Oil and grease remain the dominant contaminants in the palm oil mill effluent (POME) despite the conventional treatment of POME. The removal of residual oil from palm oil-water mixture (POME model) using the progressive freezing process was investigated. An optimization technique called response surface methodology (RSM) with the design of rotatable central composite design was applied to figure out the optimum experimental variables generated by Design-Expert software (version 6.0.4. Stat-Ease, trial version). Besides, RSM also helps to investigate the interactive effects among the independent variables compared to one factor at a time. The variables involved are coolant temperature, XA (4-12 °C), freezing time, XB (20-60 min), and circulation flow, XC (200-600 rpm). The statistical analysis showed that a two-factor interaction model was developed using the obtained experimental data with a coefficient of determination (R2) value of 0.9582. From the RSM-generated model, the optimum conditions for extraction of oil from the POME model were a coolant temperature of 6 °C in 50 min freezing time with a circulation flowrate of 500 rpm. The validation of the model showed that the predicted oil yield and experimental oil yield were 92.56 and 93.20%, respectively.
In this study, novel self-assembled carbazole-thiooctanoic acid nanoparticles (CTNs) were synthesized from amino carbazole (a mutagen) and thiooctanoic acid (an antioxidant). The nanoparticles were characterized using hyperspectral techniques. Then, the antiproliferative potential of CTNs was determined in HepG2 liver carcinoma cells. This study employed a solvent-antisolvent interaction method to synthesize a spherical CTN of size less than 50 nm. Moreover, CT was subsequently capped to gold nanoparticles (AuNPs) in the additional comparative studies. The CT derivative was synthesized from carbazole and lipoic acid by the amide bond formation reaction using a coupling agent. Furthermore, it was characterized using infrared (IR), 1H nuclear magnetic resonance, dynamic light scattering (DLS), and transmission electron microscopy techniques. The CT-capped gold nanoparticles (CTAuNPs) were prepared from CT, chloroauric acid, and NaBH4. The CTAuNPs were characterized using ultraviolet-visible, high-resolution TEM, DLS, and Fourier transform IR techniques. The cytotoxicity and apoptosis-inducing ability of both nanoparticles were determined in HepG2 cells. The results demonstrate that CTNs exhibit antiproliferative activity in the cancerous HepG2 cells. Moreover, molecular docking and molecular dynamics studies were conducted to explore the therapeutic potential of CT against human EGFR suppressor protein to gain more insights into the binding mode of the CT, which may show a significant role in anticancer therapy.
A novel resin-based nanocomposite-coated sand proppant is introduced to address the issue of proppant flowback in post-fracturing fluid flowback treatments and hydrocarbon production. Self-aggregation in the water environment is the most attractive aspect of these developed proppants. In this work, sand was sieve-coated with 0.1% multiwalled carbon nanotubes (MWCNTs) followed by optimized thin and uniform resin (polyurethane) spray coating in the concentration range of 2 to 10%. Quantitative and qualitative evaluations have been carried out to assess the self-aggregation capabilities of the proposed sand proppants where no flowback was witnessed at 4% polyurethane coating containing 0.1% MWCNTs. This applied resin incorporating MWCNT coating was characterized by field emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy depicted the dispersed presence of MWCNTs into polyurethane resin corroborated by the presence of 38% elemental carbon on the sand substrate. Proppant crushing resistance tests were conducted, including proppant pack stress-strain response, compaction, and fines production. It was found that the proposed sand proppant decreased the proppant pack compaction by ∼25% compared to commonly used silica sand with the ability to withstand high closure stress as high as 55 MPa with less than 10 wt % fines production. The surface wettability was determined by the sessile drop method. The application of resin incorporating MWCNT coating layers changed the sand proppant wetting behavior to oil-wet with a contact angle of ∼124°. Thermogravimetric analyses revealed a significant increment in thermal stability, which reached up to 280 °C due to the addition of MWCNTs as reinforcing nanofillers.
The formation of foam due to the injection of surfactant foam in FAWAG causes significant problems in the oil well production and separation facilities. The excessive foam can lead to the reduction of the separator capacity as well as its efficiency. A defoamer is needed to break and destroy the foam in the separator. There are many commercially available defoamer agents in the market, but not all defoamers are suitable for every application. For this reason, four modified silicone-based defoamers were successfully synthesized and characterized based on the data obtained from the screening process using various commercial defoamers. The performance of modified defoamers was evaluated using TECLIS FoamScan that imitate real conditions of treatment. The results show that all four of the modified silicone-based defoamers, especially amide-terminated-modified defoamers (S2) showed excellent performance as a defoaming agent to mitigate foam in specific conditions. The best-case condition for the modified defoamer to perform was at a high temperature (60 °C), gas flow rate of 1.0 L/min, and low ration concentration of the surfactant to brine (30:70). The study on the bubble count and distribution using a KRÜSS Dynamic Foam Analyzer revealed that S2 excellently contributes to the formation of unstable foam that can fasten foam destruction in the foaming system.
Among several animals, Rattus rattus (rat) lives in polluted environments and feeds on organic waste/small invertebrates, suggesting the presence of inherent mechanisms to thwart infections. In this study, we isolated gut bacteria of rats for their antibacterial activities. Using antibacterial assays, the findings showed that the conditioned media from selected bacteria exhibited bactericidal activities against Gram-negative (Escherichia coli K1, Klebsiella pneumoniae, Pseudomonas aeruginosa, Serratia marcescens, and Salmonella enterica) and Gram-positive (Bacillus cereus, methicillin-resistant Staphylococcus aureus, and Streptococcus pyogenes) pathogenic bacteria. The conditioned media retained their antibacterial properties upon heat treatment at boiling temperature for 10 min. Using MTT assays, the conditioned media showed minimal cytotoxic effects against human keratinocyte cells. Active conditioned media were subjected to tandem mass spectrometry, and the results showed that conditioned media from Bacillus subtilis produced a large repertoire of surfactin and iturin A (lipopeptides) molecules. To our knowledge, this is the first report of isolation of lipopeptides from bacteria isolated from the rat gut. In short, these findings are important and provide a platform to develop effective antibacterial drugs.
A rapid, sustainable, and ecologically sound approach is urgently needed for the production of semiconductor nanomaterials. CuSe nanoparticles (NPs) were synthesized via a microwave-assisted technique using CuCl2·2H2O and Na2SeO3 as the starting materials. The role of the irradiation time was considered as the primary concern to regulate the size and possibly the shape of the synthesized nanoparticles. A range of characterization techniques was used to elucidate the structural and optical properties of the fabricated nanoparticles, which included X-ray diffraction, energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy, field emission scanning electron microscopy, Raman spectroscopy (Raman), UV-Visible diffuse reflectance spectroscopy (DRS), and photoluminescence spectroscopy (PL). The mean crystallite size of the CuSe hexagonal (Klockmannite) crystal structure increased from 21.35 to 99.85 nm with the increase in irradiation time. At the same time, the microstrain and dislocation density decreased from 7.90 × 10-4 to 1.560 × 10-4 and 4.68 × 10-2 to 1.00 × 10-2 nm-2, respectively. Three Raman vibrational bands attributed to CuSe NPs have been identified in the Raman spectrum. Irradiation time was also seen to play a critical role in the NP optical band gap during the synthesis. The decrease in the optical band gap from 1.85 to 1.60 eV is attributed to the increase in the crystallite size when the irradiation time was increased. At 400 nm excitation wavelength, a strong orange emission centered at 610 nm was observed from the PL measurement. The PL intensity is found to increase with an increase in irradiation time, which is attributed to the improvement in crystallinity at higher irradiation time. Therefore, the results obtained in this study could be of great benefit in the field of photonics, solar cells, and optoelectronic applications.
A series of 3-amino-2-hydroxybenzofused 2-phosphalactones (4a-l) has been synthesized from the Kabachnik-Fields reaction via a facile route from a one-pot three-component reaction of diphenylphosphite with various 2-hydroxybenzaldehyes and heterocyclic amines in a new way of expansion. The in vitro anti-cell proliferation studies by MTT assay have revealed them as potential Panc-1, Miapaca-2, and BxPC-3 pancreatic cell growth inhibitors, and the same is supported by molecular docking, QSAR, and ADMET studies. The MTT assay of their SAHA derivatives against the same cell lines evidenced them as potential HDAC inhibitors and identified 4a, 4b, and 4k substituted with 1,3-thiazol, 1,3,4-thiadiazol, and 5-sulfanyl-1,3,4-thiadiazol moieties on phenyl and diethylamino phenyl rings as potential ones. Additionally, the flow cytometric analyses of 4a, 4b, and 4k against BxPC-3 cells revealed compound 4k as a lead compound that arrests the S phase cell cycle growth at low micromolar concentrations. The ADMET properties have ascertained their inherent pharmacokinetic potentiality, and the wholesome results prompted us to report it as the first study on anti-pancreatic cancer activity of cyclic α-aminophosphonates. Ultimately, this study serves as a good contribution to update the existing knowledge on the anticancer organophosphorus heterocyclic compounds and elevates the scope for generation of new anticancer drugs. Further, the studies like QSAR, drug properties, toxicity risks, and bioactivity scores predicted for them have ascertained the synthesized compounds as newer and potential drug candidates. Hence, this study had augmented the array of α-aminophosphonates by adding a new collection of 3-amino-2-hydroxybenzofused 2-phosphalactones, a class of cyclic α-aminophosphonates, to it, which proved them as potential anti-pancreatic cancer agents.
In this study, a mineral-based coated urea was fabricated in a rotary pan coater using a mixture of gypsum/sulfur/zeolite (G25S25Z50) as an effective and low-cost coating material. The effects of different coating compositions on the dissolution rate of urea and the crushing strength and morphology of the coated urea were investigated. A 25:25:50 (wt %) mixture of gypsum/sulfur/zeolite (G25S25Z50) increased the coating effectiveness to 34.1% with the highest crushing strength (31.06 N). The effectiveness of coated urea was further improved to 46.6% with the addition of a microcrystalline wax (3%) as a sealant. Furthermore, the release mechanisms of various urea fertilizers were determined by fitting the release profiles with six mathematical models, namely, the zeroth-order, first-order, second-order, Higuchi, Ritger & Peppas, and Kopcha models. The results showed that the release mechanism of the uncoated urea and all other coated urea followed the Ritger & Peppas model, suggesting the diffusional release from nonswellable delivery systems. In addition, due to the increased mass-transfer resistance, the kinetic constant was decreased from 0.2233 for uncoated urea to 0.1338 for G25S25Z50-coated urea and was further decreased to 0.0985 when 3% Witcovar 146 sealant was applied.
Predicting the incremental recovery factor with an enhanced oil recovery (EOR) technique is a very crucial task. It requires a significant investment and expert knowledge to evaluate the EOR incremental recovery factor, design a pilot, and upscale pilot result. Water-alternating-gas (WAG) injection is one of the proven EOR technologies, with an incremental recovery factor typically ranging from 5 to 10%. The current approach of evaluating the WAG process, using reservoir modeling, is a very time-consuming and costly task. The objective of this research is to develop a fast and cost-effective mathematical model for evaluating hydrocarbon-immiscible WAG (HC-IWAG) incremental recovery factor for medium-to-light oil in undersaturated reservoirs, designing WAG pilots, and upscaling pilot results. This integrated research involved WAG literature review, WAG modeling, and selected machine learning techniques. The selected machine learning techniques are stepwise regression and group method of data handling. First, the important parameters for the prediction of the WAG incremental recovery factor were selected. This includes reservoir properties, rock and fluid properties, and WAG injection scheme. Second, an extensive WAG and waterflood modeling was carried out involving more than a thousand reservoir models. Third, WAG incremental recovery factor mathematical predictive models were developed and tested, using the group method of data handling and stepwise regression techniques. HC-IWAG incremental recovery factor mathematical models were developed with a coefficient of determination of about 0.75, using 13 predictors. The developed WAG predictive models are interpretable and user-friendly mathematical formulas. These developed models will help the subsurface teams in a variety of ways. They can be used to identify the best candidates for WAG injection, evaluate and optimize the WAG process, help design successful WAG pilots, and facilitate the upscaling of WAG pilot results to full-field scale. All this can be accomplished in a short time at a low cost and with reasonable accuracy.
The energy demand of the world is skyrocketing due to the exponential economic growth and population expansion. To meet the energy requirement, the use of fossil fuels is not a good decision, causing environmental pollution such as CO2 emissions. Therefore, the use of renewable energy sources like biofuels can meet the energy crisis especially for countries facing oil shortages such as Pakistan. This review describes the comparative study of biodiesel synthesis for various edible oils, non-edible oils, and wastes such as waste plastic oil, biomass pyrolysis oil, and tyre pyrolysis oil in terms of their oil content and extraction, cetane number, and energy content. The present study also described the importance of biodiesel synthesis via catalytic transesterification and its implementation in Pakistan. Pakistan is importing an extensive quantity of cooking oil that is used in the food processing industries, and as a result, a huge quantity of waste cooking oil (WCO) is generated. The potential waste oils for biodiesel synthesis are chicken fat, dairy scum, WCO, and tallow oil that can be used as potential substrates of biodiesel. The implementation of a biodiesel program as a replacement of conventional diesel will help to minimize the oil imports and uplift the country's economy. Biodiesel production via homogeneous and heterogeneous catalyzed transesterification is more feasible among all transesterification processes due to a lesser energy requirement and low cost. Therefore, biodiesel synthesis and implementation could minimize the imports of diesel by significantly contributing to the overall Gross Domestic Product (GDP). Although, waste oil can meet the energy needs, more available cultivation land should be used for substrate cultivation. In addition, research is still needed to explore innovative solvents and catalysts so that overall biodiesel production cost can be minimized. This would result in successful biodiesel implementation in Pakistan.
The significant loss of surfactants during reservoir flooding is a challenge in oil field operations. The presence of clay minerals affects the surfactant performance, resulting in surfactant losses. This is because the mineralogical composition of the reservoir results in unpredicted adsorption quantity. Therefore, this paper seeks to investigate Aerosol-OT's adsorption on different quartz/clay mineral compositions during the flow. Also, it investigates adsorption mitigation by preflushing with lignin. The dynamic experiments were conducted on sand packs composed of quartz-sand and up to a 7% clay mineral content. The results obtained from the surfactant losses were compared with/without lignin preflush at different pH values. The main observation was the direct relationship between increasing the composition of clay minerals and the surfactant pore volume required to overcome the adsorption. The highest adsorption calculated was 46 g/kg for 7% kaolinite. Moreover, lignin successfully reduced the adsorption of Aerosol-OT by 60%. Therefore, the results demonstrate that the effects of the clay mineral content on adsorption could be efficiently minimized using lignin at a high pH.
In this work, the catalytic effects of FeCl3 toward the hydrogen storage properties of the MgH2-Na3AlH6 composite were investigated for the first time. The temperature-programed desorption results indicated that the onset temperature of the hydrogen release of a 10 wt % FeCl3-doped MgH2-Na3AlH6 composite was ∼30 °C lower than that of the undoped MgH2-Na3AlH6 composite. The addition of FeCl3 into the MgH2-Na3AlH6 composite resulted in improved absorption and desorption kinetics performance. The absorption/desorption kinetics measurements at 320 °C (under 33 and 1 atm hydrogen pressure, respectively) indicated that within 10 min, the doped sample absorbed ∼4.0 wt % and desorbed ∼1.5 wt % hydrogen. By comparison, the undoped sample absorbed only ∼2.1 wt % and desorbed only ∼0.6 wt % hydrogen under the same conditions and time. Comparably, the apparent activation energy value of the doped composite is 128 kJ/mol, which is 12 kJ/mol lower than that of the undoped composite (140 kJ/mol). The formation of the new species of MgCl2 and Fe in the doped composite was detected from X-ray diffraction analysis after heating and absorption processes. These two components were believed to play a vital role in reducing the decomposition temperature and kinetics enhancement of the MgH2-Na3AlH6 composite.
Acacia gum (AG) is a branched-polysaccharide gummy exudate that consists of arabinose and galactose. The traditional practice in African-Middle Eastern countries uses this gum as medicine. Traditional use of AG is to treat stomach disease, which can be a potential functional food. In this research, commercially available AG from Acacia senegal and Acacia seyal was investigated as the prebiotic. The experiment employed a pH-controlled in vitro colon model inoculated with human fecal microbiota to mimic the human colon. Fermentation samples at 0, 6, 12, and 24 h were brought for short-chain fatty acid (SCFA) analysis using high-performance liquid chromatography and bacterial enumeration via fluorescent in situ hybridization. Results showed that AG significantly promotes Bifidobacteria proliferation similar to fructo-oligosaccharides (FOS) while inhibiting the Clostridium histolyticum group, commonly associated with gut dysbiosis. Acetate, propionate, and butyrate showed a similar trend to FOS (p > 0.05). The AG shows potential against gut dysbiosis, as it promotes gut-probiotics, through modulation of microbial population and SCFA production, especially butyrate.
Removal of nitrogen and sulfur compounds from diesel fuel is essential to comply with the increasing stringent regulations. The extraction capability of two deep eutectic solvents, namely, tetrabutylphosphoniumbromide/ethylene glycol, TBPBr/EG, with molar ratio 1:2, and tetrabutylammoniumbromide/ethylene glycol, TBABr/EG, with molar ratio 1:2, in simultaneously extracting basic nitrogen, nonbasic nitrogen, and sulfur compounds represented by pyridine, indoline, and dibenzothiophene (DBT) from n-hexadecane, was investigated. Two pseudo-ternary phase diagrams of (TBPBr/EG + (pyridine + indoline + DBT) + n-hexadecane) and (TBABr/EG + (pyridine + indoline + DBT) + n-hexadecane) were predicted via a conductor-like screening model for real solvents (COSMO-RS) and experimentally validated at 298.15 K and 1 atm. Both solvents showed zero cross-contamination, indicating the suitability of all solvents as extraction solvents. The tie lines obtained for both COSMO-RS and experiments were in agreement and had root-mean-square deviation (RMSD) values of less than 5% for both systems. Selectivity and distribution ratio calculated indicates the suitability of both solvents in extracting sulfur and nitrogen compounds from hexadecane. Two new parameters, namely, extraction efficiency, α, and extraction affinity, β, were introduced to ease the performance comparison of both solvents. TBPBr/EG shows a slightly better performance than TBABr/EG. Other than that, the presence of multiple solutes shows low effects on the performance of these solvents.
This research was aimed to examine the diesel engine's performance and emission of secondary fuels (SFs), comprising waste plastic oil (WPO) and palm oil biodiesel (POB), and to analyze their tribological properties. Their compositions were analyzed by gas chromatography-mass spectrometry (GC-MS). Five SFs (10-50% POB in WPO) were prepared by mechanical stirring. The results were compared to blank WPO (WPO100) and Malaysian commercial diesel (B10). WPO90 showed the maximum brake power (BP) and brake torque (BT) among the SFs, and their values were 0.52 and 0.59% higher compared to B10, respectively. The increase in POB ratio (20-50%) showed a negligible difference in BP and BT. WPO70 showed the lowest brake-specific fuel consumption among the SFs. The brake thermal efficiency (BTE) increased with POB composition. The maximum reductions in emission of hydrocarbon (HC, 37.21%) and carbon monoxide (CO, 27.10%) were achieved by WPO50 among the SFs. WPO90 showed the maximum reduction in CO2 emission (6.78%). Increasing the POB composition reduced the CO emissions and increased the CO2 emissions. All SFs showed a higher coefficient of friction (COF) than WPO100. WPO50 showed the minimal increase in COF of 2.45%. WPO90 showed the maximum reduction in wear scar diameter (WSD), by 10.34%, compared to B10. Among the secondary contaminated samples, SAE40-WPO90 showed the lowest COF, with 5.98% reduction compared to SAE40-WPO100. However, with increasing POB content in the secondary contaminated samples, the COF increased. The same trend was also observed in their WSD. Overall, WPO90 is the optimal SF with excellent potential for diesel engines.
The bubble point pressure (P b) is a crucial pressure-volume-temperature (PVT) property and a primary input needed for performing many petroleum engineering calculations, such as reservoir simulation. The industrial practice of determining P b is by direct measurement from PVT tests or prediction using empirical correlations. The main problems encountered with the published empirical correlations are their lack of accuracy and the noncomprehensive data set used to develop the model. In addition, most of the published correlations have not proven the relationships between the inputs and outputs as part of the validation process (i.e., no trend analysis was conducted). Nowadays, deep learning techniques such as long short-term memory (LSTM) networks have begun to replace the empirical correlations as they generate high accuracy. This study, therefore, presents a robust LSTM-based model for predicting P b using a global data set of 760 collected data points from different fields worldwide to build the model. The developed model was then validated by applying trend analysis to ensure that the model follows the correct relationships between the inputs and outputs and performing statistical analysis after comparing the most published correlations. The robustness and accuracy of the model have been verified by performing various statistical analyses and using additional data that was not part of the data set used to develop the model. The trend analysis results have proven that the proposed LSTM-based model follows the correct relationships, indicating the model's reliability. Furthermore, the statistical analysis results have shown that the lowest average absolute percent relative error (AAPRE) is 8.422% and the highest correlation coefficient is 0.99. These values are much better than those given by the most accurate models in the literature.
We report a viable method to produce nanocrystalline graphene films on polycrystalline nickel (Ni) with enhanced N doping at low temperatures by a cold-wall plasma-assisted chemical vapor deposition (CVD) method. The growth of nanocrystalline graphene films was carried out in a benzene/ammonia/argon (C6H6/NH3/Ar) system, in which the temperature of the substrate heated by Joule heating can be further lowered to 100 °C to achieve a low sheet resistance of 3.3 kΩ sq-1 at a high optical transmittance of 97.2%. The morphological, structural, and electrical properties and the chemical compositions of the obtained N-doped nanocrystalline graphene films can be tailored by controlling the growth parameters. An increase in the concentration of atomic N from 1.42 to 11.28 atomic percent (at.%) is expected due to the synergetic effects of a high NH3/Ar ratio and plasma power. The possible growth mechanism of nanocrystalline graphene films is also discussed to understand the basic chemical reactions that occur at such low temperatures with the presence of plasma as well as the formation of pyridinic-N- and pyrrolic-N-dominated nanocrystalline graphene. The realization of nanocrystalline graphene films with enhanced N doping at 100 °C may open great potential in developing future transparent nanodevices.
Graphene oxide (GO)-doped MnO2 nanorods loaded with 2, 4, and 6% GO were synthesized via the chemical precipitation route at room temperature. The aim of this work was to determine the catalytic and bactericidal activities of prepared nanocomposites. Structural, optical, and morphological properties as well as elemental composition of samples were investigated with advanced techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-visible (vis) spectroscopy, photoluminescence (PL), energy-dispersive spectrometry (EDS), and high-resolution transmission electron microscopy (HR-TEM). XRD measurements confirmed the monoclinic structure of MnO2. Vibrational mode and rotational mode of functional groups (O-H, C=C, C-O, and Mn-O) were evaluated using FTIR results. Band gap energy and blueshift in the absorption spectra of MnO2 and GO-doped MnO2 were identified with UV-vis spectroscopy. Emission spectra were attained using PL spectroscopy, whereas elemental composition of prepared materials was recorded with scanning electron microscopy (SEM)-EDS. Moreover, HR-TEM micrographs of doped and undoped MnO2 revealed elongated nanorod-like structure. Efficient degradation of methylene blue enhanced the catalytic activity in the presence of a reducing agent (NaBH4); this was attributed to the implantation of GO on MnO2 nanorods. Furthermore, substantial inhibition areas were measured for Escherichia coli (EC) ranging 2.10-2.85 mm and 2.50-3.15 mm at decreased and increased levels for doped MnO2 nanorods and 3.05-4.25 mm and 4.20-5.15 mm for both attentions against SA, respectively. In silico molecular docking studies suggested the inhibition of FabH and DNA gyrase of E. coli and Staphylococcus aureus as a possible mechanism behind the bactericidal activity of MnO2 and MnO2-doped GO nanoparticles (NPs).
Durian peels are an agricultural waste in Asian countries, including Thailand, Indonesia, and Malaysia, which can be used as a precursor for the production of activated carbon. The objective of this work is to produce activated carbon from durian peels by chemical activation using sodium sulfite (Na2SO3) as an activating and sulfur-doping agent. The process parameter investigated in this study was the activation temperature (500-900 °C) at a fixed impregnation ratio (durian to activating agent of 1:1, by weight). Specific surface areas and pore structures were determined by nitrogen adsorption and desorption measurements, and elemental compositions were characterized by CHNSO analysis. The chemical structure and surface functionality were examined by X-ray photoelectron spectroscopy. The electrochemical behavior of the obtained activated carbon was characterized in 6 M KOH using a three-electrode configuration. It was found that the sulfur content decreases with activation temperature. In contrast, the specific surface area of the activated carbon increases with activation temperature. However, the sample activated at 900 °C with the highest specific surface area (1499 m2 g-1) has a lower specific capacitance (166 F g-1) than the one activated at 700 °C (183 F g-1). This could be due to the presence of a pseudocapacitance caused by the organic sulfur functional groups such as thiophene, sulfone, and sulfoxide, which can trigger a surface redox reaction, leading to a higher capacitance.
In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (αiso) polarizability value of 603.1 × 10-24 esu is shown by compound 7 which is ∼12, ∼16, ∼9, ∼11, ∼10, and ∼4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability ⟨γ⟩ with an amplitude of 7607 × 10-36 esu at the M06/6-311G** level of theory, which is ∼521, ∼505, ∼38, ∼884, ∼185, and ∼15 times more than that of compounds 1-6, respectively. The extensively larger ⟨γ⟩ amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications.