Project description:Lignin is generally considered to be a renewable and sustainable resource of aromatic chemicals. However, the depolymerization of Kraft lignin (KL) for the production of selective phenolic monomers presents a significant challenge due to its highly recalcitrant nature. Therefore, in this work, we investigated the effect of metal sites and acid active sites on Mo/SBA-15, Co/SBA-15 and CoMo/SBA-15 catalysts in supercritical ethanol for the depolymerization of KL to produce phenolic monomers. Ethanol was used as a hydrogen donor solvent instead of using external hydrogen. Results showed that the bimetallic CoMo/SBA-15 catalyst exhibited significantly higher catalytic activity compared to the monometallic, Co/SBA-15, Mo/SBA-15 or bare SBA-15. The highest phenolic monomers yield of 27.04 wt% was achieved at 290 °C for 4 h over CoMo/SBA-15 catalyst. The inter-unit linkages such as β-O-4', β-β and α-O-4' in lignin were considerably cleaved during the catalytic depolymerization in supercritical ethanol. Meanwhile, higher functionality of carbonyl compounds was present in the non-catalytic bio-oil, while more alkylated phenols were produced over CoMo/SBA-15 catalyst. The major phenolic monomers identified in the catalytic bio-oil were 4-ethylguaiacol (9.15 wt%), 4-methylguaiacol (6.80 wt%), and 4-propylguaiacol (2.85 wt%). These findings suggest that the metal sites and abundant acid active sites of CoMo/SBA-15 had a synergistic effect toward the degradation of different linkages of lignin and production of selective phenolic monomers in bio-oils.
Project description:The current work studies the reductive catalytic depolymerization (RCD) of lignin from a novel semi-industrial process. The aim was to obtain aromatic mono-, di-, tri-, and tetramers for further valorization. The substrate and products were characterized by multiple analytical methods, including high pressure size-exclusion chromatography (HPSEC), gas chromatography-mass spectrometry, GC-flame ionization detector (FID), GC-FID/thermal conductivity detector (TCD), and NMR. The RCD was studied by exploring the influence of different parameters, such as lignin solubility, reaction time, hydrogen pressure, reaction temperature, pH, type and loading of the catalyst, as well as type and composition of the organic/aqueous solvent. The results show that an elevated temperature, a redox catalyst, and a hydrogen atmosphere are essential for the depolymerization and stability of the products, while the reaction medium also plays an important role. The highest obtained mono- to tetramers yield was 98% and mono- to dimers yield over 85% in the liquid phase products. The reaction mechanisms influenced the structure of the aliphatic chain in the monomers, but left the phenolic structure along with the methoxy groups largely unaltered. The current work contributes to the development and debottlenecking of the novel and sustainable overall process, which utilizes efficiently all the fractions of wood, in line with the principles of green engineering and chemistry.
Project description:The ion/molecular imprinting technique is an efficient method for developing materials with high adsorption selectivity. However, it is still difficult to obtain an imprinted adsorbent with desirably high selectivity when the preparation processes are not well designed and optimized. In this present work, a chitosan-based ion-imprinted adsorbent was optimally prepared through Box-Behnken experimental design to achieve desirably high selectivity for Pd anions (PdCl4 2-) from aqueous solutions with high acidity. The dosage of epichlorohydrin (ECH) used in the first and second steps of cross-linking as well as the pH of the imprinting reaction medium is likely one of the key factors affecting the selectivity of the synthesized ion-imprinted chitosan adsorbent, which were selected as factors in a three-level factorial Box-Behnken design. As a result, the effects of these three factors on Pd(II) selectivity were able to be described by using a second-order polynomial model with a high regression coefficient (R 2; 0.996). The obtained optimal conditions via the response surface methodology were 0.10% (v/v) of first cross-linking ECH, an imprinting pH of 1.0, and 1.00% of second cross-linking ECH. Competitive adsorption was performed to investigate the selectivities of the ion-imprinted chitosan adsorbents prepared under the optimal conditions. The selectivity coefficient of Pd(II) versus Pt(IV) (βPd/Pt) of the Pd(II)-imprinted adsorbent was 115.83, much greater than that of the chitosan adsorbent without imprinting and various reported selective adsorbents. Therefore, the Box-Behnken design can be a useful method for optimizing the synthesis of ion-imprinted adsorbents with desirably high adsorptive selectivity for precious metals.
Project description:In view of the defects in the previous detection of cuaminosulfate, which only focused on the analysis of copper ions, there is currently no analysis method available to determine the actual state of cuaminosulfate as chelated or bound. In order to investigate the dissipation and terminal residues in soil and watermelon of cuaminosulfate for food safety and environmental risk, a highly effective technique was developed to detect cuaminosulfate residues in watermelon and soil, and field experiments were conducted in China. After single-factor experiments, residual cuaminosulfate in samples was extracted by pure water, purified using a liquid-liquid approach combined with a dispersive solid-phase extraction, and detected by liquid chromatography tandem mass spectrometry (LC-MS/MS). The Box-Behnken design (BBD) study was used to find the optimal solutions for the time of liquid-liquid purification, the amount of extraction solvent, and the amounts of cleanup sorbents for the analytical method. The average recovery of the method was in the range of 80.0% to 101.1%, the average relative standard deviation (RSD) was 5.3-9.9%, and the detection limit was lower than 0.05 mg/kg. The BBD study not only improved the extraction rate of the method, but also saved time and was operated easily. The final residues of cuaminosulfate in watermelon at different sampling intervals were all lower than 0.05 mg/kg under field conditions. The cuaminosulfate in soils dissipated following exponential kinetics, with half-life values in the range of 9.39 to 12.58 days, which varied by different locations. Based on the validated method, food safety residues and soil residues can be determined rapidly and accurately.
Project description:Concerns about the widespread use of pesticides have been growing due to the adverse effects of chemicals on the environment and human health. It has prompted worldwide research into the development of a replacement to chemical disinfection of soil. The efficiency of steam sterilization, an alternative to chemical methods, has improved as technology has advanced, and the Agricultural Research and Extension Service in Korea recommends the use of steam sterilization. However, few studies have been conducted on the effects and operating conditions of high-temperature steam disinfection. In this study, we present the optimum operating conditions of a high-steam disinfector, to maximize the cost-effectiveness and removal efficiency of total nematodes and total bacteria in soil using the Box-Behnken design. The experimental data were fitted to a second-order polynomial equation using multiple regression analysis, with coefficients of determination (R2) for each model of 0.9279, 0.9678, and 0.9979. The optimum conditions were found to be a steam temperature of 150.56 °C, running speed of 1.69 m/min, and spray depth of 15.0 cm, with a corresponding desirability value of 0.8367. In the model, these conditions cause the prediction of the following responses: nematode removal efficiency of 93.99%, bacteria removal efficiency of 97.49%, and oil consumption of 70.49 mL/m2. At the optimum conditions for the steam disinfector, the removal efficiencies of nematodes and bacteria were maximized, and the oil consumption was minimized. The results of our study can be used as basic data for efficient soil disinfection using high-temperature steam.
Project description:ZnO photocatalysts were synthesized via solvothermal method and a reduced experimental design (Box-Behnken) was applied to investigate the influence of four parameters (temperature, duration, composition of the reaction mixture) upon the photocatalytic activity and the crystal structure of ZnO. The four parameters were correlated with photocatalytic degradation of methyl orange and the ratio of two crystallographic facets ((002) and (100)) using a quadratic model. The quadratic model shows good fit for both responses. The optimization experimental results validated the models. The ratio of the crystal facets shows similar variation as the photocatalytic activity of the samples. The water content of the solvent is the primary factor, which predominantly influence both responses. An explanation was proposed for the effect of the parameters and how the ratio of (002) and (100) crystal facets is influenced and its relation to the photocatalytic activity. The present research laconically describes a case study for an original experimental work, in order to serve as guideline to deal with such complicated subjects as quantifying influence of synthesis parameters upon the catalytic activity of the obtained ZnO.
Project description:In this study, a CoO-Fe2O3/SiO2/TiO2 (CIST) nanocomposite was synthesized and utilized as an adsorbent to remove methylene blue (MB), malachite green (MG), and copper (Cu) from aqueous environments. The synthesized nanocomposite was characterized using field emission scanning electron microscopy (FE-SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). Input parameters included pH (3-10), contact time (10-30 min), adsorbent amount (0.01-0.03 g), and pollutant concentration (20-60 mg L-1). The effects of these parameters on the removal process efficiency were modeled and optimized using the response surface methodology (RSM) based on the Box-Behnken design (BBD). The RSM-BBD method demonstrated the capability to develop a second-degree polynomial model with high validity (R2 ˃ 0.99) for the removal process. The optimization results using the RSM-BBD method revealed a removal efficiency of 98.01%, 93.06%, and 88.26% for MB, MG, and Cu, respectively, under optimal conditions. These conditions were a pH of 6, contact time of 10 min, adsorbent amount of 0.025 g, and concentration of 20 mg L-1. The synthesized adsorbent was recovered through five consecutive adsorption-desorption cycles using hydrochloric acid. The results showed an approximately 12% reduction from the first to the seventh cycle. Also, MB, MG, and Cu removal from real water samples in optimal conditions was achieved in the range of 81.69-98.18%. This study demonstrates the potential use of CIST nanocomposite as an accessible and reusable option for removing MB, MG, and Cu pollutants from aquatic environments.
Project description:This work aimed to obtain poly(glycerol citraconate) (PGCitrn) for biomedical applications, analyze the obtained polyester by spectroscopic methods, and optimize its preparation. Polycondensation reactions of glycerol and citraconic anhydride were carried out. It was provided that the results in the reaction are oligomers of poly(glycerol citraconate). Optimization studies were carried out based on the Box-Behnken design. The input variables in this plan were the ratio of functional groups, temperature, and time and occurrence in coded form: -1, 0, or 1. Three output variables were optimized: the degree of esterification, the percentage of Z-mers, and the degree of carboxyl group conversion; they were determined by titration and spectroscopic methods. The optimization criterion was to maximize the values of output variables. A mathematical model and an equation describing it were determined for each output variable. The models predicted the experimental results well. An experiment was conducted under determined optimal conditions. The experimental results were very close to the calculated values. Poly(glycerol citraconate) oligomers with an esterification degree of 55.2%, a Z-mer content of 79.0%, and a degree of rearrangement of carboxyl groups of 88.6% were obtained. The obtained PGCitrn can serve as a component of an injectable implant. The obtained material can be used to produce nonwoven fabrics (with the addition of PLLA, for example), which can be subjected to a cytotoxicity test which can then serve as a dressing material.
Project description:At present, there are too few organ and tissue donors. Due to the needs of the medical market, scientists are seeking new solutions. Those can be found in tissue engineering by synthesizing synthetic cell scaffolds. We have decided to synthesize a potential UV-crosslinked bio-ink for 3D printing, poly(1,4-butanediol itaconate), in response to emerging needs. Diol polyesters are commonly investigated for their use in tissue engineering. However, itaconic acid makes it possible to post-modify the obtained polymer via UV-crosslinking. This work aims to optimize the synthesis of poly(1,4-butanediol itaconate) in the presence of a catalyst, zinc acetate, without using any toxic reactant. The experiments used itaconic acid and 1,4-butanediol using the Box-Behnken mathematical planning method. The input variables were the amount of the catalyst used, as well as the time and temperature of the synthesis. The optimized output variables were the percentage conversion of carboxyl groups, the percentage of unreacted C=C bonds, and the product's visual and viscosity analysis. The significance of the varying synthesis parameters was determined in each statistical model. The optimum conditions were as follows: amount of catalyst 0.3%nCOOH, reaction time 4 h, and temperature 150 °C. The temperature had the most significant impact on the product characteristics, mainly due to side reactions. Experimentally developed models of the polymerization process enable the effective synthesis of a polymer "tailor-made" for a specific application.
Project description:Felbinac, an active pharmaceutical ingredient (API) used clinically for the treatment of osteoarthritis, has poor solubility. Felbinac cataplasm product design was investigated using rheological and mechanical analyses. Experiments using a response surface methodology based on Box⁻Behnken design (BBD) incorporated three independent variables: the proportions of partially neutralized polyacrylate (NP800), dihydroxyaluminum aminoacetate (DAAA), and felbinac. Statistically significant quadratic models obtained using BBD demonstrated optimal NP-800, DAAA, and felbinac cataplasm proportions of 4.78⁻5.75%, 0.30⁻0.59%, and 0.70⁻0.90%, respectively. Felbinac cataplasms exhibited "gel-like" mechanical property with predominantly elastic behavior. Rheological studies correlated increasing NP-800 and DAAA concentrations with increased complex modulus (G*) values that were inversely related to peeling strength. Frequency sweep and creep tests revealed decreasing tan θ values with increasing NP-800 and DAAA concentrations. G' and G" values were higher for higher NP-800 and DAAA levels, although G" values decreased with increasing DAAA concentration. Response surface methodology was applied to develop mathematical models. Variance analysis showed that the quadratic model effectively predicted felbinac and matrix material interactions, with two verification samples upholding model predictions. Relative errors between predicted and measured G* values were 3.28% and 1.10% and for peeling strength were 1.24% and 5.59%, respectively. In conclusion, rheological and mechanical analyses of felbinac cataplasms using BBD permits optimization of cataplasms as topical drug delivery vehicles.