Application of response surface methodology for optimization of nano-TiO2 preparation using modified sol–gel method

Nano-sized TiO₂ was prepared using sol–gel process in microemulsion combining with solvent thermal technique. Response surface methodology was applied to optimize water/Triton X-100 molar ratio (w), n-hexanol/TX-100 molar ratio (m) and acetyl acetone/tetrabutyl titanate molar ratio (p) to influence the particle size (d), surface area (S), adsorptive capacity (G) and photocatalytic reaction rate (k). The relationship between responses (d, S, G and k) and preparation conditions (w, m and p) are followed second order polynomial equation and the coefficient is above 0.96. The smaller particle size, the bigger surface area it is accompanying the higher adsorption capacity and photocatalytic activity. The optimized experimental condition is w of 5.54, m of 7.41 and p of 0.44 with predicted particle size of 18.08 nm, surface area of 90.45 m²/g, adsorptive capacity of 9.63 mg/g and reaction rate of 0.12 min^?1.     

Application of response surface methodology for optimization of Orange Ⅱ removal by heterogeneous Fenton-like process using Fe_3O_4nanoparticles

In this study, Fe3O4nanoparticles（Fe3O4NPs） were successfully prepared via oxidation–precipitation method and characterized by scanning electron microscopy（SEM）, X-ray diffraction（XRD） and Fourier transform infrared spectroscopy（FT-IR）. The characterization results indicated that Fe3O4 NPs with regular crystal structure and a narrow of diameters had been synthesized successfully and had high purity. A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous Fe3O4 catalysts in the presence of H2O2. The response surface methodology（RSM） based on Box–Behnken design（BBD） was employed to design and optimize individual and interactive effects of the four main independent parameters（catalyst loading, initial p H, reaction temperature and H2O2concentration） on decolorization efficiency of Orange II. A significant quadratic model（p-value 〈0.0001, R2= 0.9369） was derived using analysis of variance（ANOVA）. Optimum conditions were catalyst loading of 1.5 g/L, initial p H of 2.7, reaction temperature of 42 8C and H2O2 concentration of 22 mmol/L, respectively. The predicted decolorization rate under the optimum conditions as determined by the proposed model was 99.55%. Confirmatory tests were carried out and the decolorization rate of 99.49% was observed under the optimum conditions, which agreed well with the model prediction.     

Anodizing parameters optimization of Ti–6Al–4V titanium alloy using response surface methodology

The present paper depicts application of response surface methodology (RSM) for optimizing the anodizing parameters of Ti–6Al–4V (TA6V) titanium alloy. Three operating parameters, i.e., voltage (V), temperature (T) and time (t), are designed as factors by using RSM design. Reliable regression models were established between the input parameters and the given responses, namely oxide thickness (e), Vickers hardness (Hv) and polarization resistance (R_p) with regression coefficients multiples of 0.940, 0.925, 0.865, respectively, indicating good agreement between the experimental values and those predicted using the quadratic model.The predicted values of V (42.67 V), t (45.9 min) and T (29.5 °C) are the optimal anodization combination leading to a TiO₂ layer with the best compromise between the oxide thickness (28.7 μm), Vickers hardness (321.90) and bias resistance (6.37 MΩ cm²). It was observed that the hardness characteristic is more affected by anodizing time and temperature, and less sensitive to voltage and parameter interactions. Polarization resistance is strongly influenced by voltage, modestly influenced by anodizing time and temperature, and less sensitive to parameter interactions. Moreover, higher anodizing parameters lead to higher thickness. Therefore, RMS could be a suitable method to optimize anodizing parameters of titanium alloys.     

Ion-pair-based surfactant-assisted dispersive liquid–liquid microextraction for the determination of cadmium in water samples: Optimization using response surface methodology

A sensitive, simple, and rapid method is developed for ion-pair-based surfactant-assisted dispersive liquid–liquid microextraction (IPSA-DLLME) and flame atomic absorption spectrometric determination of cadmium in water samples. In this procedure, trace amounts of Cd²⁺ were converted to CdI ₄ ^2– , and after addition of a tetrabutylammonium bromide (TBAB) solution as cationic surfactant the analyte was transformed to the ion-pair state. This cadmium species was extracted by fast injection of a solution containing 200 μL of chloroform and 800 μL of methanol as extraction and disperser solvents, respectively. The pH of the sample solution, concentration of iodide, TBAB amount, and the extractant volume were optimized using a 27-run Box–Behnken design with a triplicate central point. Under the optimized conditions, the calibration curve was linear in the range 1–200 μg L^–1 (R ² = 0.9959); with the detection limit (signal/noise = 3) of 0.28 μg L^–1. The relative standard deviations (RSD) for eight runs (Cd²⁺ = 10 μg L^–1) and enrichment factor were found to be 3.04 % and 50, respectively.     

Metal–organic framework assisted matrix solid-phase dispersion microextraction of saponins using response surface methodology

An efficient and simple metal–organic framework (MOF) assisted matrix solid-phase dispersion (MSPD) microextraction was developed for the extraction of the five saponins in P. ginseng leaves. The target analyses were detected by ultra high performance chromatography coupled with time-of-flight MS. Experimental conditions for MSPD microextraction were optimized by the Box–Behnken design of the response surface methodology. The optimal conditions were as follows: 20 mg adsorbent, 80% methanol–water solution for elution, 60 s grinding time, and the MOF-808 as the adsorbent. With the final optimized method, the calibration curves for five saponins showed good linearity (R² > 0.998) within range of 0.01–100 μg/mL. In addition, analytical recoveries ranged from 87.04 to 103.78%, with the RSD below 5%. The limit of detection and LOQ range from 0.087 to 0.114 μg/mL and 0.292 to 0.379 μg/mL, respectively. Compared with the traditional extraction method and published methods, the newly MOF-assisted MSPD extract exhibited higher extraction efficiency, simpler operation, and provided a cleaner extract with low consumption of organic reagents that was applied for rapid evaluation and quality control of active compounds from plants.     

Optimization of photocatalytic activity of immobilized TiO2–P25 nanoparticles in the removal of phenazopyridine using response surface methodology

Russian Journal of Applied Chemistry - The photocatalytic degradation of phenazopyridine (PhP) as a model contaminant from pharmaceutical compounds was studied using batch-recirculated photoreactor...     

Response surface methodology for modelling and determination of catechin in Pistachio green hull using surfactant-based dispersive liquid–liquid microextraction followed by UV–Vis spectrophotometry

A rapid and simple approach for the preconcentration and determination of catechin from pistachio green hull samples has been proposed by surfactant-assisted dispersive liquid–liquid microextraction followed by UV–Vis spectrophotometry (SADLLME/UV–Vis). This method involved the formation of a catechin complex with cetylpyridinium chloride (CPC) as cationic surfactant, and subsequently, DLLME was applied to extract the catechin–CPC complex into chloroform. Different parameters affected the extraction efficiency were optimized by central composite design (CCD) and response surface methodology (RSM). In optimum condition, the calibration curve was linear in the range of 0.4–5 µg mL^??1 of catechin with correlation coefficient of 0.9982. The relative standard deviation based on five replicated analyses of 1 µg mL^??1 catechin was 1.85%. The proposed method was successfully applied for preconcentration and determination of trace amounts of catechin in pistachio hull samples.     

Optimization of tensile properties of injection molded α-nucleated polypropylene using response surface methodology

Tensile properties are among the significant properties of isotactic polypropylene (iPP). The mechanical properties including the tensile properties are fairly dependent on the overall crystallinity and crystallite size and their distribution in molded product, type of crystal structure and testing conditions. In presence of α-nucleating agents, the crystallization rate and onset temperature of isotactic PP increase. In this paper, the role of externally added commercial α-nucleating agent HPN-20E (Milliken Inc.) on tensile properties was investigated with respect to tensile properties of pure iPP. The experimental part includes the use of design of experiment (DoE) - response surface methodology (RSM) with central composite design (CCD) having three factors namely mold temperature, melt temperature and injection rate. Two levels of each factor with six centre points and five numbers of replicates were selected. The nucleating agent, HPN-20E, was added 1.0% by wt. in iPP (mfr 11.0 g/10min) using a lab scale co-rotating twin screw extruder. The compounded pellets were dried at 85 °C in a circulating hot air oven for 24 h. The tensile samples (ASTM-638D, type-I) were molded on a micro-injection molding machine (make BabyPlast, Italy). The samples were tested for tensile properties on a universal testing machine (make Lloyds, USA). The measured responses were tensile strength (MPa), Young's modulus (MPa) and work to break (N.mm). The same experimental procedure was also followed for pure iPP and same responses were measured to set the baseline of experiment. The analysis of variance (ANOVA) tests unearth that mold and melt temperatures are highly interacting in nature. That is why previous attempts based on traditional way of varying one parameter at a time were not so successful to relate tensile properties with injection molding variables. The RSM tests resulted into useful quantitative relationship between the tensile properties and injection molding process variables.     

Droplet-based microfluidics for dose–response assay of enzyme inhibitors by electrochemical method

A simple but robust droplet-based microfluidic system was developed for dose–response enzyme inhibition assay by combining concentration gradient generation method with electrochemical detection method. A slotted-vials array and a tapered tip capillary were used for reagents introduction and concentration gradient generation, and a polydimethylsiloxane (PDMS) microfluidic chip integrated with microelectrodes was used for droplet generation and electrochemical detection. Effects of oil flow rate and surfactant on electrochemical sensing were investigated. This system was validated by measuring dose–response curves of three types of acetylcholinesterase (AChE) inhibitors, including carbamate pesticide, organophosphorus pesticide, and therapeutic drugs regulating Alzheimer's disease. Carbaryl, chlorpyrifos, and tacrine were used as model analytes, respectively, and their IC₅₀ (half maximal inhibitory concentration) values were determined. A whole enzyme inhibition assay was completed in 6 min, and the total consumption of reagents was less than 5 μL. This microfluidic system is applicable to many biochemical reactions, such as drug screening and kinetic studies, as long as one of the reactants or products is electrochemically active.     

Gas chromatographic–mass spectrometric methodology using solid-phase microextraction for the multiresidue determination of pesticides in surface waters

Solid-phase microextraction (SPME) coupled with gas chromatography–mass spectrometry (GC–MS) and selected ion monitoring (SIM) was used for the analytical determination of priority pesticide residues. Fibers coated with a 65-µm film thickness of polydimethylsiloxane divinylbenzene (PDMS-DVB) were used to extract 31 pesticides of different chemical groups. The quality parameters of the method demonstrated a good precision with detection limits of 1–56?ng/L. Linearity was controlled in the range of 0.1–50?µg/L. The proposed method was applied for the trace-level determination of the target pesticides in surface water samples including three rivers and one lake at the Epirus region (north-west Greece) for a period of one year. The results demonstrate the suitability of the SPME–GC–MS approach for the analysis of multi-residue pesticides in environmental water samples.     

Adapted numerical modelling of the Belousov–Zhabotinsky reaction

Adapted numerical schemes for the integration of differential equations generating periodic wavefronts have reported benefits in terms of accuracy and stability. This work is focused on differential equations modelling chemical phenomena which are characterized by an oscillatory dynamics. The adaptation is carried out through the exponential fitting technique, which is specially suitable to follow the apriori known qualitative behavior of the solution. In particular, we have merged this strategy with the information coming from existing theoretical studies and especially the observation of time series. Numerical tests will be provided to show the effectiveness of this problem-oriented approach.     

Determination of the activity of hydrogen peroxide scavenging by using blue-emitting glucose oxidase–stabilized gold nanoclusters as fluorescent nanoprobes and a Fenton reaction that induces fluorescence quenching

The authors describe a rapid and sensitive method for the determination of the activity of scavenging hydrogen peroxide in which glucose oxidase–stabilized gold nanoclusters (AuNCs) were employed as a fluorescent nanoprobe. The AuNCs are synthesized by a biomineralization process and display an intense blue fluorescence peaking at 450 nm and a quantum yield of 1.1% under 360–nm excitation. The Fenton reaction induces quenching of fluorescence, and this effect can be used to determine H₂O₂ in the 0.5 to 10 μmol?L^?1 concentration range. The substances displaying H₂O₂ scavenging activity prevent quenching and thus restore fluorescence. The intensity of restored fluorescence is directly related to the H₂O₂ scavenging activity of the antioxidant. The method was applied to the determination of the H₂O₂ scavenging activity of the model antioxidants ascorbic acid and tartaric acid which gave IC₅₀ values of 7.4 and 19.1 μmol?L^?1, respectively.

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Graphical abstract Blue-emitting gold nanoclusters (AuNCs) were prepared by using GOx as both the reducing and stabilizing agents. The Fenton reaction induces quenching of fluorescence of the AuNCs, and is employed for fluorometric measurement of the H₂O₂ scavenging activity of the model antioxidants ascorbic acid and tartaric acid.

     

Preparation of uranium oxide powder for nuclear fuel pellet fabrication with uranium peroxide recovered from uranium oxide scraps by using a carbonate–hydrogen peroxide solution

This work studied a way to reclaim uranium from contaminated UO₂ oxide scraps as a sinterable UO₂ powder for UO₂ fuel pellet fabrication, which included a dissolution of the uranium oxide scraps in a carbonate solution with hydrogen peroxide and a UO₄ precipitation step. Dissolution characteristics of reduced and oxidized uranium oxides were evaluated in a carbonate solution with hydrogen peroxide, and the UO₄ precipitation were confirmed by acidification of uranyl peroxo–carbonate complex solution. An agglomerated UO₄ powder obtained by the dissolution and precipitation of uranium in the carbonate solution could not be pulverized into fine UO₂ powder by the OREOX process, because of submicron-sized individual UO₄ particles forming the agglomerated UO₄ precipitate. The UO₂ powder prepared from the UO₄ precipitate could meet the UO₂ powder specifications for UO₂ fuel pellet fabrication by a series of steps such as dehydration of UO₄ precipitate, reduction, and milling. The sinterability of the reclaimed UO₂ powder for fuel pellet fabrication was improved by adding virgin UO₂ powder in the reclaimed UO₂ powder. A process to reclaim the contaminated uranium scraps as UO₂ fuel powder using a carbonate solution was finally suggested.     

Optimization of ultrasonic-assisted extraction of three main taxoids in the twigs of Taxus × media using multi-objective response surface methodology

A multi-objective response surface methodology (RSM) based on a desirability function analysis (DFA) was used to model and optimize the operational parameters of ultrasonic-assisted extraction of three main taxoids in the twigs of Taxus × media. Liquid–solid ratio, extraction temperature, extraction time, and ultrasonic power were chosen as four independent variables, with three objective variables considered: the extraction yields of 10-deacetylbaccatin III (10-DAB III), cephalomannine and paclitaxel. Under the predicted conditions with the highest “desirability’’, compared with the predicted value, the goodness of fit for the experiment extraction yields of 10-DAB III, cephalomannine and paclitaxel was 97.36, 100.81, and 97.46%, respectively. Analysis of variance (ANOVA), regression analysis, and verification test indicated a satisfactory correlation between the experimental data and predicted values. These results showed that RSM and DFA were good methods to solve the problem of multi-objective optimization.     

Mn3O4–Au nanozymes as peroxidase mimic and the surface-enhanced Raman scattering nanosensor for the detection of hydrogen peroxide

The artificial enzyme-mimicking system using nanomaterials has attracted significant research interest in chemical and biological sensing for industrial and environmental applications. Mn₃O₄ nanostructure serves as an effective catalyst in oxidation and reduction reactions that mimic natural peroxidase enzymes. In this study, we synthesized Mn₃O₄–Au spindle nanocomposites (Mn₃O₄–Au SNCs) stabilized by L-cysteine using a simple hydrothermal reduction. The enzyme-mimicking peroxidase activity of these Mn₃O₄–Au SNCs with hydrogen peroxide (H₂O₂) was investigated in the presence of a chromogenic substrate, 3,3′,5,5′-tetramethylbenzidine that catalyzed reduction of H₂O₂ in water and milk giving rise to a blue color inferring the nanozyme activity of Mn₃O₄–Au SNCs. The exceptional enzyme-like catalytic activity of Mn₃O₄–Au SNC probes later proved to be excellent surface-enhanced Raman scattering (SERS) sensor nanoprobes for sensitive H₂O₂ detection over a wide concentration range from 0.005 to 10 μM. The developed Mn₃O₄–Au SERS sensor exhibited a lower detection limit (LoD) of 2 nM in water and 0.6 μM in spiked milk indicating sensitivity for H₂O₂ detection with excellent selectivity, reproducibility, and long-term stability. The developed Mn₃O₄–Au nanoprobes demonstrated unique combination of properties with visual and SERS methods for sensitively detecting H₂O₂ in food, overcoming limitations of existing H₂O₂ sensors. The developed SERS method using nanozymes potentially be extended to detecting a variety of other redox chemicals or explosives in industries, environments, and biomedical fields.     

Application of dispersive liquid–liquid microextraction for the determination of donepezil in urine by HPLC using a core–shell column

A rapid and novel method combining dispersive liquid–liquid microextraction and high-performance liquid chromatography coupled with fluorescence detection was developed for the determination of donepezil in human urine. Parameters affecting extraction efficiency and chromatographic determination, such as the type and volume of the extraction and disperser solvent, pH of sample for dispersive liquid–liquid microextraction, mobile-phase composition, pH, column oven temperature, and flow rate for chromatographic determination, were evaluated and optimized. Using a C₁₈ core–shell column (7.5 × 4.6?mm, 2.7?μm), the determination of donepezil was accomplished within 5?min. Under optimum conditions, developed method was linear in the range of 0.5–25?ng?mL^?1 with the correlation coefficient >0.99. Limit of detection was 0.15?ng?mL^?1. The relative standard deviation at three concentration levels (2, 12.5, and 20?ng?mL^?1) was less than 11% with accuracy in the range of 96.9–102.8%. The results of this study demonstrate that the use of dispersive liquid–liquid microextraction and core–shell column can be considered as a powerful tool for the analysis of donepezil in human urine.     

Heterogeneous oxidation of alcohols with hydrogen peroxide catalyzed by polyoxometalate metal–organic framework

HSiW-MOF, PMo-MOF, HPMo-MOF and PW-MOF were synthesized and characterized by elemental analysis, UV–Vis, FT-IR, cyclic voltammetry and XRD. These compounds were used as catalyst for the selective oxidation of alcohols by hydrogen peroxide. Within them, PW-MOF showed a higher catalytic activity compared to other catalysts in a similar reaction condition. Therefore, PW-MOF catalyst system was successfully used for the selective oxidation of the benzylic, linear and secondary alcohols to the corresponding aldehydes and ketones. Also, allylic alcohols were converted to the corresponding aldehydes with high conversion and significant selectivity. Moreover, PW-MOF was stable to leaching, behaved as true heterogeneous catalysts, easily recovered by filtration, and reused four times with the preserve of the catalytic performance.     

Silica aerogel–iron oxide nanocomposites: recoverable catalysts for the oxidation of alcohols with hydrogen peroxide

Various aerogels of silica gel doped with Fe₂O₃ were prepared by sol–gel method. They were calcined to produce nanoparticle solids. The nanosized mixed oxides were active in the oxidation of alcohols and produced carbonyl compounds in very good to excellent yields using hydrogen peroxide.     

A full probabilistic analysis of a randomized kinetic model for reaction–deactivation of hydrogen peroxide decomposition with applications to real data

Journal of Mathematical Chemistry - The classical kinetic equation has been broadly used to describe reaction and deactivation processes in chemistry. The mathematical formulation of this...