Advances in Chemistry and Chemical Engineering

The reaction mechanism of ClO${}_2$-mediated TEMPO oxidation was investigated by EPR spectroscopy and UV–Vis spectroscopy in the context of an alternative TEMPO sequence for cellulose fiber oxidation. Without the presence of a cellulosic substrate, a reversibility between TEMPO and its oxidation product, TEMPO${}^{+}$, was displayed, with an effect of the pH and reagent molar ratios. The involvement of HOCl and Cl${}^{-}$, formed as byproducts in the oxidation mechanism, was also evidenced. Trapping HOCl partly inhibits the reaction, whereas adding methylglucoside, a cellulose model compound, inhibits the reversibility of the reaction to TEMPO. Full article

The present study investigated the degradation of an aqueous Allura Red AC (AR–AC) solution by activating hydrogen peroxide with bicarbonate using cobalt ion (Co²⁺) as the catalyst. Four independent variables (H₂O₂, NaHCO₃, Co²⁺, and dye concentrations) were analyzed in the composite central design (CCD). AR–AC degradation was optimized using the response surface methodology (RSM). Under optimal degradation conditions (41.86 mg/L AR–AC, 5.58 mM H₂O₂, 2.00 mM NaHCO₃, and 9.00 µM Co²⁺), decolorization > 99.86%, mineralization (CO₂ to conversion) of 12.99%, and total nitrogen removal of 51.97% were achieved. The predicted values for the three response variables were consistent with the experimental values, with determination coefficients (R²) greater than 0.9053. Because cobalt ions (Co²⁺) are a source of water pollution, after oxidation, these were adsorbed on sodium bentonite (Na–Bent), obtaining a final concentration of <0.01 mg/L. Bicarbonate-activated hydrogen peroxide is a potential technology for dye wastewater treatment that operates at an alkaline pH and at ambient temperature. Full article

This study investigates the adsorption of methanol, water, and their mixture in a hybrid silica stationary phase with supercritical carbon dioxide as a mobile phase in supercritical fluid chromatography (SFC). The adsorption isotherms of methanol and water were determined by two dynamic methods: the elution by characteristic point (ECP) method and the inverse method (IM). Both the single-component and competitive bi-Langmuir models were pre-selected for the inverse method. The initial parameters of the single-component isotherm for both methanol and water were estimated with the ECP method by fitting the experimental data to the bi-Langmuir isotherm model. Then, using the inverse method, we refined the single-component isotherm parameter values, which were then further used for determining the competitive isotherm of the methanol–water mixture. The elution profile of the (methanol–water) mixture sample was calculated by the equilibrium-dispersive (ED) model. The results indicated that there is a good agreement between the experimental band profile and the calculated band profile, which was obtained from the parameters of the competitive bi-Langmuir isotherm model, revealing a competition between methanol and water to reach the adsorption sites. Furthermore, the saturation capacity of the adsorption sites in the stationary phase decreased in the case of the mixture sample compared to those for the single-component sample. Full article

Fundamental microscopic investigations are based on the interaction between filter fiber and particles. The fibrous filter theory is based on a single fiber of a fiber array, and experiments focus either on a single fiber or a fiber array. This study investigates the particle loading process of a fiber array and focuses on the microscopic development of particle structures on the fiber array. Gravimetric measurements and image analysis of the array were used to study the development of the particle structure and morphology. Microscopic analysis of the video data focused on the evolution of particle accumulation within the fiber spacing, the development of boundary lines of the particle structure, and the number/size of bridges and pores within the particle structure. For the tested flow velocities, an increase in mass was observed to increase the duration of the filtration process. An extreme increase in deposited mass was observed at the moment of complete blocking (clogging) of the fiber spacing at flow velocities of 0.65 m/s. The size of pores (hydraulic diameter) increased with the flow velocity during the loading procedure. However, the total number of pores was higher in tests with lower Stokes numbers due to the dendritic and more porous structure. This work provides insights into the growth kinetics and structural setup of the particle structure (on a microscopic level). This will improve the understanding of the change of the filtration process from the transition phase to the clogging phase in fibrous filters. Full article

The primary objective of this study was to pragmatically implement an extraction process using slug flow, wherein two immiscible phases, aqueous and oil, are alternatively channeled through a conduit to encourage mass exchange across the interface. To facilitate this, we introduced and empirically validated an in-line technique to precisely quantify the length of the slug and the potential extraction concentration of the two aforementioned phases. The length of the slug and its concentration were ascertained through conductivity, utilizing platinum wire as the electrode. This method consistently produced results with a maximum error margin of ±5%. Using this apparatus, we determined key mass transfer parameters, including the overall mass transfer coefficient. Notably, as the linear velocity amplified, so did the extraction rate. These findings present a significant opportunity for enhancing the efficiency of the extraction process and enabling its optimization. Full article

This study aimed to address the challenges faced by mature oilfields in extracting substantial oil quantities. It focused on improving the efficiency of alkaline–surfactant–polymer (ASP) flooding technique, which is a proven tertiary recovery technology, to overcome scaling issues and other hindrances in its large-scale implementation. Appropriate materials and their suitable concentrations were selected to enhance the ASP flooding technique. Special surfactants from Indonesia were introduced to improve the interfacial tension reduction and wettability alteration. Reservoir rock model that resembling Langgak oilfield in Sumatra was utilized, and low-salinity water was employed to mimic the oilfield conditions. Starches derived from cassava nanoparticles (CSNPs) and purple yam nanoparticles (PYNPs) were combined separately with conventional hydrolyzed polyacrylamide (HPAM) polymer to enhance its performance. Sodium hydroxide and sodium carbonate were used as alkaline in final ASP formula. It was demonstrated from this research that only two combinations of ASP formulations have led to improved oil recovery. One combination utilizing PYNPs resulted in 39.17% progressive recovery, while the other combination incorporating CSNPs achieved 35% incremental oil recovery. The ASP combination that resulted in recovery rate of 39.17% was composed of sodium hydroxide (NaOH) at a concentration of 1.28 wt.%, PSC EOR 2.2 (0.98 wt.%), and a combined polymer consisting of HPAM (0.2 wt.%) and PYNPs nano-starch (0.6 wt.%). The second combination led to 35% recovery rate and involved NaOH also at concentration 1.28 wt.%, PSC HOMF (0.63 wt.%), and a combined polymer comprising from HPAM (0.2 wt.%) and CSNPs nano-starch (0.8 wt.%). These findings of this study highlighted the potential of this modified ASP flooding to enhance oil recovery in mature oilfields, thereby offering valuable insights for oil industry. Full article

Molecularly imprinted membranes (MIMs), the incorporation of a given target molecule into a membrane, are generally used for separating and purifying the effective constituents of various natural products. They have been in use since 1990. The application of MIMs has been studied in many fields, including separation, medicine analysis, solid-phase extraction, and so on, and selective separation is still an active area of research. In MIM separation, two important membrane performances, flux and permselectivities, show a trade-off relationship. The enhancement not only of permselectivity, but also of flux poses a challenging task for membranologists. The present review first describes the recent development of MIMs, as well as various preparation methods, showing the features and applications of MIMs prepared with these different methods. Next, the review focuses on the relationship between flux and permselectivities, providing a detailed analysis of the selective transport mechanisms. According to the majority of the studies in the field, the paramount factors for resolving the trade-off relationship between the permselectivity and the flux in MIMs are the presence of effective high-density recognition sites and a high degree of matching between these sites and the imprinted cavity. Beyond the recognition sites, the membrane structure and pore-size distribution in the final imprinted membrane collectively determine the selective transport mechanism of MIM. Furthermore, it also pointed out that the important parameters of regeneration and antifouling performance have an essential role in MIMs for practical applications. This review subsequently highlights the emerging forms of MIM, including molecularly imprinted nanofiber membranes, new phase-inversion MIMs, and metal–organic-framework-material-based MIMs, as well as the construction of high-density recognition sites for further enhancing the permselectivity/flux. Finally, a discussion of the future of MIMs regarding breakthroughs in solving the flux–permselectivity trade-off is offered. It is believed that there will be greater advancements regarding selective separation using MIMs in the future. Full article

This study aims to investigate the catalytic co-pyrolysis of beech wood with polystyrene as a synergic and catalytic effect on liquid oil production. For this purpose, a tubular semi-continuous reactor under an inert nitrogen atmosphere was used. Several zeolite catalysts were modified via incipient wetness impregnation using iron and/or nickel. The liquid oil recovered was analyzed using GC-MS for the identification of the liquid products, and GC-FID was used for their quantification. The effects of catalyst type, beechwood-to-polystyrene ratio, and operating temperature were investigated. The results showed that the Fe/Ni-ZSM-5 catalyst had the best deoxygenation capability. The derived oil was mainly constituted of aromatics of about 92 wt.% for the 1:1 mixture of beechwood and polystyrene, with a remarkably high heating value of around 39 MJ/kg compared to 18 MJ/kg for beechwood-based bio-oil. The liquid oil experienced a great reduction in oxygen content of about 92% for the polystyrene–beechwood 50-50 mixture in comparison to beechwood alone. The catalytic and synergetic effects were more realized for high beechwood percentages as a 75-25 beechwood–polystyrene mix. Regarding the temperature variation between 450 and 600 °C, the catalyst seemed to deactivate faster at higher temperatures, thus constituting a quality reduction in the pyrolytic oil in high-temperature ranges. Full article

The vapor–liquid equilibrium of the fluorobenzene–polystyrene binary polymer solution at 303.15 K was measured using a static pressure device. The vapor–liquid equilibrium of the fluorobenzene–n-octane–polystyrene ternary solution in a partial concentration range under normal pressure was determined using an improved Othmer equilibrium still, in which the octane concentration was low. Three activity coefficient models, poly-NRTL, UNIQUAC, and M-UNIQUAC-LBY, were utilized to correlate the experimental data of binary and ternary solutions, and the component activities of the fluorobenzene–n-octane–polystyrene solution at 303.15 K were predicted. A mathematical model based on the Stefan flow was developed to simulate the evaporation process of composite spherical droplets. The activity predicted by the activity coefficient model was used for numerical simulations, and compared with simulations using the activity following Raoult’s law. The comparative analysis revealed that simulations based on Raoult’s law and activity coefficient models yielded similar results when the mass fraction of fluorobenzene exceeded 0.6. However, in the later stages of evaporation, the calculations based on Raoult’s law predicted a 10% shorter drying time for fluorobenzene. The activity coefficient models provided a better approximation and exhibited similar droplet diameter shrinking behaviors to the actual evaporation process. Full article

Due to the increased application of lasers in different fields (industry, medicine, etc.), there is a growing need for new laser sources with good beam quality and variable emission wavelength. At the same time, for environmental reasons, the obtaining of novel eco-friendly active optical materials, such as those based on the deoxyribonucleic acid (DNA) biopolymer, with optimal light emission properties, is of high interest. The results obtained in this study of the temporal dependence of the transmittance and of the light emission in thin films of DNA–CTMA–Rhodamine 610 (at different Rhodamine concentrations) (DNA–CTMA–Rh610), when they are illuminated with continuous wave laser light at 532 nm (frequently used in the optical pumping of dye lasers), are presented and discussed. The transmittance results obtained for thin film samples are compared to those obtained for the DNA–CTMA–Rh610 solutions in butanol, from which the films have been made, and also with those obtained for Rh610 solutions in butanol with the same concentrations. The investigation was performed in order to assess the influence of the DNA-CTMA and of the green laser light at 532 nm wavelength on relevant chromophore properties such as light transmission and fluorescence emission. The results obtained revealed that the DNA–CTMA matrix has an active influence on the Rhodamine 610 emission, in the whole range of concentrations of the investigated samples. Full article

Microdevices have been actively implemented in chemical processes, such as in mixing and reactions. However, microseparation devices, excluding extraction devices, are still under development. In distillation, the use of microdevices has been expected to improve separation performance, as their large specific surface area enables a rapid vapor–liquid equilibrium and for large temperature gradients to be easily realized. In this study, improvements in throughput and product purities in microdistillation devices were achieved for ethyl acetate–toluene distillation. At low feedstock flow rates, ethyl acetate was successfully purified to 99.5 wt%. Although the performance decreased with increasing feedstock flow rate, by increasing the channel length, this performance decrease was suppressed even at high flow rates. The thickness of the channel was also important, and the highest performance was observed at the lowest thickness of 0.5 mm. A performance evaluation using the HETP showed that the efficiency was seven times higher than that of conventional packed column distillators. Full article

This study aims to approximate the optimum sulfate content of cement, applying maximization of compressive strength as a criterion for cement produced in industrial mills. The design includes tests on four types of cement containing up to three main components and belonging to three strength classes. We developed relationships correlating to 7- and 28-day strength with the sulfate and clinker content of the cement (CL), as well as the clinker mineral composition (tricalcium silicate, C₃S, tricalcium aluminate, C₃A). We correlated strength with the ratio %SO₃/CL and the molecular ratios MSO₃/C₃S and MSO₃/C₃A. The data processing stage proved that artificial neural networks (ANNs) fit the results’ distribution better than a parabolic function, providing reliable models. The optimal %SO₃/CL value for 7- and 28-day strength was 2.85 and 3.00, respectively. Concerning the ratios of SO₃ at the mineral phases for 28-day strength, the best values were MSO₃/C₃S = 0.132–0.135 and MSO₃/C₃A = 1.55. We implemented some of the ANNs to gain a wide interval of input variables’ values. Thus, the approximations of SO₃ optimum using ANNs had a relatively broad application in daily plant quality control, at least as a guide for experimental design. Finally, we investigated the impact of SO₃ uncertainty on the 28-day strength variance using the error propagation method. Full article

Significant amounts of oil remain in the reservoir after primary and secondary operations, and to recover the remaining oil, enhanced oil recovery (EOR) can be applied as one of the feasible options remaining nowadays. In this study, new nano-polymeric materials have been prepared from purple yam and cassava starches. The yield of purple yam nanoparticles (PYNPs) was 85%, and that of cassava nanoparticles (CSNPs) was 90.53%. Synthesized materials were characterized through particle size distribution (PSA), Zeta potential distribution, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The performance of PYNPs in recovering oil was better than CSNPs, as found from the recovery experiments. Zeta potential distribution results confirmed the stability of PYNPs over CSNPs (−36.3 mV for PYNPs and −10.7 mV for CSNPs). The optimum concentration for these nanoparticles has been found from interfacial tension measurements and rheological properties, and it was 0.60 wt.% for PYNPs and 0.80 wt.% for CSNPs. A more incremental recovery (33.46%) was achieved for the polymer that contained PYNPs in comparison to the other nano-polymer (31.3%). This paves the way for a new technology for polymer flooding that may replace the conventional method, which depends on partially hydrolyzed polyacrylamide (HPAM). Full article

Deoxyadenosine triphosphate (dATP) is an important biochemical molecule. In this paper, the synthesis of dATP from deoxyadenosine monophosphate (dAMP), catalyzed by Saccharomyces cerevisiae, was studied. By adding chemical effectors, an efficient ATP regeneration and coupling system was constructed to achieve efficient synthesis of dATP. Factorial and response surface designs were used to optimize process conditions. Optimal reaction conditions were as follows: dAMP 1.40 g/L, glucose 40.97 g/L, MgCl₂·6H₂O 4.00 g/L, KCl 2.00 g/L, NaH₂PO₄ 31.20 g/L, yeast 300.00 g/L, ammonium chloride 0.67 g/L, acetaldehyde 11.64 mL/L, pH 7.0, temperature 29.6 °C. Under these conditions, the substrate conversion was 93.80% and the concentration of dATP in the reaction system was 2.10 g/L, which was 63.10% higher than before optimization, and the concentration of product was 4 times higher than before optimization. The effects of glucose, acetaldehyde, and temperature on the accumulation of dATP were analyzed. Full article

Peroxyoxalate chemiluminescence (PO-CL) is one of the most popular cold light sources, yet the drawback of aggregation-caused quenching limits their use. Here, we report a new kind of efficient bifunctional emitter derived from salicylic acid, which not only exhibits typical aggregation-induced emission (AIE) character but also has the ability to catalyze the CL process under basic conditions based on base sensitivity. By taking advantage of these unique features, we successfully confine the CL process on the surface of solid bases and provide a high-contrast visualization of CL emission. This method allows most of the common basic salts like sodium carbonate to be invisible encryption information ink and PO-CL solution to be a decryption tool to visualize the hidden information. The current study opens up an appealing way for the development of multifunction CL emitters for information encryption and decryption applications. Full article

Clary Sage extracts are of industrial interest: in particular, sclareol shows a strong pharmaceutical potential. Supercritical fluid extraction was used to recover compounds of interest from a Salvia sclarea L. waxy n-hexane extract (“concrete”), using semi-continuous fractionation and a multi-step extraction strategy. Multi-step extraction experiments were carried out in two phases: the first one operated at 90 bar and 50 °C; the second one at 100 bar and 40 °C. GC-MS traces showed that during the first extraction step, only lighter compounds (e.g., monoterpenes, sesquiterpenes, and derivatives) were collected, whereas, in the second step, only sclareol and related compounds were recovered. By adjusting operating conditions (temperature and pressure), selective extraction of different families of compounds was accomplished, with no further need for post-processing of the products. Moreover, using two separators in series, the compounds of interest were fractionated from paraffins and, by changing the operating conditions, the extraction yield increased from about 6.0% to 9.3% w/w as CO₂ density increased. Full article

Alternate pumping chromatography is applied to obtain atomically precise glutathione-stabilized gold nanoclusters in high purity from synthesized mixtures. On the basis of anion exchange chromatography, the feasibility of isolating a single cluster, Au${}_{10}$GSH${}_{10}$, as well as two different clusters simultaneously (Au${}_{25}$GSH${}_{18}$ and Au${}_{29}$GSH${}_{20}$) is demonstrated. In addition, Au${}_{18}$GSH${}_{14}$, which is present only in trace amounts, is successfully enriched. A simple design procedure is proposed that allows using columns with different retention behavior. Successful experiments with large injection amounts confirm the potential of the concept for preparative-scale productions of high-quality nanoparticulate products. Full article

The effect of doping the bisphenol A diglycidyl ether (DGEBA)/m-xylylenediamine (mXDA) system with gold nanoparticles (AuNP) has been studied with differential scanning calorimetry (DSC), thermogravimetric analysis, dynamic mechanical analysis (DMA), and dielectric analysis (DEA). The evolved heat (ΔH_t), the glass transition temperature (T_g), and the associated activation energies of this relaxation process have been determined. Below a certain concentration of AuNPs (=8.5%, in mg AuNP/g epoxy matrix), T_g decreases linearly with the concentration of AuNPs, but above it, T_g is not affected. The degree of conversion α of this epoxy system was analyzed by the semiempirical Kamal’s model, evidencing that diffusion correction is required at high values of α. Activation energy values suggest that AuNPs can cause some impediments at the beginning of the crosslinking process (n-order mechanism). The slight difference between the initial decomposition temperature, as well as the temperature for which the degradation rate is at a maximum, for both systems can be accepted to be within experimental error. Mechanical properties (tension, compression, and bending tests) are not affected by the presence of AuNPs. Dielectric measurements show the existence of a second T_g at high temperatures, which was analyzed using the Tsagarapoulos and Eisenberg model of the mobility restrictions of network chains bound to the filler. Full article

It is well known that polar organic compounds, such as alcohols and polyols, exert an appreciable influence on water structure and thus have important effects on surfactant micellization. These substances are often used to modify the properties of surfactants in aqueous solutions, increasing the practical applications they have in diverse industries. In this work, the critical micelle concentration (CMC) of decyltrimethylammonium bromide (C₁₀TAB) in water and in 1,2-propanediol aqueous solutions was determined from both sound velocity and surface tension measurements as a function of surfactant concentration in the temperature range of (293.15 to 308.15) K. The critical micelle concentration of the surfactant increases as the concentration of 1,2-propanediol becomes higher, while the effect on temperature does not show important changes within the range considered. At the selected temperatures, the standard thermodynamic parameters of micellization suggests that the addition of 1,2-propanediol makes the micellization process less favorable. Thermodynamic analysis suggests that the micelle formation of C₁₀TAB is an entropy-driven process at the temperatures considered in this study. Full article