A penalized quantitative structure-property relationship (QSPR) model with adaptive bridge penalty for predicting the melting points of 92 energetic carbocyclic nitroaromatic compounds is proposed. To ensure the consistency of the descriptor selection of the proposed penalized adaptive bridge (PBridge), we proposed a ridge estimator ([Formula: see text]) as an initial weight in the adaptive bridge penalty. The Bayesian information criterion was applied to ensure the accurate selection of the tuning parameter ([Formula: see text]). The PBridge based model was internally and externally validated based on [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], the Y-randomization test, [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and the applicability domain. The validation results indicate that the model is robust and not due to chance correlation. The descriptor selection and prediction performance of PBridge for the training dataset outperforms the other methods used. PBridge shows the highest [Formula: see text] of 0.959, [Formula: see text] of 0.953, [Formula: see text] of 0.949 and [Formula: see text] of 0.959, and the lowest [Formula: see text] and [Formula: see text]. For the test dataset, PBridge shows a higher [Formula: see text] of 0.945 and [Formula: see text] of 0.948, and a lower [Formula: see text] and [Formula: see text], indicating its better prediction performance. The results clearly reveal that the proposed PBridge is useful for constructing reliable and robust QSPRs for predicting melting points prior to synthesizing new organic compounds.
Although plastic induces environmental damages, almost the consumption of poly(vinyl chloride) never stops increasing. Therefore, this work abstracted by two parts, first, synthesis of Schiff bases 1-4 compounds through the reaction of amino group with appropriate aromatic aldehyde, reaction of PVC with Schiff bases compounds 1-4 in THF to form a new modified PVC-1, PVC-2, PVC-3, and PVC-4. The structures of Schiff bases 1-4 and the modified PVC-1, PVC-2, PVC-3, and PVC-4 have been characterized by different spectroscopic analyses. Second, the influence of introducing 4-amino-1,2,4-triazole as a pendent groups into PVC chain investigated on photostability rules of tests. The modified polymers photostability investigated by observing indices (ICO, Ipo, and IOH), weight loss, UV and morphological studies, and all results obtained indicated that PVC-1, PVC-2, PVC-3 and PVC-4 gave lower growth rate of ICO, IPO, and IOH through UV exposure time. The photostability are given as PVC-4
In light of a slow buildup in CO2 emissions since the recovery, this paper revisits the relationship between CO2 emissions and the US economy using a nonlinear autoregressive distributed lag model, in which the determinants are identified through an expanded real business cycle model. We find convincing evidence that CO2 emissions decline more rapidly during recessions than increase during expansions over the long run. Of all determinants considered, long-run asymmetry is fostered once vehicle miles traveled is controlled. This calls for a greater attention to public transportation development and vehicle miles traveled tax for slowing down stock buildup of CO2 emissions during good times.
Lignocellulosic biomass waste is a cheap, eco-friendly, and sustainable raw material for a wide array of applications. In the present study, an easy, fast, and economically feasible route has been proposed for the preparation of different zero-valent metal nanoparticles (ZV-MNPs) based on Cu, Co, Ag, and Ni NPs using empty fruit bunch (EFB) biomass residue as support material. The catalytic efficiency of ZV-MNPs/EFB catalyst was investigated against five model pollutants, such as methyl orange (MO), congo red (CR), methylene blue (MB), acridine orange (AO), and 4-nitrophenol (4-NP) using NaBH4 as a source of hydrogen and electron. Comparative study revealed that among as-prepared ZV-MNPs/EFB catalysts, Cu-NPs immobilized onto EFB (Cu/EFB) exhibited maximum catalytic efficiency towards pollutant abasement. Degradation reactions were highly efficient, and were completed within a short time (4 min) in case of MO, CR, and MB, whilst AO and 4-NP were reduced in less than 15 min. Kinetic investigation revealed that the degradation rate of model pollutants accorded with pseudo-first order model. Furthermore, supported catalysts were easily recovered after the completion of experiment by simply pulling the catalyst from reaction system. Recyclability tests performed on Cu/EFB revealed that more than 97% of the reduction was achieved in case of MO dye for four successive cycles of reuse. The as-prepared heterostructure showed multifunctional properties, such as enhanced uptake of contaminants, high catalytic efficiency, and easy recovery, hence, offers great prospects in wastewater purification.
This work explores the feasibility of orange peel, a citrus processing biomass as an alternative precursor for preparation of activated carbon (OPAC) via microwave assisted K(2)CO(3) activation. The operational parameters, chemical impregnation ratio, microwave power and irradiation time on the carbon yield and adsorption capability were investigated. The virgin characteristics of OPAC were examined by pore structural analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, nitrogen adsorption isotherm, elemental analysis, surface acidity/basicity and zeta potential measurement. The optimum conditions resulted in OPAC with a monolayer adsorption capacity of 382.75 mg/g for methylene blue and carbon yield of 80.99%. The BET surface area, Langmuir surface area and total pore volume were identified to be 1104.45 m(2)/g, 1661.04 m(2)/g and 0.615 m(3)/g, respectively. Equilibrium data were simulated using the Langmuir, Freundlich, Dubinin-Radushkevich, Redlich-Peterson, and Toth isotherms, and kinetic data were fitted to the pseudo-first-order, pseudo-second-order and Elovich kinetic models.
Immobilized Candida rugosa lipase was used for the synthesis of citronellyl laurate from citronellol and lauric acid. Screening of different types of support (Amberlite MB-1 and Celite) for immobilization of lipase and solvent (n-hexane, n-heptane, and iso-octane) and optimization of reaction conditions, such as catalyst loading, effect of substrates molar ratio and temperature, have been studied. The maximum enzyme activity was obtained at 310 K. The immobilized C. rugosa lipase onto Amberlite MB-1 support was found to be the best support with a conversion of 89% of citronellyl laurate ester in iso-octane compared to Celite 545. Deactivation of C. rugosa lipase at 313, 318 and 323 K were observed. Ordered bi bi mechanism with dead end complex of lauric acid was found to fit the initial rate data and the kinetic parameters were obtained by non-linear regression analysis.
Enzymatic reduction of carbon dioxide (CO2 ) to methanol (CH3 OH) can be accomplished using a designed set-up of three oxidoreductases utilizing reduced pyridine nucleotide (NADH) as cofactor for the reducing equivalents electron supply. For this enzyme system to function efficiently a balanced regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO2 to CH3 OH, with kinetically synchronous enzymatic cofactor regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization experiments were conducted to verify the kinetically modeled results. Repetitive reaction cycles were shown to enhance the yield of CH3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH3 OH, a TTN of 160 and BPR of 24 μmol CH3 OH/U · h during 6 hr of reaction. The study demonstrates that an optimal reaction set-up could be designed from rational kinetics modeling to maximize the yield of CH3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency.
Previous molecular dynamic simulations have reported elongation of the existing beta-sheet in prion proteins. Detailed examination has shown that these elongations do not extend beyond the proline residues flanking these beta-sheets. In addition, proline has also been suggested to possess a possible structural role in preserving protein interaction sites by preventing invasion of neighboring secondary structures. In this work, we have studied the possible structural role of the flanking proline residues by simulating mutant structures with alternate substitution of the proline residues with valine. Simulations showed a directional inhibition of elongation, with the elongation progressing in the direction of valine including evident inhibition of elongation by existing proline residues. This suggests that the flanking proline residues in prion proteins may have a containment role and would confine the beta-sheet within a specific length.
The current study dealt with the synthesis and characterization of carboxymethyl fenugreek galactomannang-g-poly(N-isopropylacrylamide-co-N,N'-methylene-bis-acrylamide)-bentonite [CFG-g-P(NIPA-co-MBA)-BEN] based nanocomposites (NCs) as erlotinib (ERL)-delivery devices for lung cancer cells to suppress excessive cell proliferation. The blank NCs exhibited outstanding biodegradability and pH/temperature-dependent swelling profiles, which were significantly influenced by their BEN contents (0-20%). The molar mass (M¯c) between the crosslinks of these NCs was declined with temperature. The composite architecture of these scaffolds was confirmed by XRD, FTIR, TGA, DSC and SEM analyses. The corresponding ERL-loaded matrices (F-1-F-3) portrayed outstanding drug encapsulation efficiency (DEE, 93-100%) with zeta potential between -8 and -16 mV and diameter between 615 and 1258 nm. These formulations demonstrated sustained ERL elution profiles (Q8h, 62-98%) with an initial burst release of drug. The drug dissolution pattern of the optimized matrices (F-3) obeyed first-order kinetic model and was driven by Fickian diffusion. The mucin adsorption behavior of F-3 was best fitted to Freudlich isotherms. The ERL-loaded formulation suppressed A549 cell proliferation and promoted apoptosis to a greater extent than the pristine drug, as detected by cellular uptake analysis, MTT cytotoxicity test and AO/EB staining assay.
In this work, a genetic algorithm is applied for the automatic detection of oil spills. The procedure is implemented using sequences from RADARSAT-2 SAR ScanSAR Narrow single-beam data acquired in the Gulf of Mexico. The study demonstrates that the implementation of crossover allows for the generation of an accurate oil spill pattern. This conclusion is confirmed by the receiver-operating characteristic (ROC) curve. The ROC curve indicates that the existence of oil slick footprints can be identified using the area between the ROC curve and the no-discrimination line of 90%, which is greater than that of other surrounding environmental features. In conclusion, the genetic algorithm can be used as a tool for the automatic detection of oil spills, and the ScanSAR Narrow single-beam mode serves as an excellent sensor for oil spill detection and survey.
A series of hexahydro-1,6-naphthyridines were synthesized in good yields by the reaction of 3,5-bis[(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones with cyanoacetamide in the presence of sodium ethoxide under simple mixing at ambient temperature for 6-10 minutes and were assayed for their acetylcholinesterase (AChE) inhibitory activity using colorimetric Ellman's method. Compound 4e with methoxy substituent at ortho-position of the phenyl rings displayed the maximum inhibitory activity with IC50 value of 2.12 μM. Molecular modeling simulation of 4e was performed using three-dimensional structure of Torpedo californica AChE (TcAChE) enzyme to disclose binding interaction and orientation of this molecule into the active site gorge of the receptor.
Thermal characteristics of turbulent nanofluid flow in a rectangular pipe have been investigated numerically. The continuity, momentum, and energy equations were solved by means of a finite volume method (FVM). The symmetrical rectangular channel is heated at the top and bottom at a constant heat flux while the sides walls are insulated. Four different types of nanoparticles Al2O3, ZnO, CuO, and SiO2 at different volume fractions of nanofluids in the range of 1% to 5% are considered in the present investigation. In this paper, effect of different Reynolds numbers in the range of 5000 < Re < 25000 on heat transfer characteristics of nanofluids flowing through the channel is investigated. The numerical results indicate that SiO2-water has the highest Nusselt number compared to other nanofluids while it has the lowest heat transfer coefficient due to low thermal conductivity. The Nusselt number increases with the increase of the Reynolds number and the volume fraction of nanoparticles. The results of simulation show a good agreement with the existing experimental correlations.
This research aims to formulate and to optimize a nanoemulsion-based formulation containing fullerene, an antioxidant, stabilized by a low amount of mixed surfactants using high shear and the ultrasonic emulsification method for transdermal delivery. Process parameters optimization of fullerene nanoemulsions was done by employing response surface methodology, which involved statistical multivariate analysis. Optimization of independent variables was investigated using experimental design based on Box-Behnken design and central composite rotatable design. An investigation on the effect of the homogenization rate (4,000-5,000 rpm), sonication amplitude (20%-60%), and sonication time (30-150 seconds) on the particle size, ζ-potential, and viscosity of the colloidal systems was conducted. Under the optimum conditions, the central composite rotatable design model suggested the response variables for particle size, ζ-potential, and viscosity of the fullerene nanoemulsion were 152.5 nm, -52.6 mV, and 44.6 pascal seconds, respectively. In contrast, the Box-Behnken design model proposed that preparation under the optimum condition would produce nanoemulsion with particle size, ζ-potential, and viscosity of 148.5 nm, -55.2 mV, and 39.9 pascal seconds, respectively. The suggested process parameters to obtain optimum formulation by both models yielded actual response values similar to the predicted values with residual standard error of <2%. The optimum formulation showed more elastic and solid-like characteristics due to the existence of a large linear viscoelastic region.
DFT and G4 results reveal that cations display the following trends in imparting its positive charge to acrylonitrile; H⁺ > Li⁺ > Na⁺ > K⁺ for group I and Be²⁺ > Mg²⁺ > Ca²⁺ for group II. Solvation by water molecules and interaction with cation make the cyano bond more polarized and exhibits ketene-imine character. Bond order in nitrile-cation complexes has been predicted based on the s character of the covalent bond orbitals. Mulliken, CHELPG, and NPA charges are in good agreement in predicting positive charge buildup and GIAO nuclear deshileding on C1. G4 enthalpies show that Mg²⁺ is more strongly bound to acrylonitrile than to acetonitrile by 3 kcal mol⁻¹, and the proton affinity of the former is higher by 0.8 kcal mol⁻¹. G4 enthalpies of reductions support prior experimental observation that metalated conjugated nitriles show enhanced reactivity toward weak nucleophiles to afford Michael addition products.
The degradation behavior of veterinary antibiotics in soil is commonly studied using the following methods of adding antibiotics to the soil: (i) adding manure collected from animals fed with a diet containing antibiotics, (ii) adding antibiotic-free animal manure spiked with antibiotics and (iii) directly adding antibiotics. No research simultaneously comparing different antibiotic addition methods was found. Oxytetracycline (OTC) was used as a model antibiotic to compare the effect of the three commonly used antibiotic addition methods on OTC degradation behavior in soil. The three treatment methods have similar trends, though OTC degradation half-lives show the following significant differences (P<0.05): manure from swine fed OTC (treatment A)
In Malaysia, large amounts of organic materials, which lead to disposal problems, are generated from agricultural residues especially from palm oil industries. Increasing landfill costs and regulations, which limit many types of waste accepted at landfills, have increased the interest in composting as a component of waste management. The objectives of this study were to characterize compost feedstock properties of common organic waste materials available in Malaysia. Thus, a ratio modelling of matching ingredients for empty fruit bunches (EFBs) co-composting using different organic materials in Malaysia was done. Organic waste materials with a C/N ratio of < 30 can be applied as a nitrogen source in EFB co-composting. The outcome of this study suggested that the percentage of EFB ranged between 50% and 60%, which is considered as the ideal mixing ratio in EFB co-composting. Conclusively, EFB can be utilized in composting if appropriate feedstock in term of physical and chemical characteristics is coordinated in the co-composting process.
Lipase-catalyzed production of triethanolamine-based esterquat by esterification of oleic acid (OA) with triethanolamine (TEA) in n-hexane was performed in 2 L stirred-tank reactor. A set of experiments was designed by central composite design to process modeling and statistically evaluate the findings. Five independent process variables, including enzyme amount, reaction time, reaction temperature, substrates molar ratio of OA to TEA, and agitation speed, were studied under the given conditions designed by Design Expert software. Experimental data were examined for normality test before data processing stage and skewness and kurtosis indices were determined. The mathematical model developed was found to be adequate and statistically accurate to predict the optimum conversion of product. Response surface methodology with central composite design gave the best performance in this study, and the methodology as a whole has been proven to be adequate for the design and optimization of the enzymatic process.
Anthocyanins not just have various benefits in food industry but also have been used as natural colourants in cosmetic, coating products and as potential natural photosensitizers in solar cell. Thus, the main purpose of this study was to obtain information on the maximum yield of anthocyanin that can be recovered from Melastoma malabathricum fruit. Factors such as extraction temperature, extraction time, and solid to liquid ratio were identified to be significantly affecting anthocyanin extraction efficiency. By using three-level three-factor Box-Behnken design, the optimized conditions for anthocyanin extraction by acidified methanol (R (2) = 0.972) were temperature of 60°C, time of 86.82 min, and 0.5 : 35 (g/mL) solid to liquid ratio while the optimum extraction conditions by acidified ethanol (R (2) = 0.954) were temperature of 60°C, time of 120 min, and 0.5 : 23.06 (g/mL) solid to liquid ratio. The crude anthocyanin extract was further purified by using Amberlite XAD-7 and Sephadex LH-20 column chromatography. Identification of anthocyanins revealed the presence of cyanidin dihexoside, cyanidin hexoside, and delphinidin hexoside as the main anthocyanins in M. malabathricum fruit.
A modeling technique based on absorbed microwave energy was proposed to model microwave-assisted extraction (MAE) of antioxidant compounds from cocoa (Theobroma cacao L.) leaves. By adapting suitable extraction model at the basis of microwave energy absorbed during extraction, the model can be developed to predict extraction profile of MAE at various microwave irradiation power (100-600 W) and solvent loading (100-300 ml). Verification with experimental data confirmed that the prediction was accurate in capturing the extraction profile of MAE (R-square value greater than 0.87). Besides, the predicted yields from the model showed good agreement with the experimental results with less than 10% deviation observed. Furthermore, suitable extraction times to ensure high extraction yield at various MAE conditions can be estimated based on absorbed microwave energy. The estimation is feasible as more than 85% of active compounds can be extracted when compared with the conventional extraction technique.