The initial rate of NH(3)/NH(4)(+) accumulation in a medium containing L(3) Teladorsagia circumcincta was 0.18-0.6 pmol h(-1) larva(-1), which increased linearly with larval density. However it appeared that the larva-generated external concentration of NH(3)/NH(4)(+) did not exceed about 130 μM. The rate of NH(3)/NH(4)(+) accumulation increased with temperature between 4 °C and 37 °C, declined with increasing pH or increasing external NH(3)/NH(4)(+) concentration and was not significantly affected by the concentration of the phosphate buffer or by exsheathing the larvae. We infer from these data that the efflux of NH(3)/NH(4)(+) is a diffusive process and that the secreted or excreted NH(3)/NH(4)(+) is generated enzymatically rather than dissociating from the surface of the nematode. The enzymatic source of the NH(3)/NH(4)(+) is yet to be identified. Since the concentration of NH(3)/NH(4)(+) in the rumen and abomasum is higher than 130 μM, it is unlikely that T. circumcincta contributes to it, but NH(3)/NH(4)(+) may be accumulated from the rumen fluid by the nematode.
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.
The combustion characteristics of Malaysia oil palm biomass (palm kernel shell (PKS), palm mesocarp fibre (PMF) and empty fruit bunches (EFB)), sub-bituminous coal (Mukah Balingian) and coal/biomass blends via thermogravimetric analysis (TGA) were investigated. Six weight ratios of coal/biomass blends were prepared and oxidised under dynamic conditions from temperature 25 to 1100°C at four heating rates. The thermogravimetric analysis demonstrated that the EFB and PKS evolved additional peak besides drying, devolatilisation and char oxidation steps during combustion. Ignition and burn out temperatures of blends were improved in comparison to coal. No interactions were observed between the coal and biomass during combustion. The apparent activation energy during this process was evaluated using iso-conversional model free kinetics which resulted in highest activation energy during combustion of PKS followed by PMF, EFB and MB coal. Blending oil palm biomass with coal reduces the apparent activation energy value.
The potential of base treated Shorea dasyphylla (BTSD) sawdust for Acid Blue 25 (AB 25) adsorption was investigated in a batch adsorption process. Various physiochemical parameters such as pH, stirring rate, dosage, concentration, contact time and temperature were studied. The adsorbent was characterized with Fourier transform infrared spectrophotometer, scanning electron microscope and Brunauer, Emmett and Teller analysis. The optimum conditions for AB 25 adsorption were pH 2, stirring rate 500 r/min, adsorbent dosage 0.10 g and contact time 60 min. The pseudo second-order model showed the best conformity to the kinetic data. The equilibrium adsorption of AB 25 was described by Freundlich and Langmuir, with the latter found to agree well with the isotherm model. The maximum monolayer adsorption capacity of BTSD was 24.39 mg/g at 300 K, estimated from the Langmuir model. Thermodynamic parameters such as Gibbs free energy, enthalpy and entropy were determined. It was found that AB 25 adsorption was spontaneous and exothermic.
Ferulic acid (FA) groups esterified to the arabinan side chains of pectic polysaccharides can be oxidatively cross-linked in vitro by horseradish peroxidase (HRP) catalysis in the presence of hydrogen peroxide (H(2)O(2)) to form ferulic acid dehydrodimers (diFAs). The present work investigated whether the kinetics of HRP catalyzed cross-linking of FA esterified to α-(1,5)-linked arabinans are affected by the length of the arabinan chains carrying the feruloyl substitutions. The kinetics of the HRP-catalyzed cross-linking of four sets of arabinan samples from sugar beet pulp, having different molecular weights and hence different degrees of polymerization, were monitored by the disappearance of FA absorbance at 316 nm. MALDI-TOF/TOF-MS analysis confirmed that the sugar beet arabinans were feruloyl-substituted, and HPLC analysis verified that the amounts of diFAs increased when FA levels decreased as a result of the enzymatic oxidation treatment with HRP and H(2)O(2). At equimolar levels of FA (0.0025-0.05 mM) in the arabinan samples, the initial rates of the HRP-catalyzed cross-linking of the longer chain arabinans were slower than those of the shorter chain arabinans. The lower initial rates may be the result of the slower movement of larger molecules coupled with steric phenomena, making the required initial reaction of two FAs on longer chain arabinans slower than on shorter arabinans.
A series of thiobarbituric acid derivatives 1-27 were synthesized and evaluated for their urease inhibitory potential. Exciting results were obtained from the screening of these compounds 1-27. Compounds 5, 7, 8, 11, 16, 17, 22, 23 and 24 showed excellent urease inhibition with IC50 values 18.1 ± 0.52, 16.0 ± 0.45, 16.0 ± 0.22, 14.3 ± 0.27, 6.7 ± 0.27, 10.6 ± 0.17, 19.2 ± 0.29, 18.2 ± 0.76 and 1.61 ± 0.18 μM, respectively, much better than the standard urease inhibitor thiourea (IC₅₀=21 ± 0.11 μM). Compound 3, 4, 10, and 26 exhibited comparable activities to the standard with IC₅₀ values 21.4 ± 1.04 and 21.5 ± 0.61 μM, 22.8 ± 0.32, 25.2 ± 0.63, respectively. However the remaining compounds also showed prominent inhibitory potential The structure-activity relationship was established for these compounds. This study identified a novel class of urease inhibitors. The structures of all compounds were confirmed through spectroscopic techniques such as EI-MS and (1)H NMR.
This study focuses on the feasibility of treating aged polycyclic aromatic hydrocarbons (PAHs)-contaminated soils using ethyl lactate (EL)-based Fenton treatment via a combination of parametric and kinetic studies. An optimised operating condition was observed at 66.7 M H2O2 with H2O2/Fe(2+) of 40:1 for low soil organic carbon (SOC) content and mildly acidic soil (pH 6.2), and 10:1 for high SOC and very acidic soil (pH 4.4) with no soil pH adjustment. The desorption kinetic was only mildly shifted from single equilibrium to dual equilibrium of the first-order kinetic model upon ageing. Pretreatment with EL fc = 0.60 greatly reduced the mass transfer coefficient especially for the slow desorbed fraction (kslow) of high molecular weight (HMW) PAHs, largely contributed by the concentration gradient created by EL-enhanced solubility. As the major desorption obstacle was almost fully overcome by the pretreatment, the pseudo-first-order kinetic reaction rate constant of PAHs degradation of aged soils was statistically discernible from that of freshly contaminated soils but slightly reduced in high SOC and high acidity soil. Stabilisation of H2O2 by EL addition in combination with reduced Fe(2+) catalyst were able to slow the decomposition rate of H2O2 even at higher soil pH.
The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures.
This paper demonstrates Pseudomonas cepacia lipase catalyzed hydrolysis of p-nitrophenyl palmitate under irradiation of light with wavelengths of 250-750 nm. The reaction follows Michaelis-Menten Kinetics and the light irradiation increases the overall rate of hydrolysis. Using Lineweaver-Burk plot K M and V max values for the reaction in presence of light are found to be 39.07 and 66.67 mM/min/g, respectively; while for the same reaction under dark condition, the values are 7.08 and 10.21 mM/min/g. The linear form of enzyme dependent rate of reaction confirms that no mass-transfer limitations are present and the reaction is a kinetically controlled enzymatic reaction.
This study demonstrates the potential of Na-silica waste sponge as a source of low cost catalyst in the transesterification of waste cooking oil aided by ultrasound. In this work an environmentally friendly and efficient transesterification process using Na-loaded SiO2 from waste sponge skeletons as a solid catalyst is presented. The results showed that the methyl esters content of 98.4±0.4wt.% was obtainable in less than an hour (h) of reaction time at 55°C. Optimization of reaction parameters revealed that MeOH:oil, 9:1; catalyst, 3wt.% and reaction duration of 30min as optimum reaction conditions. The catalyst is able to tolerant free fatty acid and moisture content up to 6% and 8%, respectively. In addition, the catalyst can be reused for seven cycles while maintaining the methyl esters content at 86.3%. Ultrasound undoubtedly assisted in achieving this remarkable result in less than 1h reaction time. For the kinetics study at 50-60°C, a pseudo first order model was proposed, and the activation energy of the reaction is determined as 33.45kJ/mol using Arrhenius equation.
This work describes methacrylic acid functionalized β-cyclodextrin (MAA-βCD) as a novel functional monomer in the preparation of molecular imprinted polymer (MIP MAA-βCD) for the selective removal of 2,4-dichlorophenol (2,4-DCP). The polymer was characterized using Fourier Transform Infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) and Field Emission Scanning Electron Microscopy (FESEM) techniques. The influence of parameters such as solution pH, contact time, temperature and initial concentrations towards removal of 2,4-DCP using MIP MAA-βCD have been evaluated. The imprinted material shows fast kinetics and the optimum pH for removal of 2,4-DCP is pH 7. Compared with the corresponding non-imprinted polymer (NIP MAA-βCD), the MIP MAA-βCD exhibited higher adsorption capacity and outstanding selectivity towards 2,4-DCP. Freundlich isotherm best fitted the adsorption equilibrium data of MIP MAA-βCD and the kinetics followed a pseudo-second-order model. The calculated thermodynamic parameters showed that adsorption of 2,4-DCP was spontaneous and exothermic under the examined conditions.
A novel adsorbent, magnetic, macro-reticulated cross-linked chitosan (MRC) was synthesised for the removal of tetracycline (TC) from water using a source of biogenic waste (gastropod shells) as a pore-forming agent. The insertion of crosslinks into the chitosan frame was confirmed by FTIR analysis, while the stability of the MRC was demonstrated via a stability test performed in an acidic solution. The enhanced porosity of the MRC was confirmed by the evaluation of its porosity, a swelling test and the determination of its specific surface area. The time-concentration profile of the sorption of TC onto the MRC demonstrated that equilibrium was attained relatively quickly (120 min), and the data obtained fitted a pseudo second order (r(2)>0.99) kinetic equation better than a pseudo first order or reversible first order kinetic equation. The optimisation of process variables indicated that the sorption of TC onto the MRC was favoured at a low solution pH and that the presence of organics (simulated by the addition of humic acid) negatively impacted the magnitude of TC removal. The area of coverage of TC on the MRC (2.51 m(2)/g) was low compared to the specific surface area of the MRC (47.95 m(2)/g). The value of the calculated energy of adsorption of TC onto the MRC was 100 kJ/mol, which is far above the range of 1-16 kJ/mol stipulated for physical adsorption.
With the exponential growth of the global population, the agricultural sector is bound to use ever larger quantities of fertilizers to augment the food supply, which consequently increases food production costs. Urea, when applied to crops is vulnerable to losses from volatilization and leaching. Current methods also reduce nitrogen use efficiency (NUE) by plants which limits crop yields and, moreover, contributes towards environmental pollution in terms of hazardous gaseous emissions and water eutrophication. An approach that offsets this pollution while also enhancing NUE is the use of controlled release urea (CRU) for which several methods and materials have been reported. The physical intromission of urea granules in an appropriate coating material is one such technique that produces controlled release coated urea (CRCU). The development of CRCU is a green technology that not only reduces nitrogen loss caused by volatilization and leaching, but also alters the kinetics of nitrogen release, which, in turn, provides nutrients to plants at a pace that is more compatible with their metabolic needs. This review covers the research quantum regarding the physical coating of original urea granules. Special emphasis is placed on the latest coating methods as well as release experiments and mechanisms with an integrated critical analyses followed by suggestions for future research.
To identify the effect of additional elastic force on the kinetic and kinematic characteristics, as well as the magnitude of leg stiffness, during the performance of accentuated countermovement jumps (CMJs).
Oil palm shell, a waste from palm oil industry, was cleaned and utilized as adsorbent. Its particle size distribution gave the uniformity coefficient of approximately two indicating that it can be used as filter bed media for continuous operation without resting. Its measured pH(pzc) of 4.1 is below the common pH of constructed wetland water body suggesting positive adsorption for heavy metal. The effect of various parameters on its adsorption was studied via batch experiments. The adsorption of Cu(II) and Pb(II) ions by oil palm shell showed a slightly better fit with the Freundlich compared to Langmuir. Its monolayer adsorption capacities were found to be 1.756 and 3.390mg/g for Cu(II) and Pb(II), respectively. High correlation coefficient of over 0.99 given by the pseudo-second-order model suggests that the rate limiting factor may be chemisorption. These findings suggest its potential application as constructed wetland media for the removal of heavy metal.
The effects of organic solvents and their binary mixture in the glucose functionalization of bacterial poly-3-hydroxyalkanoates catalyzed by Lecitase™ Ultra were studied. Equal volume binary mixture of DMSO and chloroform with moderate polarity was more effective for the enzyme catalyzed synthesis of the carbohydrate polymer at ≈38.2 (±0.8)% reactant conversion as compared to the mono-phasic and other binary solvents studied. The apparent reaction rate constant as a function of medium water activity (aw) was observed to increase with increasing solvent polarity, with optimum aw of 0.2, 0.4 and 0.7 (±0.1) observed in hydrophilic DMSO, binary mixture DMSO:isooctane and hydrophobic isooctane, respectively. Molecular sieve loading between 13 to 15gL(-1) (±0.2) and reaction temperature between 40 to 50°C were found optimal. Functionalized PHA polymer showed potential characteristics and biodegradability.
Utilization of macroalgae biomass for bioethanol production appears as an alternative source to lignocellulosic materials. In this study, for the first time, Amberlyst (TM)-15 was explored as a potential catalyst to hydrolyze carbohydrates from Eucheuma cottonii extract to simple reducing sugar prior to fermentation process. Several important hydrolysis parameters were studied for process optimization including catalyst loading (2-5%, w/v), reaction temperature (110-130°C), reaction time (0-2.5 h) and biomass loading (5.5-15.5%, w/v). Optimum sugar yield of 39.7% was attained based on the following optimum conditions: reaction temperature at 120°C, catalyst loading of 4% (w/v), 12.5% (w/v) of biomass concentration and reaction time of 1.5h. Fermentation of the hydrolysate using Saccharomyces cerevisiae produced 0.33 g/g of bioethanol yield with an efficiency of 65%. The strategy of combining heterogeneous-catalyzed hydrolysis and fermentation with S. cerevisiae could be a feasible strategy to produce bioethanol from macroalgae biomass.
In this investigation, palm empty fruit bunch (EFB) and almond shell (AS) were implemented as two natural catalysts rich in alkali metals, especially potassium, to enhance the reactivity of tire-char through co-gasification process. Co-gasification experiments were conducted at several blending ratios using isothermal Thermogravimetric analysis (TGA) under CO2. The pronounced effect of inherent alkali content of biomass-chars on promoting the reactivity of tire-char was proven when acid-treated biomass-chars did not exert any catalytic effect on improving the reactivity of tire-char in co-gasification experiments. In kinetic studies of the co-gasified samples in chemically-controlled regime, modified random pore model (M-RPM) was adopted to describe the reactive behavior of the tire-char/biomass-char blends. By virtue of the catalytic effect of biomass, the activation energy for tire-char gasification was lowered from 250 kJ/mol in pure form 203 to 187 kJ/mol for AS-char and EFB-char co-gasified samples, respectively.
In this work, preparation of granular activated carbon from oil palm biodiesel solid residue, oil palm shell (PSAC) by microwave assisted KOH activation has been attempted. The physical and chemical properties of PSAC were characterized using scanning electron microscopy, volumetric adsorption analyzer and elemental analysis. The adsorption behavior was examined by performing batch adsorption experiments using methylene blue as dye model compound. Equilibrium data were simulated using the Langmuir, Freundlich and Temkin isotherm models. Kinetic modeling was fitted to the pseudo-first-order, pseudo-second-order and Elovich kinetic models, while the adsorption mechanism was determined using the intraparticle diffusion and Boyd equations. The result was satisfactory fitted to the Langmuir isotherm model with a monolayer adsorption capacity of 343.94mg/g at 30°C. The findings support the potential of oil palm shell for preparation of high surface area activated carbon by microwave assisted KOH activation.
The effects of polyethyleneimine (PEI) impregnation on the Pb(2+) adsorption kinetics of palm shell-activated carbon and pH profile of bulk solution were investigated. Adsorption data were fitted to four established adsorption kinetics models, namely, pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion. It was found that PEI impregnation at 16.68 and 29.82 wt% PEI/AC increased the Pb(2+) uptake rate while the opposite was observed for PEI impregnation at 4.76 and 8.41 wt% PEI/AC. The increased uptake rates were due to higher concentration of PEI molecules on the surface of clogged pores as well as varying pore volumes. The adsorption kinetics data fitted the pseudo-second-order model better than the pseudo-first-order model, implying chemisorption was the rate-controlling step. The bulk solution pH generally showed an increasing trend from the use of virgin to PEI-impregnated activated carbon.