricultural applications.

Modification of microenvironmental pH of nanoparticles for enhanced solubility and oral bioavailability of poorly water-soluble celecoxib

This study aimed to develop a novel pH-modified nanoparticle with improved solubility and oral bioavailability of poorly water-soluble celecoxib by modifying the microenvironmental pH. After assessing the impact of hydrophilic polymers, surfactants and alkaline pH modifiers on the drug solubility, copovidone, sodium lauryl sulfate (SLS) and meglumine were chosen. The optimal formulation of solvent-evaporated, surface-attached and pH-modified nanoparticles composed of celecoxib/copovidone/SLS/meglumine at weight ratios of 1:1:0.2:0, 1:0.375:1.125:0 and 1:1:1:0.2:0.02, respectively, were manufactured using spray drying technique. Their physicochemical characteristics, solubility, dissolution and pharmacokinetics in rats were evaluated compared to the celecoxib powder. The solvent-evaporated and pH-modified nanoparticles converted a crystalline to an amorphous drug, resulting in a spherical shape with a reduced particle size compared to celecoxib powder. However, the surface-attached nanoparticles with insignificant particle size exhibited the unchangeable crystalline drug. All of them gave significantly higher solubility, dissolution, and oral bioavailability than celecoxib powder. Among them, the pH-modified nanoparticles demonstrated the most significant improvement in solubility (approximately 1600-fold) and oral bioavailability (approximately 4-fold) compared to the drug powder owing to the alkaline microenvironment formation effect of meglumine and the conversion to the amorphous drug. Thus, the pH-modified nanoparticle system would be a promising strategy for improving the solubility and oral bioavailability of poorly water-soluble and weakly acidic celecoxib.

Improving Oral Bioavailability of Meloxicam: Development and Characterization of Solid Dispersions

This study investigated the development of a solid dispersion to improve the solubility and dissolution of meloxicam, a poorly water-soluble drug. Meloxicam is used to treat pain and inflammation in various conditions. The challenge was to enhance the drug's oral bioavailability by overcoming its low solubility. Two approaches were explored:&#x0D; &#x0D; 1. Kneading method with Poloxamer 407: This method resulted in a formulation with significantly improved solubility compared to the pure drug.&#x0D; Solvent evaporation method with PVP K-30: While this method offered satisfactory solubility enhancement, it was not as effective as the kneading method with Poloxamer 407.Following the development of the optimized solid dispersion, a suspension formulation was prepared using various suspending agents. The optimized drug formula was then incorporated into the suspension mix. Characterization studies confirmed compatibility between the drug and excipients. FT-IR analysis showed no interaction between the drug and the carriers. Scanning electron microscopy (SEM) revealed a change in meloxicam particle morphology from crystalline to a more amorphous form, indicating a reduction in particle size and a potential explanation for the improved dissolution profile. The dissolution profile of the solid dispersion suspension prepared by the kneading method with Poloxamer 407 outperformed the one prepared with the solvent evaporation method and PVP K-30.This study demonstrates the effectiveness of the kneading method with Poloxamer 407 in developing a solid dispersion of meloxicam with enhanced solubility and dissolution. The optimized formulation exhibited good stability, acceptable drug content and release, and satisfactory rheological properties. This approach has the potential to improve the bioavailability of meloxicam and lead to a more effective oral dosage form.&#x0D; &#x0D; Keywords: Oral Bioavailability, Meloxicam:, Solid Dispersions , FT-IR analysis, SEM

Fabrication of Amisulpride Nanosuspension for Nose to Brain Delivery in the Potential Antipsychotic Treatment

ABSTRACT: Background: This research was aimed with the development of antipsychotic drug delivery for olfactory administration which could deliver drug to the brain. Amisulpride is a psychoactive drug that belongs to the benzamide derivatives class. It enhances dopaminergic neurotransmission by inhibiting presynaptic dopamine D2/D3 auto receptors selectively at lower dosages. Method: The nanosuspension was prepared by media milling technique for nose to brain delivery. The nose to brain delivery developed an effective route to bypass the BBB and deliver the drug to the brain. Factorial design was used for the designing and optimizing formulation based on various process and formulation factors. The optimized batch further analyzed to determine particle size, PDI, zeta potential, and drug content. With appropriate selection of process parameters like speed and bead amount. The media milling method is one of the effective methodology to reduce particle size and with the help of stabilizers nanoparticles could be stabilised. Result: The average particle size range of nanosuspension batch was observed 100-150 nm with a polydispersity index of 0.0927, Zeta potential +39.14 mV and drug content 88.12 ± 2 %. Conclusion: Intranasal administration is a promising alternative for bypassing the blood-brain barrier, reducing the adverse effects, and lowering the doses.

A review of cold plasma for catalyst synthesis and modification

Cold plasma has been extensively studied and developed in the field of energy storage and conversion, with a focus on its ability to assist in catalyst synthesis, surface modification, the introduction of heteroatoms, the generation of defects and vacancies, the improvement of catalyst dispersion, and the reduction of particle size. In contrast to conventional calcination and chemical methods, the energy from cold plasma can be transferred directly to the catalyst and carrier during the treatment process, which can improve the interaction between the loaded catalyst and carrier by changing the internal structure and surface morphology of the catalyst. Therefore, these properties make cold plasma quite green, safe, and efficient for catalyst synthesis and modification. In this paper, the characteristics and applications of various cold plasma technologies, as well as the synergistic treatment of cold plasma technology with thermodynamic principles on catalysts, are analyzed. Based on current research progress, this paper provides a summary and outlook on the synthesis and modification of catalysts using cold plasma.

Biocompatible hydrophobic cross-linked cyclodextrin-based metal-organic framework as quercetin nanocarrier for enhancing stability and controlled release

Cyclodextrin-based metal-organic framework (CD-MOF) has been widely used in various delivery systems due to its excellent edibility and high drug loading capacity. However, its typically bulky size and high brittleness in aqueous solutions pose significant challenges for practical applications. Here, we proposed an ultrasonic-assisted method for rapid synthesis of uniformly-sized nanoscale CD-MOF, followed by its hydrophobic modification through ester bond cross-linking (Nano-CMOF). Proper ultrasound treatment effectively reduced particle size to nanoscale (393.14 nm). Notably, carbonate ester cross-linking method significantly improved water stability without altering its cubic shape and high porosity (1.3 cm3/g), resulting in a retention rate exceeding 90% in various media. Furthermore, the loading of quercetin did not disrupt cubic structure and showcased remarkable storage stability. Nano-CMOF achieved controlled release of quercetin in both aqueous environments and digestion. Additionally, Nano-CMOF demonstrated exceptional antioxidant (free radical scavenging 82.27%) and biocompatibility, indicating its significant potential as novel nutritional delivery systems in food and biomedical fields.

Study on the Effect of Nanoporous Copper Particle Size on Copper-Based Azide.

Preparing copper-based azide by in situ reaction is well-suited for MEMS processing technology and holds promising prospects in the field of MEMS micro-initiators. This study involved the preparation of porous copper with particle sizes of approximately 30 nm, 60 nm and 100 nm through powder sintering. These were used as precursors for a gas-solid in situ azide reaction to produce copper-based azide with varying morphologies and compositions. Copper-based azide micro-initiators were designed, and their output performance was evaluated using CL-20 and HNS-IV explosives. Analytical results revealed that the product from the reaction of the 100 nm precursor exhibited a lumpy and uneven structure with a conversion rate of 90.36%. The product from the 60 nm precursor reaction had a dense surface with a conversion rate of 94.56%, while the 30 nm precursor resulted in a needle-like form with a conversion rate of 92.82%. Detonation experiments demonstrated that the copper-based azide micro-initiators prepared with 100 nm of a porous copper precursor exhibited unstable output performance, requiring a 1.6 mg charge to successfully detonate CL-20 explosives. On the other hand, copper-based azide micro-initiators prepared from 60 nm and 30 nm of porous copper precursors exhibited stable output performance. A charge of 0.8 mg was adequate for reliably and consistently detonating CL-20 and HNS-IV explosives. The reduced particle size of the precursor enhanced the output performance of the copper-based azide micro-initiators, providing increased energy redundancy during detonation and improving overall usage reliability.

Rheological insights into 3D printing of drug products: Drug nanocrystal-poloxamer gels for semisolid extrusion

The importance of ink rheology to the outcome of 3D printing is well recognized. However, rheological properties of printing inks containing drug nanocrystals have not been widely investigated. Therefore, the objective of this study was to establish a correlation between the composition of nanocrystal printing ink, the ink rheology, and the entire printing process. Indomethacin was used as a model poorly soluble drug to produce nanosuspensions with improved solubility properties through particle size reduction. The nanosuspensions were further developed into semisolid extrusion 3D printing inks with varying nanocrystal and poloxamer 407 concentrations. Nanocrystals were found to affect the rheological properties of the printing inks both by being less self-supporting and having higher yielding resistances. During printing, nozzle blockages occurred. Nevertheless, all inks were found to be printable. Finally, the rheological properties of the inks were successfully correlated with various printing and product properties. Overall, these experiments shed new light on the rheological properties of printing inks containing nanocrystals.

Optimizing Nanosuspension Drug Release and Wound Healing Using a Design of Experiments Approach: Improving the Drug Delivery Potential of NDH-4338 for Treating Chemical Burns.

NDH-4338 is a highly lipophilic prodrug comprising indomethacin and an acetylcholinesterase inhibitor. A design of experiments approach was used to synthesize, characterize, and evaluate the wound healing efficacy of optimized NDH-4338 nanosuspensions against nitrogen mustard-induced skin injury. Nanosuspensions were prepared by sonoprecipitation in the presence of a Vitamin E TPGS aqueous stabilizer solution. Critical processing parameters and material attributes were optimized to reduce particle size and determine the effect on dissolution rate and burn healing efficacy. The antisolvent/solvent ratio (A/S), dose concentration (DC), and drug/stabilizer ratio (D/S) were the critical sonoprecipitation factors that control particle size. These factors were subjected to a Box-Behnken design and response surface analysis, and model quality was assessed. Maximize desirability and simulation experiment optimization approaches were used to determine nanosuspension parameters with the smallest size and the lowest defect rate within the 10-50 nm specification limits. Optimized and unoptimized nanosuspensions were prepared and characterized. An established depilatory double-disc mouse model was used to evaluate the healing of nitrogen mustard-induced dermal injuries. Optimized nanosuspensions (A/S = 6.2, DC = 2% w/v, D/S = 2.8) achieved a particle size of 31.46 nm with a narrow size range (PDI = 0.110) and a reduced defect rate (42.2 to 6.1%). The optimized nanosuspensions were stable and re-dispersible, and they showed a ~45% increase in cumulative drug release and significant edema reduction in mice. Optimized NDH-4338 nanosuspensions were smaller with more uniform sizes that led to improved physical stability, faster dissolution, and enhanced burn healing efficacy compared to unoptimized nanosuspensions.

Impact of Grinding Balls on the Size Reduction of Aprepitant in Wet Ball Milling Procedure

One of the widely used approaches for improving the dissolution of poorly water-soluble drugs is particle size reduction. Ball milling is a mechanical, top-down technique used to reduce particle size. The effect of ball number, ball size and milling speed on the properties of milled Aprepitant is evaluated. A full factorial design was employed to investigate the influence of affecting factors on particle size reduction. The initial suspension was made by suspending the drug in distilled water using excipients followed by milling in a planetary ball mill. Ball size, ball number and milling speed modulated particle size distribution of Aprepitant. Increasing the number of balls from minimum to maximum for each ball size led to approximately a 28% reduction in mean particle size, a 37% decrease in D90%, and a 25% decrease in the ratio of volume mean particle diameter to numeric mean particle diameter. On average, using 10 mm balls instead of 30 mm balls reduced mean particle size by 1.689 µm. As a result, ball size, ball number, and milling speed are three effective factors in the process of ball milling. By increasing the ball number and decreasing the ball size, efficient micronization of drug particles takes place and the particle size is more uniform.

Optimizing Paclitaxel Oral Absorption and Bioavailability: TPGS Co-Coating via Supercritical Anti-Solvent Fluidized Bed Technology.

Supercritical anti-solvent fluidized bed (SAS-FB) coating technology has the advantages of reducing particle size, preventing high surface energy particle aggregation, improving the dissolution performance and bioavailability of insoluble drugs. The poor solubility of Biopharmaceutics Classification System (BCS) class IV drugs poses challenges in achieving optimal bioavailability. Numerous anti-cancer drugs including paclitaxel (PTX) belong to the BCS class IV, hindering their therapeutic efficacy. To address this concern, our study explored SAS-FB technology to coat PTX with D-α-tocopherol polyethylene glycol 1000 succinate (TPGS) onto lactose. Under our optimized conditions, we achieved a PTX coating efficiency of 96.8%. Further characterization confirmed the crystalline state of PTX in the lactose surface coating by scanning electron microscopy and X-ray powder diffraction. Dissolution studies indicated that SAS-FB processed samples release over 95% of the drug within 1 min. Moreover, cell transmembrane transport assays demonstrated that SAS-FB processed PTX samples co-coated with TPGS had an enhanced PTX internalization into cells and a higher permeability coefficient compared to those without TPGS. Finally, compared to unprocessed PTX, SAS-FB (TPGS) and SAS-FB processed samples showed a 2.66- and 1.49-fold increase in oral bioavailability in vivo, respectively. Our study highlights the efficacy of SAS-FB co-coating for PTX and TPGS as a promising strategy to overcome bioavailability challenges inherent in BCS class IV drugs. Our approach holds broader implications for enhancing the performance of similarly classified medications.

Ceria-Terbium-based electrospun nanofiber catalysts for soot oxidation activity and its kinetics

BackgroundCeria-based materials have an excellent potential to be catalysts for catalytic three-way converters in the automobile industry. Developing Ceria-based nanofiber catalysts can be a significant approach for further exploring the application of these materials in automobile industries. MethodsIn this study, Ag, Cu, or Co doped Ceria–Terbium nanofibers were synthesized using the electrospinning technique. The obtained nanofiber catalysts were characterized using FE-SEM, XRD, FT-Raman Spectroscopy, and BET-BJH analysis and tested for soot oxidation activity and its kinetics. Significant findingsFE-SEM examination reveals that the obtained nanofibers have a diameter ranging from around 100 to 600 nm. CeTbCo nanofibers exhibited a reduced particle size and enhanced pore formation. The XRD investigation revealed that all the nanofibers displayed a face-centered fluorite structure of CeO2. In Raman spectroscopy analysis, CeTbCo nanofibes showed the emergence of a secondary Co3O4 phase. The CeTbCo nanofiber catalyst showed better SBET (specific surface area) (66 m2/g) and average pore size (12.08 nm) and total pore volume (0.223 cc/g)), better soot oxidation activity (T50 = 347 ℃) than other nanofiber catalysts. The CeTbCo nanofiber catalyst exhibited an activation energy of 132 kJ mol−1 and a pre-exponential factor (ln (A)) of 25.63 min−1.

Dispersion state analysis in hot melt extruded, highly drug-loaded 3D printing filaments applying Raman microscopy

Abstract Objectives Highly drug-loaded polymer formulations are favorable intermediates in pharmaceutical applications, for example, for the individualized production of medicines via 3D printing with the maximum flexibility regarding dose strength and drug combination in a single dosage form. However, high-disperse drug loads are challenging for the process itself and the (intermediate) product properties, making the knowledge about the dispersion state of the drug particles achieved by the production process helpful to overcome such challenges. Methods Therefore, a novel dispersion state analysis technique based on scanning Raman microscopy is proposed in the present study and applied to HPMC filaments loaded with 20 wt%, 40 wt%, and 60 wt% theophylline. The qualitative and quantitative evaluations of the scans were correlated to melt viscosities, process data, and mechanical properties of the filaments. Key findings The analyses revealed not only an increasing particle size reduction with increasing drug load and thus increasing viscosity and mechanical energy input. The particle size reduction also caused a change in the filaments’ mechanical properties from elastic ductile to rigid brittle. Furthermore, an alignment of the elongated drug particles with the frozen three-dimensional flow pattern of the extruder and not only with the extrusion direction was elucidated. Conclusions Therefore, the necessity to investigate the dispersion state further is highlighted for future studies on highly drug-loaded polymer formulations, providing a novel measuring technique applicable to challenging pharmaceutical formulations.

Size reduction and water dispersibility improvement of hexagonal boron nitride particles by femtosecond laser irradiation in water

Controlling the size and surface state of inorganic particles, which strongly influence their dispersibility in solvents, is important for diverse applications. Intense femtosecond laser pulses can induce plasma formation in material–dispersed solvents and interact with both materials and solvents. In this study, femtosecond laser pulses are employed to modify hexagonal boron nitride (hBN) particles dispersed in water, with the aim of evaluating the effects of the femtosecond laser process on the size reduction and surface modification of hBN particles. Shadowgraph imaging reveals the formation of the reactive environment in hBN–dispersed water, resulting from the ionization of water molecules which leads to the generation of OH radicals. Evaluation of the hBN particle sizes suggests an overall reduction from 160 to 110 nm after 60 min of irradiation and the generation of nanodots between 5 and 10 nm in size. In addition, it is confirmed that the number of particles with higher zeta potentials increases after the samples are laser-irradiated, suggesting a change in the surface state. Consequently, the duration of hBN particle dispersion in water is significantly increased, with an improvement of at least one order of magnitude, for the laser-irradiated samples. This study presents a demonstration of the formation of a reaction field that affects hBN particles in size and dispersibility in water.

Mechanically treated Mn2O3 triggers peracetic acid activation for superior non-radical oxidation of micropollutants: Identification of reactive complexes

This study used a simple mechanical ball milling strategy to significantly improve the ability of Mn2O3 to activate peracetic acid (PAA) for sustainable and efficient degradation of organic micropollutant (like bisphenol A, BPA). BPA was successfully removed and detoxified via PAA activation by the bm-Mn2O3 within 30 min under neutral environment, with the BPA degradation kinetic rate improved by 3.4 times. Satisfactory BPA removal efficiency can still be achieved over a wide pH range, in actual water and after reuse of bm-Mn2O3 for four cycles. The change in hydrophilicity of Mn2O3 after ball milling evidently elevated the affinity of Mn2O3 for binding to PAA, while the reduction in particle size exposed more active sites contributing partially to catalytic oxidation. Further analysis revealed that BPA oxidation in the ball mill-treated Mn2O3 (bm-Mn2O3)/PAA process mainly depends on the bm-Mn2O3-PAA complex (i.e., Mn(III)−OO(O)CCH3) mediated non-radical pathway rather than R-O• and Mn(IV). Especially, the existence of the Mn(III)-PAA complex was definitely verified by in situ Raman spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Simultaneously, density functional theory calculations determined that PAA adsorbs readily on manganese sites thereby favoring the formation of Mn(III)−OO(O)CCH3 complexes. This study advances an in-depth understanding of the underlying mechanisms involved in the manganese oxide-catalyzed activation of PAA for superior non-radical oxidation of micropollutants.

Differential utilisation of subcellular skeletal muscle glycogen pools: a comparative analysis between 1 and 15min of maximal exercise.

In skeletal muscle, glycogen particles are distributed both within and between myofibrils, as well as just beneath the sarcolemma. Their precise localisation may influence their degradation rate. Here, we investigated how exercise at different intensities and durations (1- and 15-min maximal exercise) with known variations in glycogenolytic rate and contribution from anaerobic metabolism affects utilisation of the distinct pools. Furthermore, we investigated how decreased glycogen availability achieved through lowering carbohydrate and energy intake after glycogen-depleting exercise affect the storage of glycogen particles (size, numerical density, localisation). Twenty participants were divided into two groups performing either a 1-min (n=10) or a 15-min (n=10) maximal cycling exercise test. In a randomised, counterbalanced, cross-over design, the exercise tests were performed following short-term consumption of two distinct diets with either high or moderate carbohydrate content (10 vs. 4gkg-1 body mass (BM) day-1) mediating a difference in total energy consumption (240 vs. 138gkg-1 BM day-1). Muscle biopsies from m. vastus lateralis were obtained before and after the exercise tests. Intermyofibrillar glycogen was preferentially utilised during the 1-min test, whereas intramyofibrillar glycogen was preferentially utilised during the 15-min test. Lowering carbohydrate and energy intake after glycogen-depleting exercise reduced glycogen availability by decreasing particle size across all pools and diminishing numerical density in the intramyofibrillar and subsarcolemmal pools. In conclusion, distinct subcellular glycogen pools were differentially utilised during 1-min and 15-min maximal cycling exercise. Additionally, lowered carbohydrate and energy consumption after glycogen-depleting exercise altered glycogen storage by reducing particle size and numerical density, depending on subcellular localisation. KEY POINTS: In human skeletal muscle, glycogen particles are localised in distinct subcellular compartments, referred to as intermyofibrillar, intramyofibrillar and subsarcolemmal pools. The intermyofibrillar and subsarcolemmal pools are close to mitochondria, while the intramyofibrillar pool is at a distance from mitochondria. We show that 1min of maximal exercise is associated with a preferential utilisation of intermyofibrillar glycogen, and, on the other hand, that 15min of maximal exercise is associated with a preferential utilisation of intramyofibrillar glycogen. Furthermore, we demonstrate that reduced glycogen availability achieved through lowering carbohydrate and energy intake after glycogen-depleting exercise is characterised by a decreased glycogen particle size across all compartments, with the numerical density only diminished in the intramyofibrillar and subsarcolemmal compartments. These results suggest that exercise intensity influences the subcellular pools of glycogen differently and that the dietary content of carbohydrates and energy is linked to the size and subcellular distribution of glycogen particles.

Ethylene glycol-modified CeO2-SiO2 support for Co catalysts applied in the ethanol steam reforming

In this work, cobalt-based catalysts supported on a CeO2-SiO2 binary oxide were synthesized. The silica was functionalized with ethylene–glycol and its effect on catalytic activity, stability and selectivity towards hydrogen in the ethanol steam reforming reaction (ESR) was evaluated. The cobalt composition in all catalysts was 15 wt% and 10 wt% CeO2. The catalytic activity was evaluated at 500 °C in a fixed-bed reactor, feeding an ethanol/water mixture with a molar ratio of 5 in the ESR.A significant improvement in the activity of the modified catalysts was observed; i.e., 100% conversion and twice the H2 yield of the un-functionalized catalysts. The materials were characterized by different techniques such as XRD, N2 adsorption/desorption, Raman spectroscopy, XPS, TPR, TEM, and TPO. These results showed that the modification of the support contributed to the reduction of the cobalt particle size and the increase of dispersion, favoring H2 production.