In the present study, a novel pH-sensitive hydrogel composite of pectin-grafted-poly (acrylic acid-co-itaconic acid)/MWCNTs- COOH was prepared by using graft copolymerization of acrylic acid and itaconic acid on pectin backbone with incorporation of MWCNTS- COOH. The prepared hydrogel composite has been employed for the adsorption and controlled release of the diclofenac sodium (DS) drug. The hydrogel composite was characterized by the analysis methods: FTIR, XRD, SEM, and TGA to analyze structural characteristics before and after DS drug adsorption. The swelling ratio of the hydrogel composite was investigated at different pH values from pH 1.2 to 10. According to the results, the swelling ratio of the hydrogel composite was found 4195% at pH 7.4. Adsorption process parameters such as pH, contact time, adsorbent dose, and temperature were investigated and found to have a significant influence on DS drug adsorption. The maximum DS drug loading through adsorption of 91% was obtained at pH 3, adsorbent dose of 0.05 g, contact time of 150 min, and temperature of 15 °C. The adsorption isotherm and kinetic results were well-fitted to Freundlich and second-order models. Thermodynamic parameters including changes in Gibb’s free energy, enthalpy, and entropy suggested that the adsorption of DS drug onto hydrogel composite was a spontaneous and exothermic process. The in vitro drug release experiment showed that the cumulative release of DS drug from hydrogel composite after 35 h was significantly higher in simulated intestinal fluid at pH 7.4 than in simulated gastric fluid at pH 1.2.
pH plays a pivotal role in influencing various aspects of proton-coupled electron transfer (PCET) reactions in electrochemical systems. These reactions are affected by pH in terms of mass transport, electrochemical double layer (EDL) structure, and surface adsorption energy, all of which impact the overall electrochemical processes. This review article aims to provide a comprehensive understanding of the research progress made in elucidating the effects of pH on different electrochemical reactions, the hydrogen evolution reaction/hydrogen oxidation reaction (HER/HOR), oxygen reduction reaction/oxygen evolution reaction (ORR/OER), and carbon dioxide reduction reaction ( CO2RR). To embark on this endeavor, we have conducted a bibliometric analysis to clearly outline of the research trends and advancements in the field concerning the pH effects. Subsequently, we present a systematic overview of the mechanisms governing these reactions, with a special focus on pH’s influence on both the proton and electron aspects. We conclude by discussing the current challenges in this area and suggesting future research avenues that could further our understanding of pH's role in electrochemical reactions.
A semi-natural composite of κ-carrageenan and bentonite, two natural biopolymers, was synthesized through free radical polymerization. This synthesis aimed to obtain a biodegradable, biocompatible, and swellable composite that is environmentally friendly. The components used in this synthesis are readily available, making it economically feasible and promising for potential biomedical applications. The composite is pH-responsive and intended for oral delivery of metformin hydrochloride and aminophylline, which have low bioavailability and undesirable side effects, respectively. The organic composite exhibits the advantage of reducing drug release in the acidic gastric medium. This composite is a stimuli-responsive polymeric material that has garnered significant attention in recent years for its application in oral drug delivery systems. These materials enable site-specific and controlled drug release while minimizing toxicity. The carrageenan-g-poly(acrylamide-co-acrylic acid)/bentonite composite was characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM), which confirmed the successful synthesis of the composite. The swelling behaviour and point of zero charge of the composite were studied at different pH values, which showed a strong influence on the swelling properties of the composite. The drug loading capacity of the composite was measured at pH 5.3, and it was 70.60 mg/g for metformin and 95.66 mg/g for aminophylline at pH(3). The in vitro release profile of both drugs from the composite was also affected by the ionic strength, and it exhibited a lower release rate with higher salt concentration. The maximum release percentage of the drugs from carrageenan-g-poly(acrylic acid-acrylamide)/bentonite in simulated gastric, intestinal, and colon fluids was achieved within 40 h. The maximum release was 80% for metformin in simulated intestinal fluid (SIF) and 75% for aminophylline after 40 h.
Chelating agents like ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and nitrilotriacetic acid (NTA) find extensive application in the removal of residual substances due to their high stability constants with a wide range of metal ions. They also play a crucial role in nuclear decontamination operations aimed at eliminating metallic radionuclides such as 60Co, 90Sr, and 239Pu. However, improper disposal of chelated radioactive waste can lead to significant increases in radionuclide migration rates from disposal sites. Therefore, it is imperative to comprehend the behavior of chelating agents under varying conditions, including pH, temperature, and metal ion concentrations. In this study, we present the results of a pH-dependent composition analysis of nickel-chelate complexes using UV-Vis spectrophotometry. Nickel (Ni) serves as an ideal metal ion for investigating its interactions with chelating agents due to its solubility over a wide pH range and high stability constants with all three chelating agents mentioned earlier. Initially, UV-Vis spectra of Ni-EDTA, Ni-DTPA, and Ni-NTA complexes were recorded at various pH levels. We assigned absorption maxima and compared our findings with existing literature on each Ni-chelate complex. Furthermore, we examined mixed samples of all three complexes, varying the pH to monitor changes in composition. The results and their implications will be presented in our poster presentation.
Chelating agents, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and nitrilotriacetic acid (NTA) are widely used in industry and agriculture as water softeners, detergents, and metal chelating agents. In wastewater treatment plants, a significant amount of chelating agents can be discharged into natural waters because they are difficult to degrade. Since those compounds affect the mobility of radionuclides or heavy metals in decontamination operations at nuclear facilities and radioactive waste disposal, quantification of the amount of ligand is very important for safe nuclear waste management. To predict the behavior of the main complexation in sample matrices of radioactive wastes, it is essential to evaluate the distribution of the metal-chelating species and their stabilities in order to develop analytical techniques for quantifying chelating agents. We have investigated to collect information on the pH speciation of metal chelation and the stability constants of metal complexes depending on three chelating agents (EDTA, DTPA, and NTA). For example, Zhang’s group recently reported that the initial coordination pH of Cu(II) and EDTA4− is delayed with the addition of Fe(III), and the pH range for the stable existence of [Cu(EDTA)]2− is narrowed compared to when it is alone in the sample matrix. The addition of Fe(III) clearly impacts the chemical states of the Cu(II)-EDTA solution. Additionally, Eivazihollagh’s group demonstrated differences in the speciation and stability of Cu(II) species between Cu(II) and three chelating ligands (EDTA, DTPA, and NTA). This study will be greatly helpful in identifying the sample matrix for binding major chelating agents and metals as well as developing chemically sample pretreatment and separation methods based on the sample matrix. Finally, these advancements will enable reliable quantitative analysis of chelating agents in decommissioning radioactive wastes.
Bisphenol-A, also known as BPA, is commonly used as a building block for epoxy and polycarbonate plastics. However, it has been recently identified as a major source of water pollution due to its release into the water from plastic products. BPA-based resins can also contaminate the water with high concentrations of BPA, which can enter the water bodies through production units and wastewater discharge. Photocatalysis, particularly the photo-Fenton process, is an effective method for wastewater treatment and degrading pollutants. Titanium dioxide (TiO2) is usually chosen based on its high photocatalytic properties and high performance. However, its wide band gap energy is a major issue for the photocatalytic process. This means that the catalyst can only exhibit high photocatalytic performance under UV-light irradiation and usually requires an acidic pH, which limits its use. In order to address the aforementioned issues, a visible-light photoactive photo-Fenton reaction has been successfully developed to degrade bisphenol A at natural pH using H2O2. The process was highly efficient, achieving complete degradation of phenol in just three hours of visible light irradiation with Cu-MOF. This environmentally friendly Fenton process has the advantage of occurring at natural pH levels with the presence of H2O2, providing a new perspective for efficient degradation. The photocatalyst was characterized using single X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), and UV–vis diffuse reflectance spectroscopy (DRS).
The mobility of radionuclides in the subsurface environment is governed by a interaction of radioactivity characteristics and geochemical conditions with adsorption reactions playing a critical role. This study investigates the characteristics and mechanisms of radionuclides adsorption on site media in viewpoint of nuclear safety, particularly focusing on the potential effect of seawater infiltration in coastal site near nuclear power plant. Seawater intrusion alters the chemistry in groundwater, including parameters such as pH, redox potential, and ionic strength, thereby affecting the behavior of radionuclides. To assess the safety of site near nuclear power plant and the environmental implications of nuclide leakage, this research conducted various experiments to evaluate the behavior of radionuclides in the subsurface environment. High distribution coefficients (50-2,500 ml/g) were observed at 10 mg/L Co, with montmorillonite > hydrobiotite > illite > kaolinite. It decreased with competing cations (Ca2+) and was found to decrease significantly by 90% with a decrease in pH to 4. It is believed that the adsorption capacity of cationic radionuclides decreases significantly as the clay mineral surface becomes less negatively charged. For Cs, the distribution coefficient (180-560 ml/g) was higher for montmorillonite > hydrobiotite > illite > kaolinite. Compared to Co, it was found to be less influenced by pH and more influenced by competing cations. For Sr, the distribution coefficient (100-380 ml/g) was higher in the order of hydrobiotite > montmorillonite > illite > kaolinite. Compared to Cs, it was found to be less affected by pH and also less affected by the effect of competing cations compared to Cs. Seawater samples from Gampo and Uljin site near Nuclear Power Plant in Korea were analyzed to determine their chemical composition, which was subsequently used in adsorption experiments. Additionally, the seawater-infiltrated groundwater was synthesized in laboratory according to previous literature. The study focused on the adsorption and behavior of three key radionuclides such as cesium, strontium, and cobalt onto four low permeability media (clay minerals) such as kaolinite, illite, hydrobiotite, and montmorillonite known for their high adsorption capacity at a site of nuclear power plant. At concentrations of 5 and 10 mg/L, the adsorption coefficients followed the order of cobalt > cesium > strontium for each radionuclide. Notably, the distribution coefficient (Kd) values exhibited higher values in seawater-infiltrated groundwater environments compared to seawater with relatively high ionic strength. Cobalt exhibited a substantial adsorption coefficient, with a marked decrease in Kd values in seawater conditions due to elevated ionic strength. In contrast, cesium displayed less dependency on seawater compared to other radionuclides, suggesting distinct adsorption mechanisms, possibly involving fractured edge sites (FES) in clay. Strontium exhibited a significant reduction in adsorption in seawater compared to groundwater in all Kd sorption experiments. The adsorption data of cobalt, cesium, and strontium on clay minerals in contact with seawater and seawater-infiltrated solutions offer valuable insights for assessing radioactive contamination of groundwater beneath coastal site near nuclear power plant sites. This research provides a foundation for enhancing the safety assessment protocols of nuclear power plant sites, considering the potential effects of seawater infiltration on radionuclide behavior in the subsurface environment.
In this study, we synthesized pH-controlled resorcinol-formaldehyde (RF) gels through the polymerization of two starting materials: resorcinol and formaldehyde. The prepared RF gels were dried using an acetone substitution method, and they were subsequently carbonized under nitrogen atmosphere to obtain carbon xerogels (CX_Y) prepared at different pH (Y). The carbon xerogels were utilized as active materials for coin-type organic supercapacitor electrodes to investigate the influence of pH on the electrochemical properties of the carbon xerogels. The carbon xerogels prepared at lower pH (CX_9.5 and CX_10) exhibited sufficient particle growth, with a three-dimensional network of particles during the RF gel formation, resulting in the development of abundant mesopores. Conversely, the carbon xerogels prepared at higher pH (CX_11 and CX_12) retained densely packed structures of small particles, leading to pore collapse and low specific surface areas. Consequently, CX_9.5 and CX_10 showed high specific surface areas, and provided ample adsorption sites for the formation of electric double layers with electrolyte ions. Moreover, the three-dimensional particle network in CX_9.5 and CX_10 significantly enhanced electrical conductivity. The presence of well-developed mesopores in these materials further facilitated the effective transport of electrolyte ions, contributing to their superior performance as organic supercapacitor electrodes. This study confirmed that pH-controlled carbon xerogels are one of the promising active materials for organic supercapacitor electrodes. Furthermore, we concluded that pH during RF gel formation is a crucial factor determining the electrode performance of the carbon xerogels, highlighting the need for precise pH control to obtain high-performance carbon xerogel electrodes.
본 연구에서는 부산신항에서 스크러버를 장착한 선박이 세정수를 배출하였을 때 인근 해역에 미치는 영향을 검토하기 위해 확산예측을 수행하였다. 세정수에 포함된 용존무기탄소(DIC)의 농도를 통제한 채로 세정수의 pH 조건별로 해역에 미치는 영향을 대조기 와 소조기로 나누어 평가하였다. 선박 1대에서 24시간 동안 세정수를 배출할 때, pH가 최대 0.076, 0.083 감소하였다. DIC의 경우 0.561mg/L, 0.612mg/L 증가하였다. 부산신항에 수용가능한 선박수인 24대를 전부 가정하여 실험하였을 경우 pH는 0.200, 0.545 감소하였고, DIC는 1.464mg/L, 3.629mg/L 증가하였다. 일반적으로 스크러버가 세정수를 처리하였을 때 pH 6.1인 것을 감안하여 선박 1대에서 pH 6.1인 조건으 로 24시간 동안 세정수를 배출하는 경우 우리나라 연근해의 연간 pH 변화량보다 약 33.7배 더 큰 폭으로 감소하는 것으로 계산되었다. 선 박이 24대일 경우에는 하루이상 표층의 성층화를 유발하고 수심 4m까지 영향을 주는 것으로 예측되었다.
The bioreduction process from soluble U(VI) to insoluble U(IV) has been extensively studied in the field of radionuclides migration. Since acetic acid (AcOH) is widely used as an electron donor for bioreduction of U(VI), it is necessary to understand the effect of U(VI)-AcOH complexes that exist in different species depending on pH on this process. Changes in samples before and after bioreduction can be compared using time-resolved laser luminescence spectroscopy (TRLLS), which measures the characteristic luminescence spectra of different U(VI) species. Although luminescence properties of U(VI)-AcOH species were reported, experiments were conducted under conditions below pH 4.5. In this study, spectrophotometry and TRLLS for U(VI)-AcOH species (10−100 μM U(VI) and 20 mM AcOH) were performed in pH ranges extending to neutral and alkaline pH regions similar to groundwater conditions as well as acidic pH region. Two different complexes (UO2(AcO)+, UO2(AcO)2 with U(VI) and acetate ratios of 1:1, 1:2) were observed in the acidic pH region. The 1:1 complex, which appears as the pH increases, has no luminescence properties, but its presence can be confirmed because it serves to reduce the luminescence intensity of UO2 2+. In contrast, the 1:2 complex exhibits distinct luminescence properties that distinguish it from UO2 2+. The 1:3 complex (UO2(AcO)3 -) expected to appear with increasing pH was not observed. Two different complexes ((UO2)3(OH)5 +, (UO2)3(OH)7 - with U(VI) and OH ratios of 3:5, 3:7) were observed as the major species in the neutral pH region, but their luminescence lifetimes are remarkably short compared those in the absence of AcOH. Solid U(VI) particles were observed in the alkaline pH region, and they also had completely different luminescence properties from the aforementioned U(VI)-AcOH and U(VI)-hydrolysis species. Based on these results, the effect of pH in the presence of AcOH on the bioreduction process from U(VI) to U(IV) will be discussed.
In this study, we evaluated the performance of phosphate-functionalized silica in adsorbing uranium and provided insights into optimizing the initial conditions of the uranium solution (concentration and pH), which are often overlooked in uranium adsorption studies. While most studies take into account the effect of pH on both the surface charge of the adsorbents and the dissolved speciation of uranium in solution, they often overlook the formation of solid phases such as β-UO2(OH)2 (cr) and UO3· 2H2O(cr), leading to an overestimation of the adsorption capacity. To address this issue, we considered the speciation of U(VI) calculated using thermodynamic data. Our findings suggest that it is reasonable to evaluate the adsorption performance at pH 4 and concentration below 1.35 mM. The formation of β-UO2(OH)2 (cr) starts at 23 μM (pH 5) and 1 μM (pH 6) and increases sharply with increasing concentration. To avoid interference from the formation of solid phases, experiments should be conducted at lower concentrations, which in turn require very small msorbent/Vsolution ratios. However, controlling small amounts of sorbent can be challenging, and increasing the volume of the solution can generate significant amounts of radioactive waste. We also used UV-vis spectra analysis to investigate the formation of solid phases. We found that a 100 mg L-1 uranium solution resulted in the formation of colloidal particles in the solid phase after 2.5 hours at pH 6, while at pH 4, no significant changes in absorbance were observed over 120 hours, indicating a stable ion phase. Based on these conditions, we obtained an excellent adsorption capacity of 110 mg g-1.