Removal of pharmaceutical compounds and toxicology study in wastewater using Malaysian fungal Ganoderma lucidum.

Elevated usage of pharmaceutical products leads to the accumulation of emerging contaminants in sewage. In the current work, Ganoderma lucidum (GL) was used to remove pharmaceutical compounds (PCs), proposed as a tertiary method in sewage treatment plants (STPs). The PCs consisted of a group of painkillers (ketoprofen, diclofenac, and dexamethasone), psychiatrists (carbamazepine, venlafaxine, and citalopram), beta-blockers (atenolol, metoprolol, and propranolol), and anti-hypertensives (losartan and valsartan). The performance of 800 mL of synthetic water, effluent STP, and hospital wastewater (HWW) was evaluated. Parameters, including treatment time, inoculum volume, and mechanical agitation speed, have been tested. The toxicity of the GL after treatment is being studied based on exposure levels to zebrafish embryos (ZFET) and the morphology of the GL has been observed via Field Emission Scanning Electron Microscopy (FESEM). The findings conclude that GL can reduce PCs from <10% to >90%. Diclofenac and valsartan are the highest (>90%) in the synthetic model, while citalopram and propranolol (>80%) are in the real wastewater. GL effectively removed pollutants in 48 h, 1% of the inoculum volume, and 50 rpm. The ZFET showed GL is non-toxic (LC50 is 209.95 mg/mL). In the morphology observation, pellets GL do not show major differences after treatment, showing potential to be used for a longer treatment time and to be re-useable in the system. GL offers advantages to removing PCs in water due to their non-specific extracellular enzymes that allow for the biodegradation of PCs and indicates a good potential in real-world applications as a favourable alternative treatment.

Sequential Esterification-Diels-Alder Reactions for Improving Pine Rosin Durability within Road Marking Paint.

Pine rosin, which is derived from Pinus merkusii resin, a natural product, has demonstrated potential as a road marking binder. Although pine rosin has an excellent shinning property, it has some limitations, such as instability and color change. To tackle these issues, modified rosin has been developed through sequential esterification and Diels-Alder reactions, and it has shown better properties than untreated rosin. In this study, from the evaluation of untreated and treated rosins, the treated rosin showed some improvements, such as a lower acid value and higher stability, as shown by the color consistency during the oxidation test at 150 °C for 24 h in open-air conditions. Additionally, as road marking paint, the modified rosin is blended with blending materials in the range of 18-28 wt.%. The modified rosin has a softening point of 170-210 °C, a hardness of 50-71 HD, and a weight loss of 1.33-5.12 mg during the wearing test. These results are comparable to or better than those of commercially available road marking products.

Synthesis of zinc oxide nanoparticles using methanol propolis extract (Pro-ZnO NPs) as antidiabetic and antioxidant.

In recent times, the overall health of individuals has been declining due to unhealthy lifestyles, leading to various diseases, including diabetes. To address this issue, antidiabetic and antioxidant agents are required to back-up human well-being. Zinc oxide (ZnO) is one such substance known for its antidiabetic and antioxidant effects. To enhance its capability and effectiveness, propolis was utilized to synthesize zinc oxide nanoparticles (Pro-ZnO NPs). The objective of this study was to synthesize Pro-ZnO NPs and assess their performance by conducting inhibition assays against α-amylase and α-glucosidase enzymes, as well as a 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay. The results showed that Pro-ZnO NPs were formed in a hexagonal wurtzite structure, with particle sizes ranging from 30 to 50 nm and an absorption band observed at 341 nm. The stability, chemical properties, and crystallography of Pro-ZnO NPs were also thoroughly examined using appropriate methods. The Pro-ZnO NPs demonstrated significant inhibitory effects against α-amylase and α-glucosidase enzymes, with inhibition rates reaching 69.52% and 73.78%, respectively, whereas the antioxidant activity was as high as 70.76%. Consequently, with their high inhibition rates, the Pro-ZnO NPs demonstrate the potential to be employed as a natural agent for combating diabetes and promoting antioxidant effects.

Thermal stabilization of polyvinyl chloride by calcium and zinc carboxylates derived from byproduct of palm oil refining.

Calcium and zinc carboxylates were prepared from palm fatty acid distillate, a byproduct of palm oil refining, via metathesis in aqueous ethanol. The formations of both metal carboxylates have been confirmed by infrared spectroscopy and x-ray diffraction analysis. Thermogravimetric analysis has shown that the prepared calcium and zinc carboxylates are practically stable while their weight losses are 14% at 393 °C and 19% at 311 °C, respectively. The efficacy of the metal carboxylates in their mixtures in stabilizing polyvinyl chloride against heat has also been studied by using static and dynamic tests. The calcium to zinc ratio of 4:1 has been found to give the longest stability time under the studied condition. The mixed calcium/zinc carboxylates demonstrate a synergism effect with pentaerythritol. The results reveal that mixed calcium/zinc carboxylates from palm fatty acid distillate are effective in stabilizing polyvinyl chloride against heat.

Sustainable Diesel from Pyrolysis of Unsaturated Fatty Acid Basic Soaps: The Effect of Temperature on Yield and Product Composition.

The production of sustainable diesel without hydrogen addition remains a challenge for low-cost fuel production. In this work, the pyrolysis of unsaturated fatty acid (UFA) basic soaps was studied for the production sustainable diesel (bio-hydrocarbons). UFAs were obtained from palm fatty acids distillate (PFAD), which was purified by the fractional crystallization method. Metal hydroxides were used to make basic soap composed of a Ca, Mg, and Zn mixture with particular composition. The pyrolysis reactions were carried out in a batch reactor at atmospheric pressure and various temperatures from 375 to 475 °C. The liquid products were obtained with the best yield (58.35%) at 425 °C and yield of diesel fraction 53.4%. The fatty acids were not detected in the pyrolysis liquid product. The gas product consisted of carbon dioxide and methane. The liquid products were a mixture of hydrocarbon with carbon chains in the range of C7 and C20 containing n-alkane, alkene, and iso-alkane.

Enhanced adsorption capacity of activated carbon over thermal oxidation treatment for methylene blue removal: kinetics, equilibrium, thermodynamic, and reusability studies.

Activated carbon (AC) is an effective and inexpensive adsorbent material for dye removal, but it cannot always be used repeatedly. Furthermore, the adsorbed dyes with toxicity usually remain on its surface. In this study, a thermal air oxidation process was used to modify the surface of AC and decompose adsorbed methylene blue (MB). The behavior of this process on spent AC was investigated using TGA-DTA, while the degradation of MB before and after the regeneration process was analyzed using a carbon, hydrogen, nitrogen, sulfur (CHNS) analyzer. It was discovered that thermal air oxidation could promote the formation of oxygenated functional groups on AC produced from steam-activated carbon coconut shell (SACCS), which when treated at 350 °C (denoted as SACCS-350), demonstrated an adsorption capacity 2.8 times higher than the non-air-oxidized AC (SACCS). The key parameters for the MB adsorption of SACCS and SACCS-350, such as kinetics, equilibrium, and thermodynamics, were compared. Moreover, the SACCS-350 could be reused at least 3 times for the adsorption of MB. Based on these results, thermal air oxidation treatment could successfully improve the adsorption performance of AC and regenerate spent AC through a reasonable and environmentally friendly process compared to other regeneration methods.

The promising performance of manganese gluconate as a liquid redox sulfur recovery agent against oxidative degradation.

This work studied the oxidative degradation performance of manganese gluconate as a liquid redox sulfur recovery (LRSR) agent. The degradation of gluconate in an aerated sulfide containing 0.1 M manganese/0.8 M gluconate/pH 13 solution was 11% in 47 h and 20% in 100 h of reaction time. With the total price of chelates being more or less comparable, these were superior to the degradation resistance of EDTA chelate in a solution of 0.1 M iron/0.2 M EDTA/pH 8 which degraded by about 30% in 47 h, and NTA in Fe-NTA (0.1 M metal/0.2 M chelate/pH 6.5), which was degraded by 40% in 100 h of reaction time. At pH of 13, 0.1 M Metal, and 0.8 M gluconate, manganese degraded gluconate more severely than iron and copper. At a lower chelate to metal molar ratio (RCM) of 2 and as well as at a lower pH of 10, the manganese gluconate degradation, expressed as relative concentration to its initial concentration, was faster than at RCM of 8 and pH of 13. All of these observations can be explained among others by the well-known Fenton reaction hydroxyl radicals mechanism as the main cause of the degradation process.

H2S-CO2 gas separation with ionic liquids on low ratio of H2S/CO2.

Acid gas removal, especially H2S and CO2, is an essential process in natural gas processing. In this research, 1-butyl-3-methylimidazolium bromide [bmim][Br] ionic liquid was analyzed as a hydrophobic solvent with has high selectivity to H2S as an environmentally friendly solvent to absorb acid gas from natural gas with low H2S/CO2 concentration in ambient temperature and pressure. The absorption performance of pure [bmim][Br] ionic liquid was compared with various amine solutions, such as monoethanolamine (MEA), triethanolamine (TEA), and methyldiethanolamine (MDEA), as well as the mixture of [bmim][Br]-MDEA with various concentration. As a result, pure [bmim][Br] ionic liquid had high selectivity to H2S compared with conventional amine solutions. In addition, the mixture of [bmim][Br]-MDEA with the mass ratio of 1:3 provided the highest H2S/CO2 selectivity of 6.2 in certain absorption conditions due to free tertiary amine attached in the cations of ionic liquids that can attract more H2S to its functional site.

A method to control terpineol production from turpentine by acid catalysts mixing.

Terpineol, a promising valorisation product of pine industry, is widely used as an active ingredient for disinfectant soap, cleansers, perfumes, and pharmaceutical purposes. Synthesis of terpineol is generally carried out by separation of α-pinene compounds from crude turpentine through fractionation and then hydrated (addition of water) with the help of acid catalysts. However, direct turpentine hydration without pre-fractionation process can be more beneficial from economic and process point of views. This study aims to investigate the effect of both single and mixed/combined catalysts towards terpineol yield. Combined strong and weak acid catalysts were required to obtain high feed conversion and terpineol yield. The selectivity of terpineol is then correlated to the solubility of a weak/organic acid. In this study, the highest yield of terpineol was 54.0 ± 8.2%-w/w using combination of formic acid and sulphuric acid.

Manganese gluconate, A greener and more degradation resistant agent for H2S oxidation using liquid redox sulfur recovery process.

Iron chelate liquid redox sulfur recovery (LRSR) has been one of the most frequently recommended technologies for the oxidation of H2S in natural gas into elemental sulfur, particularly when the acid gas has a high CO2/H2S molar ratio. The process is however known to suffer from extensive oxidative ligand degradation that results in high operational costs. Moreover, poor biodegradability or toxicity of the existing ligand has become a concern. In this research, we demonstrated that gluconate, a naturally greener ligand, when coupled with manganese as the metal, has considerable potential to be a better redox agent. Manganese gluconate solution was more resistant against ligand degradation compared with iron NTA. As required, aerated solution was capable of converting dissolved NaHS into elemental sulfur. At sufficiently high pH, manganese gluconate solutions were stable enough from precipitation of manganese hydroxide, carbonate, or sulfides. An equilibrium calculation has been developed to understand the precipitation behavior.

Cocoa bean skin waste as potential raw material for liquid smoke production.

Cocoa bean skin is a waste of chocolate industries that mostly contains hemicellulose, cellulose, and lignin. This material shows to be a promising feedstock for the production of liquid smoke and charcoal. The study was aimed to analyse the influence of temperature and heating rate of cocoa bean skin pyrolysis to the production of liquid smoke. Optimization of pyrolysis process variables, i.e. by adjusting the suitable temperature and heating rate, is the key to obtain a high-quality product. The pyrolysis process was carried out using heating rates between 5°C/min and 15°C/min at three pyrolysis temperatures of 450°C, 500°C, and 550°C. The yield of the produced liquid smoke was in the range of 18-23%. It showed that at a faster heating rate, the reaction produced more charcoal, ash, and water content for all pyrolysis temperatures. The highest yield of charcoal was ca. 39% with a caloric value of 22.97 MJ/kg, while the lowest ash and water content was in the range of 16.5-19% and 6.5-8.5%, respectively. This result shows that the utilization of this organic waste compounds could be promising for large-scale production.

Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes.

Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔEAB. Counterpoise-corrected interaction energies ΔEAB are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A-B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [EMP2/CBS] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔECC-MP, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔEAB with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting deviation from the computational reference of less than 1 kcal mol(-1). The zero-point vibrational energy corrected estimates Δ(EAB+ZPE), obtained with the three functionals and the 6-31G(d) and N07T basis sets, are compared with experimental D0 measures, when available. In particular, this comparison is finally extended to the naphthalene and coronene dimers and to three π-π associations of different PAHs (R, made by 10, 16, or 24 C atoms) and P (80 C atoms).

Decomposition of dichlorobenzene in a dielectric barrier discharge.

This paper presents a decomposition study of 1,2-dichlorobenzene (DCB) using a dielectric barrier discharge (DBD). The discussion is focused on the effects of variations of carrier gases, DCB concentrations and input voltages on the decomposition performance. The DCB conversion was conducted inside a cylindrical reactor consists of silver film as the outside electrode and a spring coil as the inside electrode. Two carrier gases, i.e. air and nitrogen, were introduced to the reactor at a total flow rate of 500 mL/min with DCB concentrations of 100, 300 and 500 ppm. Gaseous products, before and after plasma treatment, were analysed by a gas chromatography and FT-IR spectroscopy, and the consumed power was calculated from Lissajous' figure analysis. In order to improve the decomposition performance, various TiO2-supported catalysts were employed.

Polycyclic aromatic hydrocarbon formation mechanism in the "particle phase". A theoretical study.

The synthesis of polycyclic aromatic hydrocarbons (PAHs) and the formation of soot platelets occur both during combustion at relatively low [O(2)], or under pyrolysis conditions. When the PAH size grows beyond the number of three-four condensed cycles, the partitioning of PAHs between the gas and particle phases favours the latter (i.e. adsorption). This study aims to assess which role the soot particle plays during PAH synthesis, in particular if catalytic or template effects of some sort can be exerted by the soot platelet on the adsorbed growing PAH-like radical. Our theoretical calculations indicate that chain elongation by ethyne addition cannot compete with cyclization when both can take place in the growing PAH-like radical, already in the gas phase. When it is adsorbed, cyclization is found to become easier than in the gas phase (more so, in terms of Gibbs free energy barriers, at higher temperatures), hinting at some sort of template effect, while chain elongation by ethyne addition becomes somewhat more difficult. The underlying soot platelet can assist (at lower temperatures) the formation of a larger aromatic hydrocarbon, by a final hydrogen abstraction from that endocyclic saturated carbon the newly formed cycle still bears. As an alternative (at higher temperature), a spontaneous hydrogen atom loss can take place. Finally, at rather low temperatures, the addition of the growing radical to the underlying soot platelet might occur and cause some reticulation, form more disordered structures, i.e. soot precursors instead of PAHs.

A density functional theory study of phenyl formation initiated by ethynyl radical (C2H*) and ethyne (C2H2).

An ab initio computational density functional theory (DFT) was used to study the formation of the first cyclic molecule (phenyl) initiated by the ethynyl radical (C(2)H*). The study covers a competition reaction between the addition reactions of C(2)H* with ethyne (C(2)H(2)) and some molecular re-arrangement schemes. The minimum energy paths of the preferred cyclic formation route were characterized. A thorough thermochemical analysis was performed by evaluating the differences in the energy of activation (DeltaE), enthalpy (DeltaH), and Gibb's free energy (DeltaG) of the optimized stable and transition state (TS) molecules. The reaction temperatures were set to normal (T = 298 K) and combustion (T = 1,200 K) conditions.

Gliding arc plasma processing of CO2 conversion.

Conversion of carbon dioxide (CO2) using gliding arc plasma was performed. The research was done to investigate the effect of variation of total gas flow rates and addition of auxiliary gases--N2, O2, air, water--to the CO2 conversion process. This system shows higher power efficiency than other nonthermal plasma methods. Experiment results indicate the conversion of CO2 reaches 18% at total gas flow rate of 0.8 L/min and produces CO and O2 as the main gaseous products. Among auxiliary gases, only N2 gives positive effect on CO2 conversion and the power efficiency at N2 concentration of 95% and total gas flow rate of 2 L/min increases about three times compared to pure CO2 process.

Decomposition of CCl4 and CHCl3 on gliding are plasma.

Decomposition of chlorinated hydrocarbons, CCl4 and CHCl3, in gliding plasma was examined. The effects of initial concentrations, total gas flow rates, and power consumption have been investigated. The conversion result was relatively high. It reached 80% for CCl4 and 97% for CHCl3. Using atmospheric air as the carrier gas, the plasma reaction occurred at exothermic reaction and the main products were CO2, CO, and Cl2. Transformation into CCl4 was also detected for CHCl3 decomposition reaction. The conversion of CCl4 and CHCl3 were increased with the increasing applied frequency and decreasing total gas flow rate.