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.
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.
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.
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.
Thermodynamic and kinetic parameters of catalytic pyrolysis of rice hull (RH) pyrolysis using two different types of renewable catalysts namely natural limestone (LS) and eggshells (ES) using thermogravimetric analysis (TG) approach at different heating rates of 10-100 K min-1 in temperature range of 323-1173 K are investigated. Catalytic pyrolysis mechanism of both catalysts had shown significant effect on the degradation of RH. Model free kinetic of iso-conversional method (Flynn-Wall-Ozawa) and multi-step reaction model (Distributed Activation Energy Model) were employed into present study. The average activation energy was found in the range of 175.4-177.7 kJ mol-1 (RH), 123.3-132.5 kJ mol-1 (RH-LS), and 96.1-100.4 kJ mol-1 (RH-ES) respectively. The syngas composition had increased from 60.05 wt% to 63.1 wt% (RH-LS) and 63.4 wt% (RH-ES). However, the CO2 content had decreased from 24.1 wt% (RH) to 20.8 wt% (RH-LS) and 19.9 wt% (RH-ES).
Lovastatin (LVS) is an effective therapeutic and prophylactic agent in several cardiovascular disorders. However, it has low bioavailability. This study investigated solute-solvent and solute-cosolute interactions and assessed thermodynamic parameters that contributed to LVS solubility enhancement in the presence of arginine (ARG) as a hydrotropic agent. The electrolytic conductance of LVS-ARG binary system was measured at temperatures from 298.15 K to 313.15 K. Conductometric parameters such as limiting molar conductance was evaluated. Additionally, thermodynamic parameters (ΔG0, ΔH0, ΔS0 and ES) involved in the association process of the solute in the aqueous solution of ARG solution were determined systematically. Solubility markedly improved 43-fold in the LVS-ARG complex compared to LVS alone. The analysed data from values of molar conductance and activation energy suggested favourable solubilisation, with a stronger solute-solvent interaction between LVS-ARG in water at higher temperatures. ARG and LVS complexation caused by strong molecular interactions was confirmed by spectral results. Hence, the addition of ARG as a co-solute was proven to enhance LVS solubility in water. The obtained data will ultimately enable the development of desired highly soluble, more efficient and safer LVS preparations.
The physicality of subjectivity is explained through a theoretical conceptualization of guidance waves informing meaning in negentropically entangled non-electrolytic brain regions. Subjectivity manifests its influence at the microscopic scale of matter originating from de Broglie 'hidden' thermodynamics as action of guidance waves. The preconscious experienceability of subjectivity is associated with a nested hierarchy of microprocesses, which are actualized as a continuum of patterns of discrete atomic microfeels (or "qualia"). The mechanism is suggested to be through negentropic entanglement of hierarchical thermodynamic transfer of information as thermo-qubits originating from nonpolarized regions of actin-binding proteinaceous structures of nonsynaptic spines. The resultant continuous stream of intrinsic information entails a negentropic action (or experiential flow of thermo-quantum internal energy that results in a negentropic force) which is encoded through the non-zero real component of the mean approximation of the negentropic force as a 'consciousness code'. Consciousness consisting of two major subprocesses: (1) preconscious experienceability and (2) conscious experience. Both are encapsulated by nonreductive physicalism and panexperiential materialism. The subprocess (1) governing "subjectivity" carries many microprocesses leading to the actualization of discrete atomic microfeels by the 'consciousness code'. These atomic microfeels constitute internal energy that results in the transfer intrinsic information in terms of thermo-qubits. These thermo-qubits are realized as thermal entropy and sensed by subprocess (2) governing "self-awareness" in conscious experience.
The crab carapace is a waste which cannot be decomposed. This waste was used to
remove the Reactive Orange 16 (RO16) and Basic Blue 3 (BB3) from aqueous solution
at different operational parameters such as pH, mass load, the concentrations of dye and
the temperature. The crab collected was modified to obtain quaternized crab (QC) using
(3-chloro-2-hydroxypropyl) trimethylammonium chloride solution (C6H15Cl2NO, 65% w/w
in water). The pH of the dyes solution was varied from pH 4 to 10. The highest adsorption
percentage was achieved at pH 7 for both dyes. Increasing the QC mass for the adsorption
process had granted an increase of dyes removal percentage. The highest adsorption
percentage was achieved at 91.00% for RO16 and 29.40% for BB3 dyes with 7.5 g/L QC
used. However, the adsorption capacity of QC decreased with higher QC mass because the
dye molecules occupied on the surface and prevented other molecules to diffuse into the
QC. At higher concentration beyond 20 mg/L and 10 mg/L of RO16 and BB3, respectively,
the maximum adsorption was achieved at 2.5362 mg/g and 0.6812 mg/g. The adsorption of
both dyes by QC was best fitted using Langmuir isotherm model, explaining the adsorption
mainly occurred as a single layer on the surface of QC. Comparison to the results obtained
from the kinetic models, the adsorption was
chemisorption in nature. According to the
thermodynamic studies, the adsorption of
RO16 was an exothermic, while BB3 was
an endorthermic process.
In the present study, catalytic pyrolysis of Chlorella vulgaris biomass was conducted to analyse the kinetic and thermodynamic performances through thermogravimetric approach. HZSM-5 zeolite, limestone (LS), bifunctional HZSM-5/LS were used as catalysts and the experiments were heated from 50 to 900 °C at heating rates of 10-100 °C/min. Iso-conversional model-free methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Starink's, and Vyazovkin (V) were employed to evaluate the kinetic parameters meanwhile the thermodynamic parameters were determined by using FWO and KAS methods. The calculated EA values of non-catalytic and catalytic pyrolysis of HZSM-5 zeolite, LS, and bifunctional HZSM-5/LS were determined to be in the range of 156.16-158.10 kJ/mol, 145.26-147.84 kJ/mol, 138.81-142.06 kJ/mol, and 133.26 kJ/mol respectively. The results have shown that catalytic pyrolysis with the presence of bifunctional HZSM-5/LS resulted to a lower average EA and ΔH compared to HZSM-5, and LS which indicated less energy requirement in the process.
Molecular interaction of the 3,4-methylenedioxy-β-nitrostyrene (MNS), an inhibitor of platelet aggregation with the main transport protein, albumin from human serum (HSA) was explored using absorption, fluorescence and circular dichroism (CD) spectroscopy in combination with in silico analyses. The MNS-HSA complexation was corroborated from the fluorescence and absorption spectral results. Implication of static quenching mechanism for MNS-HSA system was predicted from the Stern-Volmer constant, KSV-temperature relationship as well as the bimolecular quenching rate constant, kq values. Stabilization of the complex was affirmed by the value of the binding constant (Ka = 0.56-1.48 × 104 M-1). Thermodynamic data revealed that the MNS-HSA association was spontaneously driven mainly through hydrophobic interactions along with van der Waal's interaction and H-bonds. These results were well supported by in silico interpretations. Far-UV and near-UV CD spectral results manifested small variations in the protein's secondary and tertiary structures, respectively, while three-dimensional fluorescence spectra displayed microenvironmental fluctuations around protein's fluorophores, upon MNS binding. Significant improvement in the protein's thermostability was evident from the temperature-stability results of MNS-bound HSA. Binding locus of MNS, as identified by competitive drug displacement findings as well as in silico analysis, was found to be located in subdomain IIA (Sudlow's site I) of the protein.Communicated by Ramaswamy H. Sarma.
Multi-layer structure of functional materials often involves the integration of different crystalline phases. The film growth orientation thus frequently exhibits a transformation, owing to multiple possibilities caused by incompatible in-plane structural symmetry. Nevertheless, the detailed mechanism of the transformation has not yet been fully explored. Here we thoroughly probe the heteroepitaxially grown hexagonal zinc oxide (ZnO) films on cubic (001)-magnesium oxide (MgO) substrates using advanced scanning transition electron microscopy, X-ray diffraction and first principles calculations, revealing two distinct interface models of (001) ZnO/(001) MgO and (100) ZnO/(001) MgO. We have found that the structure alternatives are controlled thermodynamically by the nucleation, while kinetically by the enhanced Zn adsorption and O diffusion upon the phase transformation. This work not only provides a guideline for the interface fabrication with distinct crystalline phases but also shows how polar and non-polar hexagonal ZnO films might be manipulated on the same cubic substrate.
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
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.
The purpose of this research is to synthesize environmentally friendly nanosorbents for the novel adsorption of diesel range organics (DRO) from contaminated water. Central composite design (CCD) analysis of response surface methodology (RSM) was employed in a model fitting of the variables predicting the adsorption efficiency of Moringa oleifera-functionalized zerovalent iron particles (ZINPs) for the removal of DRO. The effects of the reaction parameters on the response were screened using 24 factorial designs to determine the statistically significant independent variables. A quadratic model predicting the DRO adsorption efficiency of ZINPs with an F value of 276.84 (p value
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.
We utilized molecular dynamics (MD) simulations and Molecular Mechanics Poisson-Boltzmann Surface Area (MMPBSA) free energy calculations to investigate the specificity of two oligonucleotide probes, namely probe B and probe D, in detecting single-stranded DNA (ssDNA) within three bacteria families: Enterobacteriaceae, Pasteurellaceae, and Vibrionaceae. Due to the limited understanding of molecular mechanisms in the previous research, we have extended the discussion to focus specifically on investigating the binding process of bacteria-probe DNA duplexes, with an emphasis on analyzing the binding free energy. The role of electrostatic contributions in the specificity between the oligonucleotide probes and the bacterial ssDNAs was investigated and found to be crucial. Our calculations yielded results that were highly consistent with the experimental data. Through our study, we have successfully exhibited the benefits of utilizing in-silico approaches as a powerful virtual-screening tool, particularly in research areas that demand a thorough comprehension of molecular interactions.
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.
Inclusion complexes require higher concentration of Beta cyclodextrins (βCD) resulting in increased formulation bulk, toxicity, and production costs. This systematic review offers a comprehensive analysis using Quality by design (QbD) as a tool to predict potential applications of Polyvinylpyrrolidone (PVP) as a ternary substance to address issues of inclusion complexes. We reviewed 623 documents from 2013 to 2023 and Eighteen (18) research papers were selected for statistical and meta-analysis using the QbD concept to identify the most critical factors for selecting drugs and effect of PVP on inclusion complexes. The QbD analysis revealed that Molecular weight (MW), Partition coefficient (Log P), and the auxiliary substance ratio directly affected complexation efficiency (CE), thermodynamic stability in terms of Gibbs free energy (ΔG), and percent drug release. However, Stability constant (Ks) remained unaffected by any of these parameters. The results showed that low MW (250), median Log P (6), and a βCD: PVP ratio of 2:3 would result in higher CE, lower G, and improved drug release. PVP improves drug solubility, enhances delivery and therapeutic outcomes, and counteracts increased drug ionization due to decreased pH. In certain cases, its bulky nature and hydrogen bonding with CD molecules can form non-inclusion complexes. The findings of the study shows that there is potential molecular interaction between PVP and β-cyclodextrins, which possibly enhances the stability of inclusion complexes for drug with low MW and log P values less than 9. The systematic review shows a comprehensive methodology based on QbD offers a replicable template for future investigations into drug formulation research.
Water bodies with the dye methylene blue pose serious environmental and health risks to humans. Therefore, the creation and investigation of affordable, potential adsorbents to remove methylene blue dye from water resources as a long-term fix is one focus of the scientific community. Food plants and other carbon-source serve as a hotspot for a wider range of application on different pollutants that impact the environment and living organisms. Here, we reviewed the use of treated and untreated biosorbents made from plant waste leaves for removing the dye methylene blue from aqueous media. After being modified, activated carbon made from various plant leaves improves adsorption performance. The range of activating chemicals, activation methods, and bio-sorbent material characterisation using FTIR analysis, Barunauer-Emmett-Teller (BET) surface area, scanning electron microscope (SEM-EDX), and SEM-EDX have all been covered in this review. It has been thoroughly described how the pH solution of the methylene blue dye compares to the pHPZC of the adsorbent surface. The presentation also includes a thorough analysis of the application of the isotherm model, kinetic model, and thermodynamic parameters. The selectivity of the adsorbent is the main focus of the adsorption kinetics and isotherm models. It has been studied how adsorption occurs, how surface area and pH affect it, and how biomass waste compares to other adsorbents. The use of biomass waste as adsorbents is both environmentally and economically advantageous, and it has been discovered to have exceptional color removal capabilities.