Ultrarelativistic heavy ion collisions recreate in the laboratory the thermodynamical conditions prevailing in the early universe up to 10^{-6} sec, thereby allowing the study of the quark-gluon plasma (QGP), a state of quantum chromodynamics (QCD) matter with deconfined partons. The top quark, the heaviest elementary particle known, is accessible in nucleus-nucleus collisions at the CERN LHC, and constitutes a novel probe of the QGP. Here, we report the first evidence for the production of top quarks in nucleus-nucleus collisions, using lead-lead collision data at a nucleon-nucleon center-of-mass energy of 5.02 TeV recorded by the CMS experiment. Two methods are used to measure the cross section for top quark pair production (σ_{tt[over ¯]}) via the selection of charged leptons (electrons or muons) and bottom quarks. One method relies on the leptonic information alone, and the second one exploits, in addition, the presence of bottom quarks. The measured cross sections, σ_{tt[over ¯]}=2.54_{-0.74}^{+0.84} and 2.03_{-0.64}^{+0.71} μb, respectively, are compatible with expectations from scaled proton-proton data and QCD predictions.
Dough mixing and thermal properties including the pasting profiles of various commercial wheat flour (WF)-banana pseudostem flour (BP)-hydrocolloid blends were determined using a farinograph, differential scanning calorimetry (DSC) and a rapid-visco analyser (RVA). The prepared blends were WF, WF substituted with 10% BP (10BP) and 10BP with added 0.8% w/w (flour weight basis) xanthan gum (XG) or sodium carboxymethylcellulose (CMC) (10BPX and 10BPC, respectively). The dough of 10BP and the doughs containing XG or CMC reduced stability and breakdown time compared with the WF dough. All dough containing BP demonstrated greater water absorption and mixing tolerance index values than the WF dough. The substitution of 10% BP into WF and the addition of hydrocolloids did not significantly affect the conclusion temperature (Tc) of the mixture, but did increased the onset temperature (To), peak temperature (Tp) and decreased the gelatinisation enthalpy change (ΔHg) of the blends. Samples of 10BP, 10BPX and 10BPC significantly decreased (p
Mixed culture anaerobic fermentation generates a wide range of products from simple sugars, and is potentially an effective process for producing renewable commodity chemicals. However it is difficult to predict product spectrum, and to control the process. One of the key control handles is pH, but the response is commonly dependent on culture history. In this work, we assess the impact of pH regulation mode on the product spectrum. Two regulation modes were applied: in the first, pH was adjusted from 4.5 to 8.5 in progressive steps of 0.5 and in the second, covered the same pH range, but the pH was reset to 5.5 before each change. Acetate, butyrate, and ethanol were produced throughout all pH ranges, but there was a shift from butyrate at pH < 6.5 to ethanol at pH > 6.5, as well as a strong and consistent shift from hydrogen to formate as pH increased. Microbial analysis indicated that progressive pH resulted in dominance by Klebsiella, while reset pH resulted in a bias towards Clostridium spp., particularly at low pH, with higher variance in community between different pH levels. Reset pH was more responsive to changes in pH, and analysis of Gibbs free energy indicated that the reset pH experiments operated closer to thermodynamic equilibrium, particularly with respect to the formate/hydrogen balance. This may indicate that periodically resetting pH conforms better to thermodynamic expectations.
The biomass of Urochloa mutica was subjected to thermal degradation analyses to understand its pyrolytic behavior for bioenergy production. Thermal degradation experiments were performed at three different heating rates, 10, 30 and 50°Cmin-1 using simultaneous thermogravimetric-differential scanning calorimetric analyzer, under an inert environment. The kinetic analyses were performed using isoconversional models of Kissenger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The high heating value was calculated as 15.04MJmol-1. The activation energy (E) values were shown to be ranging from 103 through 233 kJmol-1. Pre-exponential factors (A) indicated the reaction to follow first order kinetics. Gibbs free energy (ΔG) was measured to be ranging from 169 to 173kJmol-1 and 168 to 172kJmol-1, calculated by KAS and FWO methods, respectively. We have shown that Para grass biomass has considerable bioenergy potential comparable to established bioenergy crops such as switchgrass and miscanthus.
Thermodynamic chemical equilibrium analysis using, total Gibbs energy minimization method, was carried out for methane oxidation to higher hydrocarbons. For a large methane conversion and a high selectivity to higher hydrocarbons, the system temperature and oxygen concentration played a vital role, whereas, the system pressure only slightly influenced the two variables. Numerical results showed that the conversion of methane increased with the concentration of oxygen and reaction temperature, but it decreased with pressure. Nevertheless, the presence of oxygen suppressed the formation of higher hydrocarbons which mostly consisted of aromatics, but enhanced the formation of hydrogen. As the system pressure increased, the aromatics, olefins and hydrogen yields diminished, but the paraffin yield improved. Carbon monoxide seemed to be the major oxygen-containing equilibrium product from methane oxidation, whilst almost no H2O, CH3OH and HCOH were detected although traces amount of carbon dioxide were formed at relatively lower temperature and higher pressure. The total Gibbs energy minimization method is useful to theoretically analyze the feasibility of methane conversion to higher hydrocarbons and syngas at the selected temperature and pressure.
Industrial heat pumps are heat-recovery systems that allow the temperature of waste-heat stream to be increased to a higher, more efficient temperature. Consequently, heat pumps can improve energy efficiency in industrial processes as well as energy savings when conventional passive-heat recovery is not possible. In this paper, possible ways of saving energy in the chemical industry are considered, the objective is to reduce the primary energy (such as coal) consumption of power plant. Particularly the thermodynamic analyses of integrating backpressure turbine of a power plant with distillation units have been considered. Some practical examples such as conventional distillation unit and heat pump are used as a means of reducing primary energy consumption with tangible indications of energy savings. The heat pump distillation is operated via electrical power from the power plant. The exergy efficiency of the primary fuel is calculated for different operating range of the heat pump distillation. This is then compared with a conventional distillation unit that depends on saturated steam from a power plant as the source of energy. The results obtained show that heat pump distillation is an economic way to save energy if the temperature difference between the overhead and the bottom is small. Based on the result, the energy saved by the application of a heat pump distillation is improved compared to conventional distillation unit.
While the economy is rapidly expanding in most emerging countries, issues coupled with a higher population has created foreseeable tension among food, water, and energy. It is crucial for more sustainable valorization of resources, for instance, nanocellulose, to address the core challenges in environmental sustainability. As the complexity of the system evolved, the timescale of project development has increased exponentially. However, research on the design and operation of integrated nanomaterials, along with energy supply, monitoring, and control infrastructure, has seriously lagged. The development cost of new materials can be significantly reduced by utilizing molecular simulation technology in the design of nanostructured materials. To realize its potential, nanocellulose, an amphiphilic biopolymer with the presence of rich -OH and -CH structural groups, was investigated via molecular dynamics simulation to reveal its full potential as Pickering emulsion stabilizer at the molecular level. This work has successfully quantified the Pickering stabilization mechanism profiles by nanocellulose, and the phenomenon could be visualized in three stages, namely the initial homogenous phase, rapid formation of micelles and coalescence, and lastly the thermodynamic equilibrium of the system. It was also observed that the high bead order was always coupled with a high volume of phase separation activities, through a coarse-grained model within 20,000 time steps. The outcome of this work would be helpful to provide an important perspective for the future design and development of nanocellulose-based emulsion products, which cater for food, cosmeceutical, and pharmaceutical industries.
In this paper, the adsorptive performance of synthesized thiourea (TU) modified poly(acrylonitrile-co-acrylic acid) (TU-P(AN-co-AA)) polymeric adsorbent for capturing p-nitrophenol (PNP) from aqueous solution was investigated. TU-P(AN-co-AA) was synthesized via the redox polymerization method with acrylonitrile (AN) and acrylic acid (AA) as the monomers, then modified chemically with thiourea (TU). Characterization analysis with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), elemental microanalysis for CHNS, zeta potential measurement, Brunauer-Emmett-Teller (BET) surface analysis and thermal analyses were carried out to determine the morphology and physico-chemical properties of the synthesized polymer. The characterization results indicated successful surface modification of polymer with TU. The performance of TU-P(AN-co-AA) for the removal of PNP was investigated under various experimental parameters (adsorbent dosage, initial adsorbate concentration, contact time and temperature). The results demonstrated that the Freundlich isotherm model and pseudo-second-order kinetic model best described the equilibrium and kinetic data, respectively. Thermodynamic studies showed that the uptake of PNP by TU-P(AN-co-AA) was spontaneous and exothermic in nature. The results of the regeneration studies suggested that the TU-P(AN-co-AA) polymer is a reusable adsorbent with great potential for removing PNP from wastewater.
This study examines the effects of varying the concentrations of sorbitol (S) and glycerol (G) on the physical, morphological, thermal, and mechanical properties of Dioscorea hispida, starch-based films. In this context, the films of Dioscorea hispida starch were developed using solution casting technique with glycerol (G), sorbitol (S), and a mixture of sorbitol-glycerol (SG) as plasticizers at the ratios of 0, 30, 45, and 60 wt%. The films' moisture contents were increased when increasing the plasticizer contents. The tensile strengths were decreased, but elongations at break were increased; 7.38%-11.54% for G-plasticized films, 10.17%-15.76% for S-plasticized films, and 14.41%- 16.10% for SG-plasticized films with increasing plasticizer concentrations of the film samples. Varying plasticizer concentrations exhibited a minor effect on the S-plasticized film's thermal properties. Significant decrement in the glass transition temperatures of Dioscorea hispida starch films was observed when the plasticizer contents were raised from 30% to 60%. Significantly, the present work has shown that plasticized Dioscorea hispida starch can be considered a promising biopolymer for the applications of biodegradable films.
A wavy shape was used to enhance the thermal heat transfer in a shell-tube latent heat thermal energy storage (LHTES) unit. The thermal storage unit was filled with CuO-coconut oil nano-enhanced phase change material (NePCM). The enthalpy-porosity approach was employed to model the phase change heat transfer in the presence of natural convection effects in the molten NePCM. The finite element method was applied to integrate the governing equations for fluid motion and phase change heat transfer. The impact of wave amplitude and wave number of the heated tube, as well as the volume concertation of nanoparticles on the full-charging time of the LHTES unit, was addressed. The Taguchi optimization method was used to find an optimum design of the LHTES unit. The results showed that an increase in the volume fraction of nanoparticles reduces the charging time. Moreover, the waviness of the tube resists the natural convection flow circulation in the phase change domain and could increase the charging time.
Increased scientific interest has led to the rise in biotechnological uses of halophilic and halotolerant microbes for hypersaline wastewater bioremediation. Hence, this study performed molecular docking, molecular dynamic (MD) simulations, and validation by Molecular Mechanic Poisson-Boltzmann Surface Area (MM-PBSA) calculations on the DehH2 from Bacillus thuringiensis H2. We aimed to identify the interactions of DehH2 with substrates haloacids, haloacetates, and chlorpyrifos under extreme salinity (35% NaCl). MD simulations revealed that DehH2 preferentially degraded haloacids and haloacetates (-6.3 to -4.7 kcal/mol) by forming three or four hydrogen bonds to the catalytic triad, Asp125, Arg201, and Lys202. Conversely, chlorpyrifos was the least preferred substrate in both MD simulations and MM-PBSA calculations. MD simulation results ranked the DehH2-L-2CP complex (RMSD □0.125-0.23 nm) as the most stable while the least was the DehH2-chlorpyrifos complex (RMSD 0.32 nm; RMSF 0.0 - 0.29). The order of stability was as follows: DehH2-L-2CP > DehH2-MCA > DehH2-D-2CP > DehH2-3CP > DehH2-2,2-DCP > DehH2-2,3-DCP > DehH2-TCA > DehH2-chlorpyrifos. The MM-PBSA calculations further affirmed the DehH2-L-2CP complex's highest stability with the lowest binding energy of -45.14 kcal/mol, followed closely by DehH2-MCA (-41.21 kcal/mol), DehH2-D-2CP (-31.59 kcal/mol), DehH2-3CP (-30.75 kcal/mol), DehH2-2,2- DCP (-29.72 kcal/mol), DehH2-2,3-DCP (-22.20 kcal/mol) and DehH2-TCA (-18.46 kcal/mol). The positive binding energy of the DehH2-chlorpyrifos complex (+180.57 kcal/mol) proved the enzyme's non-preference for the substrate. The results ultimately illustrated the unique specificity of the DehH2 to degrade the above-said pollutants under a hypersaline condition.Communicated by Ramaswamy H. Sarma.
Transition metal chalcogenides (TMCs) have gained worldwide interest owing to their outstanding renewable energy conversion capability. However, the poor mechanical flexibility of most existing TMCs limits their practical commercial applications. Herein, triggered by the recent and imperative synthesis of highly ductile α-Ag2S, an effective approach based on evolutionary algorithm and ab initio total-energy calculations for determining stable, ductile phases of bulk and two-dimensional Ag x Se1-x and Ag x Te1-x compounds was implemented. The calculations correctly reproduced the global minimum bulk stoichiometric P212121-Ag8Se4 and P21/c-Ag8Te4 structures. Recently reported metastable AgTe3 was also revealed but it lacks dynamical stability. Further single-layered screening unveiled two new monolayer P4/nmm-Ag4Se2 and C2-Ag8Te4 phases. Orthorhombic Ag8Se4 crystalline has a narrow, direct band gap of 0.26 eV that increases to 2.68 eV when transforms to tetragonal Ag4Se2 monolayer. Interestingly, metallic P21/c-Ag8Te4 changes to semiconductor when thinned down to monolayer, exhibiting a band gap of 1.60 eV. Present findings confirm their strong stability from mechanical and thermodynamic aspects, with reasonable Vickers hardness, bone-like Young's modulus (E) and high machinability observed in bulk phases. Detailed analysis of the dielectric functions ε(ω), absorption coefficient α(ω), power conversion efficiency (PCE) and refractive index n(ω) of monolayers are reported for the first time. Fine theoretical PCE (SLME method ∼11-28%), relatively high n(0) (1.59-1.93), and sizable α(ω) (104-105 cm-1) that spans the infrared to visible regions indicate their prospects in optoelectronics and photoluminescence applications. Effective strategies to improve the temperature dependent power factor (PF) and figure of merit (ZT) are illustrated, including optimizing the carrier concentration. With decreasing thickness, ZT of p-doped Ag-Se was found to rise from approximately 0.15-0.90 at 300 K, leading to a record high theoretical conversion efficiency of ∼12.0%. The results presented foreshadow their potential application in a hybrid device that combines the photovoltaic and thermoelectric technologies.
Over-the-air dissemination of code updates in wireless sensor networks have been researchers' point of interest in the last few years, and, more importantly, security challenges toward the remote propagation of code updating have occupied the majority of efforts in this context. Many security models have been proposed to establish a balance between the energy consumption and security strength, having their concentration on the constrained nature of wireless sensor network (WSN) nodes. For authentication purposes, most of them have used a Merkle hash tree to avoid using multiple public cryptography operations. These models mostly have assumed an environment in which security has to be at a standard level. Therefore, they have not investigated the tree structure for mission-critical situations in which security has to be at the maximum possible level (e.g., military applications, healthcare). Considering this, we investigate existing security models used in over-the-air dissemination of code updates for possible vulnerabilities, and then, we provide a set of countermeasures, correspondingly named Security Model Requirements. Based on the investigation, we concentrate on Seluge, one of the existing over-the-air programming schemes, and we propose an improved version of it, named Seluge++, which complies with the Security Model Requirements and replaces the use of the inefficient Merkle tree with a novel method. Analytical and simulation results show the improvements in Seluge++ compared to Seluge.
The steady boundary layer flow of a viscous and incompressible fluid over a moving vertical flat plate in an external moving fluid with viscous dissipation is theoretically investigated. Using appropriate similarity variables, the governing system of partial differential equations is transformed into a system of ordinary (similarity) differential equations, which is then solved numerically using a Maple software. Results for the skin friction or shear stress coefficient, local Nusselt number, velocity and temperature profiles are presented for different values of the governing parameters. It is found that the set of the similarity equations has unique solutions, dual solutions or no solutions, depending on the values of the mixed convection parameter, the velocity ratio parameter and the Eckert number. The Eckert number significantly affects the surface shear stress as well as the heat transfer rate at the surface.
In this study, the kinetic parameters of rice husk ash (RHA)/CaO/CeO(2) sorbent for SO(2) and NO sorptions were investigated in a laboratory-scale stainless steel fixed-bed reactor. Data experiments were obtained from our previous results and additional independent experiments were carried out at different conditions. The initial sorption rate constant (k(0)) and deactivation rate constant (k(d)) for SO(2)/NO sorptions were obtained from the nonlinear regression analysis of the experimental breakthrough data using deactivation kinetic model. Both the initial sorption rate constants and deactivation rate constants increased with increasing temperature, except at operating temperature of 170 °C. The activation energy and frequency factor for the SO(2) sorption were found to be 18.0 kJ/mol and 7.37 × 10(5)cm(3)/(g min), respectively. Whereas the activation energy and frequency factor for the NO sorption, were estimated to be 5.64 kJ/mol and 2.19 × 10(4)cm(3)/(g min), respectively. The deactivation kinetic model was found to give a very good agreement with the experimental data of the SO(2)/NO sorptions.
Binding mechanisms of two selected pesticides, propazine (PRO) and quinoxyfen (QUI) with bovine serum albumin (BSA) was examined using fluorescence, absorption and molecular docking methods. Intrinsic fluorescence of BSA was quenched in the presence of both PRO and QUI. The quenching was ascertained to be conversely linked to temperature, which suggested the contribution of static quenching process in the PRO-BSA and QUI-BSA complex formations. This results were validated by the enhancement in absorption spectrum of BSA upon binding with PRO and QUI. Binding constant values (Kf = 9.55-0.60 × 10-3 M-1 for PRO-BSA system; Kf = 7.08-5.01 × 102 M-1 for QUI-BSA system) and number of binding site (n) values for the PRO-BSA and QUI-BSA systems at different temperatures affirmed a weak binding strength with a set of equivalent binding sites on BSA. Thermodynamic data obtained for both the PRO-BSA and QUI-BSA interactions predicted that the association process was spontaneous and non-covalent contacts such as hydrophobic interactions, van der Waals forces and hydrogen bonds participated in the binding reactions. This result was further supported by the molecular docking assessments. Three-dimensional spectral results revealed the microenvironmental alterations near tryptophan (Trp) and tyrosine (Tyr) residues in BSA by the addition of PRO and QUI. The docking analysis demonstrated the binding pattern for the PRO-BSA and QUI-BSA systems and disclosed the preferred binding site of both PRO and QUI as site I (subdomain IIA) of BSA.
The synthesis and spectral characterization of the 5-(2,6-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione;3 was reported. The solid state molecular structure of 3 was studied using X-ray crystallography. The relative stabilities of the seven possible isomers of 3 were calculated by DFT/B3LYP method using 6-311 G(d,p) basis set. The calculated total energies and thermodynamic parameters were used to predict the relative stabilities of these isomers. The effect of solvent polarity on the relative stability of these isomers was studied at the same level of theory using PCM. It was found that the keto form, (T0), is the most stable isomer both in the gaseous state and solution. In solution, the calculated total energies of all isomers are decreased indicating that all isomers are stabilized by the solvent effect. The vibrational spectra of the most stable isomer, 3(T0) are calculated using the same level of theory and the results are compared with the experimentally measured FTIR spectra. Good correlation was obtained between the experimental and calculated vibrational frequencies (R(2)=0.9992). The electronic spectra of 3(T0) in gas phase as well as in solutions were calculated using the TD-DFT method. All the predicted electronic transitions showed very little spectral shifts and increase in the intensity of absorption due to solvent effect. Also the (1)H- and (13)C-NMR chemical shifts of the stable isomer were calculated and the results were correlated with the experimental data. Good correlations between the experimental and calculated chemical shifts were obtained.
The present study investigated the biosorption capacity of live and dead cells of a novel Bacillus strain for chromium. The optimum biosorption condition was evaluated in various analytical parameters, including initial concentration of chromium, pH, and contact time. The Langmuir isotherm model showed an enhanced fit to the equilibrium data. Live and dead biomasses followed the monolayer biosorption of the active surface sites. The maximum biosorption capacity was 20.35 mg/g at 25 °C, with pH 3 and contact time of 50 min. Strain 139SI was an excellent host to the hexavalent chromium. The biosorption kinetics of chromium in the dead and live cells of Bacillus salmalaya (B. salmalaya) 139SI followed the pseudo second-order mechanism. Scanning electron microscopy and fourier transform infrared indicated significant influence of the dead cells on the biosorption of chromium based on cell morphological changes. Approximately 92% and 70% desorption efficiencies were achieved using dead and live cells, respectively. These findings demonstrated the high sorption capacity of dead biomasses of B. salmalaya 139SI in the biosorption process. Thermodynamic evaluation (ΔG⁰, ΔH⁰, and ΔS⁰) indicated that the mechanism of Cr(VI) adsorption is endothermic; that is, chemisorption. Results indicated that chromium accumulation occurred in the cell wall of B. salmalaya 139SI rather than intracellular accumulation.
Lansium domesticum peel (LDP), a waste material generated from the fruit consumption, was evaluated as a biosorbent for nickel removal from aqueous media. The effects of dosage, contact time, initial pH, initial concentration and temperature on the biosorption process were investigated in batch experiments. Equilibrium data were fitted by the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models using nonlinear regression method with the best-fit model evaluated based on coefficient of determination (R(2)) and Chi-square (χ(2)). The best-fit isotherm was found to be the Langmuir model exhibiting R(2) very close to unity (0.997-0.999), smallest χ(2) (0.0138-0.0562) and largest biosorption capacity (10.1mg/g) at 30°C. Kinetic studies showed that the initial nickel removal was rapid with the equilibrium state established within 30min. Pseudo-second-order model was the best-fit kinetic model indicating the chemisorption nature of the biosorption process. Further data analysis by the intraparticle diffusion model revealed the involvement of several rate-controlling steps such as boundary layer and intraparticle diffusion. Thermodynamically, the process was exothermic, spontaneous and feasible. Regeneration studies indicated that LDP biosorbent could be regenerated using hydrochloric acid solution with up to 85% efficiency. The present investigation proved that LDP having no economic value can be used as an alternative eco-friendly biosorbent for remediation of nickel contaminated water.
This study explores the plausible molecular interaction between a potent hepatitis C virus inhibitor, PSI-6206 (PSI), and human serum albumin (HSA), a primary transporter in blood plasma. Results obtained from both computational viz. molecular docking and molecular dynamics (MD) simulation and wet lab techniques such as UV absorption, fluorescence, circular dichroism (CD), and atomic force microscopy (AFM) complemented each other. While docking results identified PSI binding to subdomain IIA (Site I) of HSA by forming six hydrogen bonds, MD simulations signified the complex stability throughout the 50,000 ps. A consistent cutback in the Stern-Volmer quenching constant (Ksv) along with rising temperatures supported the static mode of fluorescence quenching in response to PSI addition and implied the development of the PSI-HSA complex. This discovery was backed by the alteration of the HSA UV absorption spectrum, a larger value (>1010 M-1.s-1) of the bimolecular quenching rate constant (kq) and the AFM-guided swelling of the HSA molecule, in the presence of PSI. Moreover, the fluorescence titration results revealed a modest binding affinity (4.27-6.25×103 M-1) in the PSI-HSA system, involving hydrogen bonds, van der Waals and hydrophobic interactions, as inferred from ΔS = + 22.77 J mol-1 K-1 and ΔH = - 11.02 KJ mol-1values. CD and 3D fluorescence spectra reminded significant adjustment in the 2° and 3° structures and modification in the Tyr/Trp microenvironment of the protein in the PSI-bound state. The results obtained from drug competing experiments also advocated the binding location of PSI in HSA as Site I.