The present study synthesized nano-magnetite (Fe3O4) from milled steel chips using the high energy ball milling (HEBM) method, characterized it, and then utilized it as a sorbent to remediate boron concentration at various pH (4-9), dosages (0.1-0.5 g), contact times (20-240 min), and initial concentrations (10-100 mg/L). The nano-sorbents were characterized based on SEM structure, elemental composition (EDX), surface area analysis (BET), crystallinity (XRD), and functional group analysis (FTIR). The highest adsorption capacity of 8.44 mg/g with removal efficiency of 84% was attained at pH 8, 0.5 g dosage, contact time of 180 min, and 50 mg/L initial concentration. The experimental data fit best with the pseudo-second-order kinetic model with R2 of 0.998, while the Freundlich adsorption isotherm describes the adsorption process with an R2 value of 0.9464. A regeneration efficiency of 47% was attained even after five cycles of reusability studies. This efficiency implies that the nano-magnetite has the potential for sustainable industrial application.
This deals with fabrication of macromolecular prodrugs (MPDs) of salicylic acid (SA) and aspirin (ASP) based on a hydrophilic cellulose ether, hydroxyethyl cellulose (HEC). Degrees of substitution (DS) of SA and ASP per HEC repeating unit (HEC-RU) were achieved ranging from 0.60 to 2.18 and 0.53 to1.50, respectively. The amphiphilic HEC-SA conjugate 2 assembled into nanowire-like structures, while HEC-ASP conjugate 6 formed nanoparticles (diameter 300-00nm) at a water/DMSO interface. After oral administration in rabbit models, conjugates 2 and 6 showed plasma half-life of 6.96 and 7.01h with maximum plasma concentration (Cmax) of 15.27 and 23.01μg L-1, respectively, and each reached peak plasma concentration (tmax) at 4.0h. Immunomodulatory assays (interleukin 6 and tumor necrosis factor-α values) revealed that anti-inflammatory properties of SA and ASP were unaltered in conjugates. Swelling inhibition of 61 and 71% was observed for conjugates 2 and 6, respectively, in a carrageenan induced paw edema test. Cytotoxic profiling (MTT assay) showed that conjugates were safe for administration in the concentration range of 2-10mM up to 24h. Thermal analyses revealed that Tdm values of SA and ASP conjugates were increased by 99 and 154̊C, respectively, indicating extraordinary thermal stability imparted to drugs after MPD formation.
Novel bi-heterocyclic benzamides were synthesized by sequentially converting 4-(1H-indol-3-yl)butanoic acid (1) into ethyl 4-(1H-indol-3-yl)butanoate (2), 4-(1H-indol-3-yl)butanohydrazide (3), and a nucleophilic 5-[3-(1H-indol-3-yl)propyl]-1,3,4-oxadiazole-2-thiol (4). In a parallel series of reactions, various electrophiles were synthesized by reacting substituted anilines (5a-k) with 4-(chloromethyl)benzoylchloride (6) to afford 4-(chloromethyl)-N-(substituted-phenyl)benzamides (7a-k). Finally, the nucleophilic substitution reaction of 4 was carried out with newly synthesized electrophiles, 7a-k, to acquire the targeted bi-heterocyclic benzamides, 8a-k. The structural confirmation of all the synthesized compounds was done by IR, 1 H NMR, 13 C NMR, EI-MS, and CHN analysis data. The inhibitory effects of these bi-heterocyclic benzamides (8a-k) were evaluated against alkaline phosphatase, and all these molecules were identified as potent inhibitors relative to the standard used. The kinetics mechanism was ascribed by evaluating the Lineweaver-Burk plots, which revealed that compound 8b inhibited alkaline phosphatase non-competitively to form an enzyme-inhibitor complex. The inhibition constant Ki calculated from Dixon plots for this compound was 1.15 μM. The computational study was in full agreement with the experimental records and these ligands exhibited good binding energy values. These molecules also exhibited mild cytotoxicity toward red blood cell membranes when analyzed through hemolysis. So, these molecules might be deliberated as nontoxic medicinal scaffolds to render normal calcification of bones and teeth.
The present study comprises the synthesis of a new series of sulfonamides derived from 4-methoxyphenethylamine (1). The synthesis was initiated by the reaction of 1 with 4-methylbenzenesulfonyl chloride (2) in aqueous sodium carbonate solution at pH 9 to yield N-(4-methoxyphenethyl)-4-methylbenzensulfonamide (3).This parent molecule 3 was subsequently treated with various alkyl/aralkyl halides, (4a-j), using N,N-dimethylformamide (DMF) as solvent and LiH as activator to produce a series of new N-(4-methoxyphenethyl)-N-(substituted)-4-methylbenzenesulfonamides (5a-j). The structural characterization of these derivatives was carried out by spectroscopic techniques like IR, 1H-NMR, and 13C-NMR. The elemental analysis data was also coherent with spectral data of these molecules. The inhibitory effects on acetylcholinesterase and DPPH were evaluated and it was observed that N-(4-Methoxyphenethyl)-4-methyl-N-(2-propyl)benzensulfonamide (5c) showed acetylcholinesterase inhibitory activity 0.075 ± 0.001 (IC50 0.075 ± 0.001 µM) comparable to Neostigmine methylsulfate (IC50 2.038 ± 0.039 µM).The docking studies of synthesized ligands 5a-j were also carried out against acetylcholinesterase (PDBID 4PQE) to compare the binding affinities with IC50 values. The kinetic mechanism analyzed by Lineweaver-Burk plots demonstrated that compound (5c) inhibits the acetylcholinesterase competitively to form an enzyme inhibitor complex. The inhibition constants Ki calculated from Dixon plots for compound (5c) is 2.5 µM. It was also found from kinetic analysis that derivative 5c irreversible enzyme inhibitor complex. It is proposed on the basis of our investigation that title compound 5c may serve as lead structure for the design of more potent acetylcholinesterase inhibitors.
In the presented work, a new series of three different 4-((3,5-dichloro-2-[(2/4-halobenzyl)oxy]phenyl)sulfonyl)morpholines was synthesized and the structure of these compounds were corroborated by 1 H-NMR & 13 C-NMR studies. The in vitro results established all the three compounds as potent tyrosinase inhibitors relative to the standard. The Kinetics mechanism plots established that compound 8 inhibited the enzyme non-competitively. The inhibition constants Ki calculated from Dixon plots for this compound was 0.0025 μM. Additionally, computational techniques were used to explore electronic structures of synthesized compounds. Fully optimized geometries were further docked with tyrosinase enzyme for inhibition studies. Reasonably good binding/interaction energies and intermolecular interactions were obtained. Finally, drug likeness was also predicted using the rule of five (RO5) and Chemical absorption, distribution, metabolism, excretion, and toxicity (ADMET) characteristics. It is anticipated that current experimental and computational investigations will evoke the scientific interest of the research community for the above-entitled compounds.
Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic compounds, composed of benzene rings. The objective of this research was to identify the optimum condition for the degradation of PAHs contaminated water using photo-Fenton oxidation process via response surface methodology (RSM). Aqueous solution was prepared and potable water samples were collected from water treatment plants in Perak Tengah, Perak, Malaysia in September 2016. The reaction time, pH, molarity of H2O2 and FeSO4 were analyzed followed by RSM using aqueous solution. A five level central composite design with quadratic model was used to evaluate the effects and interactions of these parameters. The response variable was the percentage of total organic carbon (TOC) removal. PAHs quantification was done using gas chromatography mass spectrometry analysis. The regression line fitted well with the data with R2 value of 0.9757. The lack of fit test gives the highest value of Sum of Squares (15,666.64) with probability F value 0.0001 showing significant quadratic model. The optimum conditions were established corresponding to the percentage of TOC removal. The PAHs removal efficiency for potable water samples ranged from 76.4% to 91% following the first order of kinetic rates with R2 values of >0.95. Conventional water treatment techniques are not effective for PAHs removal. Thus, advanced oxidation processes may be considered as an alternative to conventional water treatment techniques in Malaysia and other developing countries.
Short-chain fructooligosaccharides (scFOSs) can be produced from the levan hydrolysis using levanase. Levanase from Bacillus lehensis G1 (rlevblg1) is an enzyme that specifically converts levan to scFOSs. However, the use of free levanase presents a lack of stability and reusability, thus hindering the synthesis of scFOSs for continuous reactions. Here, CLEAs for rlevblg1 were prepared and characterized. Cross-linked levanase aggregates using glutaraldehyde (CLLAs-ga) and bovine albumin serum (CLLAs-ga-bsa) showed the best activity recovery of 92.8% and 121.2%, respectively. The optimum temperature of CLLAs-ga and CLLAs-ga-bsa was increased to 35 °C and 40 °C, respectively, from its free rlevblg1 (30 °C). At high temperature (50 °C), the half-life of CLLAs-ga-bsa was higher than that of free rlevblg1 and CLLAs-ga. Both CLLAs exhibited higher stability at pH 9 and pH 10. Hyperactivation of CLLAs-ga-bsa was achieved with an effectiveness factor of more than 1 and with improved catalytic efficiency. After 3 h reaction, CLLAs-ga-bsa produced the highest total scFOSs yield of 35.4% and total sugar of 60.4% per gram levan. Finally, the reusability of CLLAs for 8 cycles with more than 50% activity retained makes them as a potential synthetic catalyst to be explored for scFOSs synthesis.
Photocatalytic degradation of p-cresol was carried out using ZnO under UV irradiation. The amount of photocatalyst, concentration of p-cresol and pH were studied as variables. The residual concentration and mineralization of p-cresol was monitored using a UV-visible spectrophotometer and total organic carbon (TOC) analyzer, respectively. The intermediates were detected by ultra high pressure liquid chromatography (UPLC). The highest photodegradation of p-cresol was observed at 2.5 g/L of ZnO and 100 ppm of p-cresol. P-cresol photocatalytic degradation was favorable in the pH range of 6-9. The detected intermediates were 4-hydroxy-benzaldehyde and 4-methyl-1,2-benzodiol. TOC studies show that 93% of total organic carbon was removed from solution during irradiation time. Reusability shows no significant reduction in photocatalytic performance in photodegrading p-cresol.
Elevated levels of nutrients in agroindustry wastewaters, and higher reliance on chlorination pose health threats due to formation of chlorinated organics as well as increased chlorination costs. Removals of ammonium and nitrate compounds were studied using activated carbon from palm shells, as adsorbent and support media. Experiments were carried out at several loadings, F:M from 0.31 to 0.58, and hydraulic residence times (HRT) of 24 h, 12 h and 8 h. Results show that the wastewater treatment process achieved removals of over 90% for COD and 62% for Total-N. Studies on removals from river water were carried out in sequencing batch reactor (SBR) and activated carbon biofilm (ACB) reactor. Removals achieved by the SBR adsorption-biodegradation combination were 67.0% for COD, 58.8% for NH3-N and 25.5% for NO3-N while for adsorption alone the removals were only 37.0% for COD, 35.2% for NH3-N and 13.8% for NO3-N. In the ACB reactor, at HRT of 1.5 to 6 h, removals ranged from 12.5 to 100% for COD, 16.7 to 100% for NO3-N and 13.5 to 100% for NH3-N. Significant decrease in removals was shown at lower HRT. The studies have shown that substantial removals of COD, NO3-N and NH3-N from both wastewater and river water may be achieved via adsorption-biodegradation by biofilm on activated carbon processes.
A significant breakthrough and progress have been made in the study of the kinetics of microbial transformation in sewers under aerobic and under changing aerobic/anaerobic conditions. Fundamental knowledge on anoxic kinetics of wastewater is still lacking, so it is not now possible to apply an integrated approach to municipal wastewater treatment incorporating sewer networks as a bio-chemical reactor. This paper presents the results of studies on determining half saturation constants for nitrate, KNO3, and nitrite, KNO2, in raw wastewater. The average values of KNO3 and KNO2, determined from experiments conducted on 7 different wastewater samples were found to be 0.76 gNO3-N/m3 and 0.33 gNO2-N/m3 respectively.
The sewer is an integral part of the urban wastewater system: the sewer, the wastewater treatment plant and the local receiving waters. The sewer is a reactor for microbial changes of the wastewater during transport, affecting the quality of the wastewater and thereby the successive treatment processes or receiving water impacts during combined sewer overflows. This paper presents the results of studies on anoxic processes, namely denitrification, in the bulk water phase of wastewater as it occurs in sewers. Experiments conducted on 12 different wastewater samples have shown that the denitrification process in the bulk wastewater can be simplified by the reduction of nitrate to nitrogen with significant accumulation of nitrite in the water phase. Utilization of nitrate was observed not to be limited by nitrate for concentrations above 5 gNO3-N/m3. The denitrification rates, under conditions of excess substrate and electron acceptor, were found to be in the range of 0.8-2.0 g NO3-N/(m3h). A discussion on the interaction of the sewer processes and the effects on a downstream located wastewater treatment plant (WWTP) is provided.
Chitosan-ethylene glycol diglycidyl ether/TiO2 nanoparticles (CS-EGDE/TNP) composite was synthesized to be biosorbent for the removal of reactive orange 16 (RO16) dye from aqueous solution. The CS-EGDE/TNP composite was characterized via BET, XRD, FTIR, and SEM-EDX techniques. Response surface methodology (RSM) with Box-Behnken design (BBD) was applied to optimize the adsorption key parameters such as adsorbent dose (A: 0.02-0.08 g/L), RO16 dye concentration (B: 20-80 mg/L), solution pH (C: 4-10), temperature (D: 30-50 °C), and contact time (E: 30-90 min). The adsorption isotherm followed Freundlich model and pseudo-second order (PSO) kinetic model. The adsorption capacity of CS-EGDE/TNP for RO16 dye was 1407.4 mg/g at 40 °C. The adsorption mechanism of RO16 dye on the surface of CS-EGDE/TNP can be attributed to various interactions such as electrostatic attraction, n-π interaction, Yoshida H-bonding, and H-bonding. Results supported the potential use of CS-EGDE/TNP as effective adsorbent for the treatment of acid reactive dye.
In this study, a new biocomposite magnetic adsorbent (magnetic glyoxal-chitosan Schiff base/organically modified montmorillonite (MCTS-GOX/OMMT)) was synthesized and employed for the adsorption of reactive blue 19 dye (RB19) from aqueous environment. The physicochemical properties of the MCTS-GOX/OMMT were confirmed by using various characterization techniques such as BET, XRD, FTIR, SEM-EDX, VSM, and pHpzc. The adsorption key variables were statistically optimized via Box-Behnken design (BBD) And accordingly the best operational conditions to achieve maximum RB19 removal were recorded at MCTS-GOX/OMMT dosage = 0.1 g/0.1 L, solution pH = 4, and working temperature = 25 °C. The adsorption process for RB19 appeared to follow the pseudo-second-order kinetic and the Langmuir isotherm models, according to the findings of the adsorption kinetics and equilibrium investigations. The maximum adsorption capacity of the MCTS-GOX/OMMT towards RB19 was 122.3 mg/g, demonstrating its preferable adsorption capability. The successful development of this novel magnetic bioadsorbent with excellent adsorption ability towards organic dyes and efficient separation ability opens possibilities for its practical application in wastewater treatment and dye removal processes.
In this study, chitosan/nano SiO2 (CTS/NS) was chemically modified with bisphenol A diglycidyl ether (BADGE) cross-linker-assisted hydrothermal process to create an effective adsorbent, CTS-BADGE/NS, for the removal of reactive orange 16 (RO16) dye from aquatic systems. Box-Behnken design (BBD) was used to optimize the adsorption process by varying the adsorbent dose (0.02-0.1 g/100 mL), pH (4-10), and time (20-360 min). The adsorption isotherm results indicated that the Langmuir model fits the experimental data well, suggesting that the adsorption process involves a monolayer formation of RO16 on the surface of CTS-BADGE/NS. The kinetic modeling of RO16 adsorption by CTS-BADGE/NS demonstrated that the pseudo-first-order model fits the adsorption data. CTS-BADGE/NS achieved an adsorption capacity of 97.8 mg/g for RO16 dye at optimum desirability functions of dosage 0.099 g/100 mL, solution pH of 4.44, and temperature of 25 °C. Overall, the π-π electron donor-acceptor system significantly improved the adsorption performance of the CTS-BADGE/NS. The results of the regeneration investigation demonstrate that the CTS-BADGE/NS exhibits effective adsorption of RO16, even after undergoing five consecutive cycles. The results of this study suggest that the developed CTS-BADGE/NS composite can be a promising adsorbent for water purification applications.
The ambient sonocatalytic degradation of congo red, methyl orange, and methylene blue by titanium dioxide (TiO(2)) catalyst at initial concentrations between 10 and 50mg/L, catalyst loadings between 1.0 and 3.0mg/L and hydrogen peroxide (H(2)O(2)) concentrations up to 600 mg/L is reported. A 20 kHz ultrasonic processor at 50 W was used to accelerate the reaction. The catalysts were exposed to heat treatments between 400 and 1000 degrees C for up to 4h to induce phase change. Sonocatalysts with small amount of rutile phase showed better sonocatalytic activity but excessive rutile phase should be avoided. TiO(2) heated to 800 degrees C for 2h showed the highest sonocatalytic activity and the degradation of dyes was influenced by their chemical structures, chemical phases and characteristics of the catalysts. Congo red exhibited the highest degradation rate, attributed to multiple labile azo bonds to cause highest reactivity with the free radicals generated. An initial concentration of 10mg/L, 1.5 g/L of catalyst loading and 450 ppm of H(2)O(2) gave the best congo red removal efficiency of above 80% in 180 min. Rate coefficients for the sonocatalytic process was successfully established and the reused catalyst showed an activity drop by merely 10%.
As a remedy for environmental pollution, a versatile synthetic approach has been developed to prepare polyvinyl alcohol (PVA)/nitrogen-doped carbon dots (CDs) composite film (PVA-CDs) for removal of toxic cadmium ions. The CDs were first synthesized using carboxymethylcellulose (CMC) of oil palms empty fruit bunch wastes with the addition of polyethyleneimine (PEI) and then the CDs were embedded with PVA. The PVA-CDs film possess synergistic functionalities through increasing the content of hydrogen bonds for chemisorption compared to the pure CDs. Optical analysis of PVA-CDs film was performed by ultraviolet-visible and fluorescence spectroscopy. Compared to the pure CDs, the solid-state PVA-CDs displayed a bright blue color with a quantum yield (QY) of 47%; they possess excitation-independent emission and a higher Cd2+ removal efficiency of 91.1%. The equilibrium state was achieved within 10 min. It was found that adsorption data fit well with the pseudo-second-order kinetic and Langmuir isotherm models. The maximum adsorption uptake was 113.6 mg g-1 at an optimal pH of 7. Desorption experiments showhe that adsorbent can be reused fruitfully for five adsorption-desorption cycles using 0.1 HCl elution. The film was successfully applied to real water samples with a removal efficiency of 95.34% and 90.9% for tap and drinking water, respectively. The fabricated membrane is biodegradable and its preparation follows an ecofriendly green route.
This research aims to compare the ability of smart hydrogel in removing the methylene blue prepared by using two different radiation methods. The extracted pectin from the dragon fruit peel (Hylocereus polyrhizus) was used with acrylic acid (AA) to produce a polymerized hydrogel through gamma and microwave radiation. The optimum hydrogel swelling capacity was obtained by varying the dose of radiation, pectin to AA ratio and pH used. From the array of samples, the ideal hydrogel was obtained at pH 8 with a ratio of 2:3 (pectin: AA) using 10 kGy and 400 W radiated gamma and microwave respectively. The performance of both hydrogels namely as Pc/AA(G) (gamma) and Pc/AA(Mw) (microwave) were investigated using methylene blue (MB) adsorption studies. In this study, three variables were manipulated, pH and MB concentration and hydrogel mass in order to find the optimum condition for the adsorption. Results showed that 20 mg of Pc/AA(G) performed the highest MB removal which was about 45% of 20 mg/L MB at pH 8. While 30 mg of Pc/AA(Mw) able to remove up to 35% of 20 mg/L MB at the same pH condition. To describe the adsorption mechanism, both kinetic models pseudo-first-order, pseudo-second-order were employed. The results from kinetic data showed that it fitted the pseudo-first-order as compared to pseudo-second-order model equation. This study provides alternative of green, facile and affective biomaterial for dye absorbents that readily available.
The treatment of high-strength organic brewery wastewater with added acetaminophen (AAP) by an anaerobic digester was investigated. An anaerobic packed-bed reactor (APBR) was operated as a continuous process with an organic loading rate of 1.5-g COD per litre per day and a hydraulic retention time of three days. The results of steady-state analysis showed that the greatest APBR performances for removing COD and TOC were as high as 98 and 93%, respectively, even though the anaerobic digestibility after adding the different AAP concentrations of 5, 10 and 15 mg L(-1) into brewery wastewater can affect the efficiency of organic matter removal. The average CH4 production decreased from 81 to 72% is counterbalanced by the increased CO2 production from 11 to 20% before and after the injection of AAP, respectively. The empirical kinetic models for substrate utilisation and CH4 production were used to predict that, under unfavourable conditions, the performance of the APBR treatment process is able to remove COD with an efficiency of only 6.8%.
In this present study, adsorptive membranes for Cr(VI) ion removal were prepared by blending polyethersulfone (PES) with hydrous ferric oxide (HFO) nanoparticles (NPs). The effects of HFO NPs to PES weight ratio (0-1.5) on the physicochemical properties of the resultant HFO/PES adsorptive membranes were investigated with respect to the surface chemistry and roughness as well as structural morphologies using different analytical instruments. The adsorptive performance of the HFO NPs/PES membranes was studied via batch adsorption experiments under various conditions by varying solution pH, initial concentration of Cr(VI), and contact time. The results showed that the membrane made of HFO/PES at a weight ratio of 1.0 exhibited the highest adsorption capacity which is 13.5 mg/g. Isotherm and kinetic studies revealed that the mechanism is best fitted to the Langmuir model and pseudo-second-order model. For filtration of Cr(VI), the best promising membranes showed improved water flux (629.3 L/m2 h) with Cr(VI) ion removal of 75%. More importantly, the newly developed membrane maintained the Cr(VI) concentration below the maximum contamination level (MCL) for up to 9 h.
Aristolochic acids are naturally occurring nephrotoxins. This study aims to investigate whether physiologically based kinetic (PBK) model-based reverse dosimetry could convert in vitro concentration-response curves of aristolochic acid I (AAI) to in vivo dose response-curves for nephrotoxicity in rat, mouse and human. To achieve this extrapolation, PBK models were developed for AAI in these different species. Subsequently, concentration-response curves obtained from in vitro cytotoxicity models were translated to in vivo dose-response curves using PBK model-based reverse dosimetry. From the predicted in vivo dose-response curves, points of departure (PODs) for risk assessment could be derived. The PBK models elucidated species differences in the kinetics of AAI with the overall catalytic efficiency for metabolic conversion of AAI to aristolochic acid Ia (AAIa) being 2-fold higher for rat and 64-fold higher for mouse than human. Results show that the predicted PODs generally fall within the range of PODs derived from the available in vivo studies. This study provides proof of principle for a new method to predict a POD for in vivo nephrotoxicity by integrating in vitro toxicity testing with in silico PBK model-based reverse dosimetry.