Non-Fourier heat conduction model with dual phase lag wave-diffusion model was analyzed by using well-conditioned asymptotic wave evaluation (WCAWE) and finite element method (FEM). The non-Fourier heat conduction has been investigated where the maximum likelihood (ML) and Tikhonov regularization technique were used successfully to predict the accurate and stable temperature responses without the loss of initial nonlinear/high frequency response. To reduce the increased computational time by Tikhonov WCAWE using ML (TWCAWE-ML), another well-conditioned scheme, called mass effect (ME) T-WCAWE, is introduced. TWCAWE with ME (TWCAWE-ME) showed more stable and accurate temperature spectrum in comparison to asymptotic wave evaluation (AWE) and also partial Pade AWE without sacrificing the computational time. However, the TWCAWE-ML remains as the most stable and hence accurate model to analyze the fast transient thermal analysis of non-Fourier heat conduction model.
In this study, a sustainable NH2-MIL-101(Al) is synthesized and subjected to characterization for cryogenic CO2 adsorption, isotherms, and thermodynamic study. The morphology revealed a highly porous surface. The XRD showed that NH2-MIL-101(Al) was crystalline. The NH2-MIL-101(Al) decomposes at a temperature (>500 °C) indicating excellent thermal stability. The BET investigation revealed the specific surface area of 2530 m2/g and the pore volume of 1.32 cm3/g. The CO2 adsorption capacity was found to be 9.55 wt% to 2.31 wt% within the investigated temperature range. The isotherms revealed the availability of adsorption sites with favorable adsorption at lower temperatures indicating the thermodynamically controlled process. The thermodynamics showed that the process is non-spontaneous, endothermic, with fewer disorders, chemisorption. Finally, the breakthrough time of NH2-MIL-101(Al) is 31.25% more than spherical glass beads. The CO2 captured by the particles was 2.29 kg m-3. The CO2 capture using glass packing was 121% less than NH2-MIL-101(Al) under similar conditions of temperature and pressure.
Limited information is available about the thermodynamic evaluation for biomass gasification process using updraft gasifier. Therefore, to minimize errors, the gasification of dry refinery sludge (DRS) is carried out in adiabatic system at atmospheric pressure under ambient air conditions. The objectives of this paper are to investigate the physical and chemical energy and exergy of product gas at different equivalent ratios (ER). It will also be used to determine whether the cold gas, exergy, and energy efficiencies of gases may be maximized by using secondary air injected to gasification zone under various ratios (0, 0.5, 1, and 1.5) at optimum ER of 0.195. From the results obtained, it is indicated that the chemical energy and exergy of producer gas are magnified by 5 and 10 times higher than their corresponding physical values, respectively. The cold gas, energy, and exergy efficiencies of DRS gasification are in the ranges of 22.9-55.5%, 43.7-72.4%, and 42.5-50.4%, respectively. Initially, all 3 efficiencies increase until they reach a maximum at the optimum ER of 0.195; thereafter, they decline with further increase in ER values. The injection of secondary air to gasification zone is also found to increase the cold gas, energy, and exergy efficiencies. A ratio of secondary air to primary air of 0.5 is found to be the optimum ratio for all 3 efficiencies to reach the maximum values.
Numerical investigation of the heat transfer and friction factor characteristics of a circular fitted with V-cut twisted tape (VCT) insert with twist ratio (y = 2.93) and different cut depths (w = 0.5, 1, and 1.5 cm) were studied for laminar flow using CFD package (FLUENT-6.3.26). The data obtained from plain tube were verified with the literature correlation to ensure the validation of simulation results. Classical twisted tape (CTT) with different twist ratios (y = 2.93, 3.91, 4.89) were also studied for comparison. The results show that the enhancement of heat transfer rate induced by the classical and V-cut twisted tape inserts increases with the Reynolds number and decreases with twist ratio. The results also revealed that the V-cut twisted tape with twist ratio y = 2.93 and cut depth w = 0.5 cm offered higher heat transfer rate with significant increases in friction factor than other tapes. In addition the results of V-cut twist tape compared with experimental and simulated data of right-left helical tape inserts (RLT), it is found that the V-cut twist tape offered better thermal contact between the surface and the fluid which ultimately leads to a high heat transfer coefficient. Consequently, 107% of maximum heat transfer was obtained by using this configuration.
The fundamental mechanism of biochemistry lies on the reaction kinetics, which is determined by the reaction pathways. Interestingly, the reaction pathway is a challenging concept for undergraduate students. Experimentally, it is difficult to observe, and theoretically, it requires some degree of physics knowledge, namely statistical and quantum mechanics. However, students can utilize computational methods to study the reaction kinetics without paying too much attention but not wholly neglecting the comprehension of physics. We hereby provided an approach to study the reaction kinetics based on density-functional calculations. We particularized the study of the isomerization case involving five molecules at three different temperatures and emphasized the importance of the transition state in the study of reaction kinetics. The results we presented were in good agreement with the experiments and provided useful insights to assist students in the application of their knowledge into their research.
We study the reduced dynamics of a pair of nondegenerate oscillators coupled collectively to a thermal bath. The model is related to the trilinear boson model where the idler mode is promoted to a field. Due to nonlinear coupling, the Markovian master equation for the pair of oscillators admits non-Gaussian equilibrium states, where the modes distribute according to the Bose-Einstein statistics. These states are metastable before the nonlinear coupling is taken over by linear coupling between the individual oscillators and the field. The Gibbs state for the individual modes lies in the subspace with infinite occupation quantum number. We present the time evolution of a few states to illustrate the behaviors of the system.
The properties of fibre-reinforced composites are dependent not only on the strength of the reinforcementfibre but also on the distribution of fibre strength and the composition of the chemicals or additivesaddition within the composites. In this study, the tensile properties of abaca fibre reinforced high impactpolystyrene (HIPS) composites, which had been produced with the parameters of fibre loading (30,40,50wt.%), coupling agent maleic anhydride (MAH) (1,2,3 wt%) and impact modifier (4,5,6 wt.%) weremeasured. The optimum amount of MAH is 3% and the impact modifier is 6% and these give the besttensile properties. Meanwhile, Differential Scanning Calorimetry (DSC) was used to study the thermalbehaviour within the optimum conditions of the composites. In this research, glass transitions temperature(Tg) of neat HIPS occurred below the Tg of the optimum condition of composites as the temperature ofan amorphous state. The endothermic peak of the composites was in the range of 430-4350C, includingneat HIPS. It was observed that enthalpy of the abaca fibre reinforced HIPS composites yielded belowthe neat HIPS of 748.79 J/g.
Molecular dynamics reaction simulation showed that the rate constant is not constant over the concentration profile of reactants and products over a fixed temperature regime, and this variation is expressed in terms of the defined reactivity coefficients. The ratio of these coefficients for the forward and backward reactions were found to equal that of the activity coefficient ratio for the product and reactant species. A theory was developed to explain kinetics in general based on these observations. Several other theorems had first to be developed, most striking of all was the inference that the excess Helmholtz free energy was the thermodynamical function which had a direct relation to these activity factors than the Gibbs free energy. The theory is applied to a class of ionic reactions which could not be rationalized using the standard Bjørn-Bjerrum theory of ionic reactions.
The aim of this study was to understand the influence of catalyst in thermal degradation behavior of rice husk (RH) in catalytic fast pyrolysis (CFP) process. An iso-conversional Kissinger kinetic model was introduced into this study to understand the activation energy (EA), pre-exponential value (A), Enthalpy (ΔH), Entropy (ΔS) and Gibb's energy (ΔG) of non-catalytic fast pyrolysis (NCFP) and CFP of RH. The study revealed that the addition of natural zeolite catalyst enhanced the rate of devolatilization and decomposition of RH associated with lowest EA value (153.10 kJ/mol) compared to other NCFP and CFP using nickel catalyst. Lastly, an uncertainty estimation was applied on the best fit non-linear regression model (MNLR) to identify the explanatory variables. The finding showed that it had the highest probability to obtain 73.8-74.0% mass loss in CFP of rice husk using natural zeolite catalyst.
This study investigates the thermal decomposition, thermodynamic and kinetic behavior of rice-husk (R), sewage sludge (S) and their blends during co-pyrolysis using thermogravimetric analysis at a constant heating rate of 20 °C/min. Coats-Redfern integral method is applied to mass loss data by employing seventeen models of five major reaction mechanisms to calculate the kinetics and thermodynamic parameters. Two temperature regions: I (200-400 °C) and II (400-600 °C) are identified and best fitted with different models. Among all models, diffusion models show high activation energy with higher R2(0.99) of rice husk (66.27-82.77 kJ/mol), sewage sludge (52.01-68.01 kJ/mol) and subsequent blends (45.10-65.81 kJ/mol) for region I and for rice husk (7.31-25.84 kJ/mol), sewage sludge (1.85-16.23 kJ/mol) and blends (4.95-16.32 kJ/mol) for region II, respectively. Thermodynamic parameters are calculated using kinetics data to assess the co-pyrolysis process enthalpy, Gibbs-free energy, and change in entropy. Artificial neural network (ANN) models are developed and employed on co-pyrolysis thermal decomposition data to study the reaction mechanism by calculating Mean Absolute Error (MAE), Root Mean Square Error (RMSE) and coefficient of determination (R2). The co-pyrolysis results from a thermal behavior and kinetics perspective are promising and the process is viable to recover organic materials more efficiently.
The performance of aptamers as versatile tools in numerous analytical applications is critically dependent on their high target binding specificity and selectivity. However, only the technical or methodological aspects of measuring aptamer-target binding affinities are focused, ignoring the equally important mathematical components that play pivotal roles in affinity measurements. In this study, we aim to provide a comprehensive review regarding the utilization of different mathematical models and equations, along with a detailed description of the computational steps involved in mathematically deriving the binding affinity of aptamers against their specific target molecules. Mathematical models ranging from one-site binding to multiple aptameric binding site-based models are explained in detail. Models applied in several different approaches of affinity measurements such as thermodynamics and kinetic analysis, including cooperativity and competitive-assay based mathematical models have been elaborately discussed. Mathematical models incorporating factors that could potentially affect affinity measurements are also further scrutinized.
We propose a thermodynamic model to the study the antiferroelectric (AFE) phase transitions in antiferroelectric-ferroelectric (AFE-FE) superlattices in which the coupling at the interface between two layers is mediated by local polarizations. Phase diagram of the AFE layer in term of the degree of interfacial effect λ and temperature T involving ferrielectric (FI) and ferroelectric (FE) phases is investigated. These two phases are stabilized by the interfacial effect and internal electric field. AFE thickness L AFE versus T phase diagram is also constructed. Intermediate regions of two-phase coexistence (IM) emerge in the λ-T and L AFE-T phase diagrams, if certain interface properties λ and layer thickness L AFE criteria are met. These IM regions are metastable states, which exist as a transition state between two phases. A tricritical point locates at the boundaries across the FI, IM and FE phases is found in the L AFE-T phase diagram. Competition among the internal electric field due to the electrostatic coupling, the FE ordering arises from the interfacial effect and the antiferroelectric ordering within the AFE layer giving rises to the rich AFE phase diagram.
Fabrication of functional DNA nanostructures operating at a cellular level has been accomplished through molecular programming techniques such as DNA origami and single-stranded tiles (SST). During implementation, restrictive and constraint dependent designs are enforced to ensure conformity is attainable. We propose a concept of DNA polyominoes that promotes flexibility in molecular programming. The fabrication of complex structures is achieved through self-assembly of distinct heterogeneous shapes (i.e., self-organised optimisation among competing DNA basic shapes) with total flexibility during the design and assembly phases. In this study, the plausibility of the approach is validated using the formation of multiple 3×4 DNA network fabricated from five basic DNA shapes with distinct configurations (monomino, tromino and tetrominoes). Computational tools to aid the design of compatible DNA shapes and the structure assembly assessment are presented. The formations of the desired structures were validated using Atomic Force Microscopy (AFM) imagery. Five 3×4 DNA networks were successfully constructed using combinatorics of these five distinct DNA heterogeneous shapes. Our findings revealed that the construction of DNA supra-structures could be achieved using a more natural-like orchestration as compared to the rigid and restrictive conventional approaches adopted previously.
Metal nanoclusters have been considered as a new class of chemical sensors due to their unique electronic structures and the particular physicochemical properties. The interaction of N2 molecule with neutral and ionic magnesium nanoclusters Mg17q(q=0,±1), as well as neutral magnesium nanoclusters with the centrality of beryllium and calcium Mg16M (M=Be, Mg, and Ca) have been investigated using CAM-B3LYP/6-311+G(d) level of theory in the gas phase. The electronic properties of magnesium nanoclusters were significantly affected by the adsorption of N2 molecule. The NBO analysis revealed a charge transfer from the adsorbed N2 molecule to the nanocluster. Based on the adsorption energies and enthalpies, a thermodynamically favorable chemisorption process was predicted for the Mg16Ca-N2 complex. The negative value of the Gibbs free energy of Mg16Ca-N2 confirmed the spontaneous adsorption process. The estimated recovery time for Mg16Ca-N2 complex for 8-MR (0.089 s) and 4-MRs (0.075 s) illustrated a possible desorption process for N2 molecule from the surface of Mg16Ca. Our finding also revealed the Mg16Ca has the ability to use as a sensor for detection and absorption of N2 molecule.
Pyrolysis of agricultural biomass is a promising technique for producing renewable energy and effectively managing solid waste. In this study, groundnut shell (GNS) was processed at 500 °C in an inert gas atmosphere with a gas flow rate and a heating rate of 10 mL/min and 10 °C/min, respectively, in a custom-designed fluidized bed pyrolytic-reactor. Under optimal operating conditions, the GNS-derived pyrolytic-oil yield was 62.8 wt.%, with the corresponding biochar (19.5 wt.%) and biogas yields (17.7 wt.%). The GC-MS analysis of the GNS-based bio-oil confirmed the presence of (trifluoromethyl)pyridin-2-amine (18.814%), 2-Fluoroformyl-3,3,4,4-tetrafluoro-1,2-oxazetidine (16.23%), 5,7-dimethyl-1H-Indazole (11.613%), N-methyl-N-nitropropan-2-amine (6.5%) and butyl piperidino sulfone (5.668%) as major components, which are used as building blocks in the biofuel, pharmaceutical, and food industries. Furthermore, a 2 × 5 × 1 artificial neural network (ANN) architecture was developed to predict the decomposition behavior of GNS at heating rates of 5, 10, and 20 °C/min, while the thermodynamic and kinetic parameters were estimated using a non-isothermal model-free method. The Popescu method predicted activation energy (Ea) of GNS biomass ranging from 111 kJ/mol to 260 kJ/mol, with changes in enthalpy (ΔH), Gibbs-free energy (ΔG), and entropy (ΔS) ranging from 106 to 254 kJ/mol, 162-241 kJ/mol, and -0.0937 to 0.0598 kJ/mol/K, respectively. The extraction of high-quality precursors from GNS pyrolysis was demonstrated in this study, as well as the usefulness of the ANN technique for thermogravimetric analysis of biomass.
In order to characterize enzyme activity and stability corresponding to temperature effects, thermodynamic studies on commercial immobilized lipase have been carried out via enzymatic transesterification. An optimum temperature of 40 degrees C was obtained in the reaction. The decreasing reaction rates beyond the optimum temperature indicated the occurrence of reversible enzyme deactivation. Thermodynamic studies on lipase denaturation exhibited a first-order kinetics pattern, with considerable stability through time shown by the lipase as well. The activation and deactivation energies were 22.15 kJ mol(-1) and 45.18 kJ mol(-1), respectively, implying more energy was required for the irreversible denaturation of the enzyme to occur. At water content of 0.42%, the initial reaction rate and FAME yield displayed optimum values of 3.317 g/L min and 98%, respectively.
Knowledge about the thermal and storage behavior of produced protein is important for the purpose of storage, transport and shelve life during industrial application. Recombinant bromelain thermal and storage stability were measured and compared to the commercial bromelain using Differential Scanning Calorimetry (DSC). Recombinant bromelain is more stable than commercial bromelain at higher temperature but the stability was reduced after 7 days of storage at 4oC. Higher energy is needed to break the bond between amino acid chains in recombinant bromelain as shown by the enthalpy obtained, suggesting that recombinant bromelain has good protein structure and conformation compared to commercial.
In this study, we address the effect of the cis-double bond in 1,2-dioleoyl-sn-glycero-3-phosphoethanolamide-N-[methoxy(polyethylene glycol)-2000, DOPE PEG2000 (DP), on the Langmuir monolayer of C18 fatty acids-namely, stearic acid (SA), oleic acid (L1), linoleic acid (L2), and linolenic acid (L3)-with the same head group but different degrees of saturation on their hydrocarbon chains. Negative values of Gibbs free energy of mixing (ΔG mix) were obtained throughout the investigated ranges of the unsaturated C18 fatty-acid (L1, L2 and L3) mixed systems, indicating that very strong attractions occurred between molecules in the monolayers. The bend and kink effects from the cis-double bond(s) in the hydrocarbon chain affected the membrane fluidity and molecular packing in the monolayers, which resulted in a greater interaction between unsaturated C18 fatty acids and DP. The most thermodynamically stable mole composition of unsaturated C18 fatty acids to DP was observed at 50:1; this ratio is suggested to be the best mole ratio and will be subsequently used to prepare DP-C18 fatty-acid nanoliposomes. The presence of cis-double bonds in both hydrocarbon chains of DOPE in DP also created an imperfection in the membrane structure of lipid-drug delivery systems, which is expected to enhance lipid-based systems for antibody conjugation and drug encapsulation.
Multiple spectroscopic techniques, such as fluorescence, absorption, and circular dichroism along with in silico studies were used to characterize the binding of a potent inhibitor molecule, CCG1423 to the major transport protein, human serum albumin (HSA). Fluorescence and absorption spectroscopic results confirmed CCG1423-HSA complex formation. A strong binding affinity stabilized the CCG1423-HSA complex, as evident from the values of the binding constant (Ka = 1.35 × 106-5.43 × 105 M-1). The KSV values for CCG1423-HSA system were inversely correlated with temperature, suggesting the involvement of static quenching mechanism. Thermodynamic data anticipated that CCG1423-HSA complexation was mainly driven by hydrophobic and van der Waals forces as well as hydrogen bonds. In silico analysis also supported these results. Three-dimensional fluorescence and circular dichroism spectral analysis suggested microenvironmental perturbations around protein fluorophores and structural (secondary and tertiary) changes in the protein upon CCG1423 binding. CCG1423 binding to HSA also showed some protection against thermal denaturation. Site-specific marker-induced displacement results revealed CCG1423 binding to Sudlow's site I of HSA, which was also confirmed by the computational results. A few common ions were also found to interfere with the CCG1423-HSA interaction.
Complex dielectric permittivity measurements of propylene glycol (PG) in ethanol at various mole fractions were measured by using open-ended coaxial probe technique at different temperatures in the frequency range 0.02