Comparing Mn-based oxides filters started by KMnO4 versus K2FeO4 for ammonium and manganese removal: Formation mechanism of active species.

A pilot-scale filtration system was adopted to prepare filter media with catalytic activity to remove manganese (Mn2+) and ammonium (NH4+-N). Three different combinations of oxidants (KMnO4 and K2FeO4) and reductants (MnSO4 and FeCl2) were used during the start-up period. Filter R3 started up by KMnO4 and FeCl2 (Mn7+→MnOx) exhibited excellent catalytic property, and the NH4+-N and Mn2+ removal efficiency reached over 80% on the 10th and 35th days, respectively. Filter R1 started up by K2FeO4 and MnSO4 (MnOx←Mn2+) exhibited the worst catalytic property. Filter R2 started up by KMnO4 and MnSO4 (Mn7+→MnOx←Mn2+) were in between. According to Zeta potential results, the Mn-based oxides (MnOx) formed by Mn7+→MnOx performed the highest pHIEP and pHPZC. The higher the pHIEP and pHPZC, the more unfavorable the cation adsorption. However, it was inconsistent with its excellent Mn2+ and NH4+-N removal abilities, implying that catalytic oxidation played a key role. Combined with XRD and XPS analysis, the results showed that the MnOx produced by the reduction of KMnO4 showed early formation of buserite crystals, high degree of amorphous, high content of Mn3+ and lattice oxygen with the higher activity to form defects. The above results showed that MnOx produced by the reduction of KMnO4 was more conducive to the formation of active species for catalytic oxidation of NH4+-N and Mn2+ removal. This study provides new insights on the formation mechanisms of the active MnOx that could catalytic oxidation of NH4+-N and Mn2+.

Ultrasonic-Assisted Preparation of Biodiesel Products from Vegetable Oils.

Utilizing vegetable oil as a sustainable feedstock, this study presents an innovative approach to ultrasonic-assisted transesterification for biodiesel synthesis. This alkaline-catalyzed procedure harnesses ultrasound as a potent energy input, facilitating the rapid conversion of extra virgin olive oil into biodiesel. In this demonstration, the reaction is run in an ultrasonic bath under ambient conditions for 15 min, requiring a 1:6 molar ratio of extra virgin olive oil to methanol and a minimum amount of KOH as the catalyst. The physiochemical properties of biodiesel are also reported. Emphasizing the remarkable advantages of ultrasonic-assisted transesterification, this method demonstrates notable reductions in reaction and separation times, achieving near-perfect purity (~100%), high yields, and negligible waste generation. Importantly, these benefits are achieved within a framework that prioritizes safety and environmental sustainability. These compelling findings underscore the effectiveness of this approach in converting vegetable oil into biodiesel, positioning it as a viable option for both research and practical applications.

Adhesive Cementation of CAD/CAM Silica-based Ceramics: Effect of Adhesive Type and Long-term Aging on the Bond Strength to Composite Cement.

PURPOSE: To investigate the effect of adhesive type and long-term aging on the shear bond strength (SBS) between silica-based ceramics and composite cement (CC). MATERIALS AND METHODS: Lithium-silicate (LS), feldspathic (FD) and polymer-infiltrated ceramic (PIC) blocks were sectioned (10 x 12 x 2 mm) and divided into 24 groups considering the factors: "ceramics" (LS, FD, and PIC), "adhesive" (Ctrl: without adhesive; 2SC: 2-step conventional; 3SC: 3-step conventional; 1SU: 1-step universal), and "aging" (non-aged or aged [A]). After the surface treatments, CC cylinders (n = 15, Ø = 2 mm; height = 2 mm) were made and half of the samples were subjected to thermocycling (10,000) and stored in water at 37°C for 18 months. The samples were submitted to SBS testing (100 kgf, 1 mm/min) and failure analysis. Extra samples were prepared for microscopic analysis of the adhesive interface. SBS (MPa) data was analyzed by 3-way ANOVA and Tukey's test (5%). Weibull analysis was performed on the SBS data. RESULTS: All factors and interactions were significant for SBS (p<0.05). Before aging, there was no significant difference between the tested groups and the respective control groups. After aging, the LS_1SU (22.18 ± 7.74) and LS_2SC (17.32 ± 5.86) groups exhibited significantly lower SBS than did the LS_Ctrl (30.30 ± 6.11). Only the LS_1SU group showed a significant decrease in SBS after aging vs without aging. The LS_1SU (12.20) group showed the highest Weibull modulus, which was significantly higher than LS_2SC_A (2.82) and LS_1SU_A (3.15) groups. CONCLUSION: No type of adhesive applied after silane benefitted the long-term adhesion of silica-based ceramics to CC in comparison to the groups without adhesive.

Adsorption Potential, Speciation Transformation, and Risk Assessment of Hg-, Cd-, and Pb-Contaminated Soils Using Biochar in Combination with Potassium Dihydrogen Phosphate.

The objective of this study is to develop a remediation technology for composited heavy metal-contaminated soil. Biochars (BC300, BC400, and BC500) derived from corn were combined with potassium dihydrogen phosphate (KH2PO4) to immobilize and remove heavy metal ions, including mercury (Hg2+), cadmium (Cd2+), and lead (Pb2+). The adsorption kinetics of metal ions in aqueous solutions with different concentrations was tested, and the fitting effects of the two models were compared. The findings demonstrate that the joint application of biochar and KH2PO4 could markedly enhance the immobilization efficacy of Pb2+, whereas the utilization of KH2PO4 on its own exhibited a more pronounced immobilization impact on Cd2+. Furthermore, the present study underscores the shortcomings of various remediation techniques that must be taken into account when addressing heavy metal-contaminated soils. It also emphasizes the value of comprehensive remediation techniques that integrate multiple remediation agents. This study offers a novel approach and methodology for addressing the intricate and evolving challenges posed by heavy metal contamination in soil. Its practical value and potential for application are significant.

Optimisation and characterisation of KOH-activated carbon obtained from Baijiu spent grains for the mitigation of risk factors in alcoholic beverages.

This study aims to repurpose waste grain from the Baijiu brewing process into activated carbon for mitigating risk factors in alcoholic beverages, enhancing quality and ensuring safety. For attaining the most effective activated carbon, tailored carbon synthesis conditions were identified for diverse alcoholic beverages, optimising strategies. For beverages with low flavour compound content, optimal conditions include 900 °C calcination, 16-hour activation and a 1:2 activation ratio. In contrast, for those with abundant flavour compounds, 800 °C calcination, 16-hour activation and a 1:1 activation ratio are recommended. Post-synthesis analyses, employing nitrogen physisorption-desorption isotherms, FT-IR and SEM, validated a significant BET surface area of 244.871 m2/g for the KOH-activated carbon. Critical to adsorption efficiency, calcination temperature showcased noteworthy micro-porosity (0.8-1 nm), selectively adsorbing higher alcohols (C3-C6) and acetaldehyde while minimising acid and ester adsorption. Sensory evaluations refined optimal parameters, ensuring efficient spent grain management and heightened beverage safety without compromising aroma.

Upcycling of PVC waste to high-value sorbent with KOH-activation for efficient removal of organic dyes.

Polyvinyl chloride (PVC), known for its chemical stability and flame-retardant qualities, has many uses in various fields, such as pipes, electric wires, and cable insulation. Research has established its potential recovery as a fluidic fuel through pyrolysis, but the use of PVC pyrolysis oil, which is tainted by chlorine, is constrained by its low heat value and harmful environmental effects. This study engineered a layered double hydroxide (LDH) to tackle these challenges. The LDH facilitated dechlorination during PVC pyrolysis and bolstered thermal stability via cross-linking. During pyrolysis with LDH, PVC was transformed into carbon-rich precursors to sorbents. Chemical activation of these residues using KOH created sorbents with a specific surface area of 1495.4 m2 g⁻1, rendering them hydrophilic. These resulting sorbents displayed impressive adsorption capabilities, removing up to 486.79 mg g⁻1 of methylene blue and exhibiting the simultaneous removal of cations and anions.

Optimizing alkali-pretreatment dosage for waste-activated sludge disintegration and enhanced biogas production yield.

The rapid transition towards modernization and industrialization led to an increase in urban population, resulting in paramount challenge to municipal sewage sludge management. Anaerobic digestion (AD) serves as a promising venue for energy recovery from waste-activated sludge (WAS). Addressing the challenge of breaking down floc structures and microbial cells is crucial for releasing extracellular polymeric substances and cytoplasmic macromolecules to facilitate hydrolysis and fermentation process. The present study aims to introduce a combined process of alkaline/acid pre-treatments and AD to enhance sludge digestion and biogas production. The study investigates the influence of alkali pretreatment at ambient temperature using four alkali reagents (NaOH, Ca(OH)2, Mg(OH)2, and KOH). The primary goal is to provide insights into the intricate interplay of alkali dosages (0.04-0.12 g/gTS) on key physic-chemical parameters crucial for optimizing the pre-treatment dosage. Under the optimized alkaline/acid pre-treatment condition, the TSS reduction of 18%-30% was achieved. An increase in sCOD concentration (24%-50%) signifies the enhanced hydrolysis and solubilization rate of organic substrate in WAS. Finally, the biomethane potential test (BMPT) was performed for pre-treated WAS samples. The maximum methane (CH4) yield was observed in combination A1 (244 mL/g) and D1 (253 mL/g), demonstrating the pivotal role of alkali optimization in enhancing AD efficiency. This study serves as a valuable resource to policymakers, researchers, and technocrats in addressing challenges associated to sludge management.

Unrevealing the influence of reagent properties on disruption and digestibility of lignocellulosic biomass during alkaline pretreatment.

Beyond the conventional consideration of pretreatment severity (PS) responsible for biomass disruption, the influence of reagent properties on biomass (LCB) disruption is often overlooked. To investigate the LCB disruption as a function of reagent properties, reagents with distinct cations (NaOH and KOH) and significantly higher delignification potential were chosen. NaOH solution (3 % w/v) with a measured pH of 13.05 ± 0.01 is considered the reference, against which a KOH solution (pH = 13.05 ± 0.01) was prepared for LCB pretreatment under the same PS. Despite comparable lignin content, varying glucose yield of NaOH (68.76 %) and KOH (46.88 %) pretreated residues indicated the presence of heterogeneously disrupted substrate. Holocellulose extracted from raw poplar (ASC, control) and alkaline pretreated residues (C-NaOH and C-KOH) were analyzed using HPLC, XRD, SEM, TGA/DTG, XPS, and 13CP MAS NMR to investigate the pretreatment-induced structural modification. Results revealed that, despite the same pretreatment severity, better disruption in C-NaOH (higher accessible fibril surface and less-ordered region) leading to higher digestibility than C-KOH, likely due to the smaller ionic radius of Na+, facilitates better penetration into dense LCB matrix. This study elucidates the importance of considering the reagent properties during LCB pretreatment, eventually enhancing consciousness while selecting reagents for efficient LCB utilization.

Dinuclear gold(I) Complexes with Bidentate NHC Ligands as Precursors for Alkynyl Complexes via Mechanochemistry.

The use of alkynyl gold(I) complexes covers different research fields, such as bioinorganic chemistry, catalysis, and material science, considering the luminescent properties of the complexes. Regarding this last application, we report here the synthesis of three novel dinuclear gold(I) complexes of the general formula [(diNHC)(Au-C≡CPh)2]: two Au-C≡CPh units are connected by a bridging di(N-heterocyclic carbene) ligand, which should favor the establishment of semi-supported aurophilic interactions. The complexes can be easily synthesized through mechanochemistry upon reacting the pristine dibromido complexes [(diNHC)(AuBr)2] with phenylacetylene and KOH. Interestingly, we were also able to isolate the monosubstituted complex [(diNHC)(Au-C≡CPh)(AuBr)]. The gold(I) species were fully characterized by multinuclear NMR spectroscopy and mass spectrometry. The emission properties were also evaluated, and the salient data are comparable to those of analogous compounds reported in the literature.

Design and synthesis of novel nitrothiazolacetamide conjugated to different thioquinazolinone derivatives as anti-urease agents.

The present article describes the design, synthesis, in vitro urease inhibition, and in silico molecular docking studies of a novel series of nitrothiazolacetamide conjugated to different thioquinazolinones. Fourteen nitrothiazolacetamide bearing thioquinazolinones derivatives (8a-n) were synthesized through the reaction of isatoic anhydride with different amine, followed by reaction with carbon disulfide and KOH in ethanol. The intermediates were then converted into final products by treating them with 2-chloro-N-(5-nitrothiazol-2-yl)acetamide in DMF. All derivatives were then characterized through different spectroscopic techniques (1H, 13C-NMR, MS, and FTIR). In vitro screening of these molecules against urease demonstrated the potent urease inhibitory potential of derivatives with IC50 values ranging between 2.22 ± 0.09 and 8.43 ± 0.61 µM when compared with the standard thiourea (IC50 = 22.50 ± 0.44 µM). Compound 8h as the most potent derivative exhibited an uncompetitive inhibition pattern against urease in the kinetic study. The high anti-ureolytic activity of 8h was confirmed against two urease-positive microorganisms. According to molecular docking study, 8h exhibited several hydrophobic interactions with Lys10, Leu11, Met44, Ala47, Ala85, Phe87, and Pro88 residues plus two hydrogen bound interactions with Thr86. According to the in silico assessment, the ADME-Toxicity and drug-likeness profile of synthesized compounds were in the acceptable range.

A Novel PIFA/KOH Promoted Approach to Synthesize C2-arylacylated Benzothiazoles as Potential Drug Scaffolds.

To discover an efficient and convenient method to synthesize C2-arylacylated benzothiazoles as potential drug scaffolds, a novel [bis(trifluoroacetoxy)iodo]benzene(PIFA)/KOH synergistically promoted direct ring-opening C2-arylacylation reaction of 2H-benzothiazoles with aryl methyl ketones has been developed. Various substrates were tolerated under optimized conditions affording the C2-arylacylation products in 70-95% yields for 38 examples. A plausible mechanism was also proposed based on a series of controlled experiments.

Process Parameters Optimization, Characterization, and Application of KOH-Activated Norway Spruce Bark Graphitic Biochars for Efficient Azo Dye Adsorption.

In this work, Norway spruce bark was used as a precursor to prepare activated biochars (BCs) via chemical activation with potassium hydroxide (KOH) as a chemical activator. A Box-Behnken design (BBD) was conducted to evaluate and identify the optimal conditions to reach high specific surface area and high mass yield of BC samples. The studied BC preparation parameters and their levels were as follows: pyrolysis temperature (700, 800, and 900 °C), holding time (1, 2, and 3 h), and ratio of the biomass: chemical activator of 1: 1, 1.5, and 2. The planned BBD yielded BC with extremely high SSA values, up to 2209 m2·g-1. In addition, the BCs were physiochemically characterized, and the results indicated that the BCs exhibited disordered carbon structures and presented a high quantity of O-bearing functional groups on their surfaces, which might improve their adsorption performance towards organic pollutant removal. The BC with the highest SSA value was then employed as an adsorbent to remove Evans blue dye (EB) and colorful effluents. The kinetic study followed a general-order (GO) model, as the most suitable model to describe the experimental data, while the Redlich-Peterson model fitted the equilibrium data better. The EB adsorption capacity was 396.1 mg·g-1. The employment of the BC in the treatment of synthetic effluents, with several dyes and other organic and inorganic compounds, returned a high percentage of removal degree up to 87.7%. Desorption and cyclability tests showed that the biochar can be efficiently regenerated, maintaining an adsorption capacity of 75% after 4 adsorption-desorption cycles. The results of this work pointed out that Norway spruce bark indeed is a promising precursor for producing biochars with very promising properties.

Enzymatic Hydrolysis Lignin-Derived Porous Carbons through Ammonia Activation: Activation Mechanism and Charge Storage Mechanism.

The low energy density and low cost performance of electrochemical capacitors (ECs) are the principal factors that limit the wide applications of ECs. In this work, we used enzymatic hydrolysis lignin as the carbon source and an ammonia activation methodology to prepare nitrogen-doped lignin-derived porous carbon (NLPC) electrode materials with high specific surface areas. We elucidated the free radical mechanism of ammonia activation and the relationship between nitrogen doping configurations, doping levels, and preparation temperatures. Furthermore, we assembled NLPC∥NLPC symmetric ECs and NLPC∥Zn asymmetric ECs using aqueous sulfate electrolytes. Compared with the ECs using KOH aqueous electrolyte, the energy densities of NLPC∥NLPC and NLPC∥Zn ECs were significantly improved. The divergence of charge storage characteristics in KOH, Na2SO4, and ZnSO4 electrolytes were compared by analyzing their area surface capacitance. This work provides a strategy for the sustainable preparation of lignin-derived porous carbons toward ECs with high energy densities.

Aqueous-Microdroplet-Driven Abiotic Synthesis of Ribonucleotides.

Phosphorylation for ribonucleotide formation is a critical step in the origin of life but has had limited success due to the thermodynamic and kinetic constraints in aqueous media. Here, we report that the production of ribonucleotides from ribonucleosides in the presence of monopotassium phosphate (KH2PO4) spontaneously proceeded in aqueous microdroplets under ambient conditions and without using a catalyst. A full set of ribonucleotides including adenosine monophosphate (AMP), guanosine monophosphate (GMP), uridine monophosphate (UMP), and cytidine monophosphate (CMP) were generated on the scale of a few milliseconds. The aqueous microdroplets could transfer the ribonucleotides to oligoribonucleotides and showed mutual compatibility for individual phosphorylation. Conditions established the dependence of the conversion ratio on the droplet size and suggested that the condensation reactions occurred at or near the microdroplets' surface. This aqueous microdroplet approach also provides a route for elucidating phosphorylation chemistry in the prebiotic era.

Determination of radioactivity levels in feldspathic dental ceramics.

Activity concentrations of 42 different feldspathic dental ceramic powders were determined using a gamma spectrometer with an HPGe detector. The average 238U, 232Th and 226Ra activity concentrations of the specimens were 126 ± 8 Bq kg-1, 5.6 ± 0.5 Bq kg-1 and 12.7 ± 1.2 Bq kg-1, respectively. The average 40K activity was found as 2855 ± 89 Bq kg-1 ranging from 2252 ± 70 Bq kg-1 to 3522 ± 110 Bq kg-1 due to high potassium content in dental ceramics. None of the activity concentration measurements exceeded the limits by EC and ISO.

KOH/thiourea aqueous solution: A potential solvent for studying the dissolution mechanism and chain conformation of corn starch.

Non-derivatizing, high-efficiency and low-toxicity solvents are important for studying the dissolution behavior and potential applications of starch. In this study, we investigated the starch dissolution mechanism and molecular conformation in KOH/thiourea aqueous solutions and compared these with KOH/urea and KOH aqueous solutions. Solubility analysis revealed that the KOH/thiourea solution demonstrates a better ability to dissolve corn starch than KOH/urea and KOH solutions. Rheological behavior and dynamic and static light scattering indicated that starch is stable in KOH/thiourea solution and exists as a regular star structure. Fourier transform infrared spectroscopy, 13C NMR, and molecular dynamics simulations indicated that hydrated K+ and OH- destroy the strong starch hydrogen bond interactions; thiourea hydrate self-assembles into a shell surrounding the starch-KOH complex through interaction with KOH, whereas there is no direct strong interaction between urea and KOH. Therefore, adding thiourea to a KOH solution can promote dissolution and prevent self-aggregation of the starch chain.

Temperature-Induced Change of Water Structure in Aqueous Solutions of Some Kosmotropic and Chaotropic Salts.

The hydrogen bond structure of water was examined by comparing the temperature dependent OH-stretching bands of water and aqueous NaClO4, KClO4, Na2SO4, and K2SO4 solutions. Results called attention to the role of cations on top of the importance of anions determining the emerging structure of a multi-layered system consisting single water rings or multi-ring water-clusters.

A New and Ecological Method to Quantify Vancomycin in Pharmaceutical Product by Infrared Spectrometry.

Vancomycin, an antimicrobial, does not present quantitative method by infrared spectrometry in the literature for the evaluation of a pharmaceutical product. This technique is considered a clean alternative because in the main, there is no solvent involved and the generation of waste is reduced. So, the aim of this study was to develop and validate a new, ecological, low cost and fast method by infrared spectrometry using KBr and band between 1450-1375 cm-1. It was linear in the range of 1.0-2.0 mg/150 mg, with a correlation coefficient of 0.9994. Selective when the spectra of vancomycin reference and sample were compared. Precise by repeatability (2.29%) and intermediate precision (3.12%). Accurate with average recovery of 99.37% and robust when strength and compression time of the pellets and KBr brand were varied. Considering all the methods found in literature, there is not one using infrared spectrometry for quantitative purpose, so the method developed and validated could be considered an innovation and clean alternative. This is due to the fact that it is fast, easy to handle, low cost, and non-toxic as well as generating minimal waste. The method can be applied in the routine analysis of vancomycin dosage form and is an important option for the current and sustainable pharmaceutical analysis.

Characterization the structural property and degradation behavior of corn starch in KOH/thiourea aqueous solution.

Finding an efficient and eco-friendly solution for starch dissolution has attracted considerable attentions in recent years. This study investigated the structural characteristics, and degradation behavior of corn starch in KOH/thiourea aqueous solution by the comparison with DMSO/LiBr and 1-allyl-3-methylimidazolium chloride (AMIMCl). Results showed that KOH/thiourea solution was an effective solvent for corn starch dissolution (30 min with 97.01% solubility). X-ray diffraction (XRD) and 13C CP-MAS NMR spectroscopy revealed that native crystallinity of the corn starch was altered by all tested solvents, especially DMSO/LiBr and AMIMCl. Conversely, this new solvent did not change the primary molecular structure, chain-length distribution, or thermal stability of starch, compared with the native starch. Furthermore, KOH/thiourea solution was more suitable for measuring the molecular weight of corn starch, with a weight-average molecular weight (Mw) of 7.18 × 107 g/mol. Therefore, KOH/thiourea solution is a promising novel solvent for starch dissolution and structural exploration.

The study of laccase immobilization optimization and stability improvement on CTAB-KOH modified biochar.

BACKGROUND: Although laccase has a good catalytic oxidation ability, free laccase shows a poor stability. Enzyme immobilization is a common method to improve enzyme stability and endow the enzyme with reusability. Adsorption is the simplest and common method. Modified biochar has attracted great attention due to its excellent performance. RESULTS: In this paper, cetyltrimethylammonium bromide (CTAB)-KOH modified biochar (CKMB) was used to immobilize laccase by adsorption method (laccase@CKMB). Based on the results of the single-factor experiments, the optimal loading conditions of laccase@CKMB were studied with the assistance of Design-Expert 12 and response surface methods. The predicted optimal experimental conditions were laccase dosage 1.78 mg/mL, pH 3.1 and 312 K. Under these conditions, the activity recovery of laccase@CKMB was the highest, reaching 61.78%. Then, the CKMB and laccase@CKMB were characterized by TGA, FT-IR, XRD, BET and SEM, and the results showed that laccase could be well immobilized on CKMB, the maximum enzyme loading could reach 57.5 mg/g. Compared to free laccase, the storage and pH stability of laccase@CKMB was improved greatly. The laccase@CKMB retained about 40% of relative activity (4 °C, 30 days) and more than 50% of relative activity at pH 2.0-6.0. In addition, the laccase@CKMB indicated the reusability up to 6 reaction cycles while retaining 45.1% of relative activity. Moreover, the thermal deactivation kinetic studies of laccase@CKMB showed a lower k value (0.00275 min- 1) and higher t1/2 values (252.0 min) than the k value (0.00573 min- 1) and t1/2 values (121.0 min) of free laccase. CONCLUSIONS: We explored scientific and reasonable immobilization conditions of laccase@CKMB, and the laccase@CKMB possessed relatively better stabilities, which gave the immobilization of laccase on this cheap and easily available carrier material the possibility of industrial applications.