Change In pH Of Solution Research Articles

PEGylation of Insulin and Lysozyme To Stabilize against Thermal Denaturation: A Molecular Dynamics Simulation Study.

Biologic drugs or "biologics" (proteins derived from living organisms) are one of the fastest-growing classes of FDA-approved therapeutics. These compounds are often fragile and require conjugation to polymers for stabilization, with many proteins too ephemeral for therapeutic use. During storage or administration, proteins tend to unravel and lose their secondary structure due to changes in solution temperature, pH, and other external stressors. To enhance their lifetime, protein drugs currently in the market are conjugated with polyethylene glycol (PEG), owing to its ability to increase the stability, solubility, and pharmacokinetics of protein drugs. Here, we perform all-atom molecular dynamics simulations to study the unfolding process of egg-white lysozyme and insulin at elevated temperatures. We test the validity of two force fields─CHARMM36 and Amber ff99SB-ILDN─in the unfolding process. By calculating global and local properties, we capture residues that deteriorate first─these are the "weak links" in the proteins. Next, we conjugate both proteins with PEG and find that PEG preserves the native structure of the proteins at elevated temperatures by blocking water molecules from entering the hydrophobic core, thereby causing the secondary structure to stabilize.

Sample pH Can Drift during Native Mass Spectrometry Experiments: Results from Ratiometric Fluorescence Imaging.

The ability of nanoelectrospray ionization (nanoESI) to generate a continuous flow of charged droplets relies on the electrolytic nature of the process. This electrochemistry can lead to the accumulation of redox products in the sample solution. This consequence can have significant implications for native mass spectrometry (MS), which aims to probe the structures and interactions of biomolecules in solution. Here, ratiometric fluorescence imaging and a pH-sensitive, fluorescent probe are used to quantify changes in solution pH during nanoESI under conditions relevant to native MS. Results show that the extent and rate of change in sample pH depends on several experimental parameters. There is a strong correlation between the extent and rate of change in solution pH and the magnitude of both the nanoESI current and electrolyte concentration. Smaller changes in solution pH are observed during experiments when a negative potential is applied than for those when a positive potential is applied. Finally, we make specific recommendations for designing native MS experiments that control for these effects.

DECOMPOSITION MECHANISM AND DISSOCIATION CONSTANTS OF BICARBONATE IONS

Using carbonic acid to explain pH changes in aqueous solutions is invalid due to its undetectability under normal temperature and pressure conditions. Instead, two reversible reactions involving the decomposition of HCO3- ions into OH- and CO2 or H+ and CO32- should be employed. The second reaction (H-mechanism) is well known as the basis for the second dissociation constant of “carbonic acid”. For the first reaction (OH-mechanism), the formula has been derived from the first imaginary constant of the same acid. That is, the researchers experimentally determined the proposed constant based on the results of pH value, CO2 and HCO3- concentrations, but calculated the imaginary constant from these values. The pH increase observed following filtration on the cationic resin in Na+ form is attributed to the weakened HCO3- decomposition via the H-mechanism, resulting in decreased H+ and CO32- concentrations. A significant decrease in Ca2+ concentration (from 5.0 to 0.05 mmol/dm3) is the main reason for the observed phenomenon, as it leads to a decrease in the driving force of calcium carbonate formation. The mechanism of bicarbonate ions decomposition based on two reactions has been confirmed experimentally. An increase in the pH of the mixture of CaCl2 and NaHCO3 solutions (both with the same pH and concentration) indicates the H-mechanism, while a decrease in the pH indicates the OH-mechanism decomposition of bicarbonate ions. The pH value at which the pH does not change indicates a change in the decomposition mechanism. The change in the HCO3- dissociation mechanism depends on hardness and alkalinity, and the pH of this change decreases from softened water (pH 8.30) to seawater (pH 7.5).

Effect of Boric Acid on the Ionization Equilibrium of α-Hydroxy Carboxylic Acids and the Study of Its Applications.

To investigate the synergistic catalytic effects of boric acid and α-hydroxycarboxylic acids (HCAs), we analyzed and measured the effects of the complexation reactions between boric acid and HCAs on the ionization equilibrium of the HCAs. Eight HCAs, glycolic acid, D-(-)-lactic acid, (R)-(-)-mandelic acid, D-gluconic acid, L-(-)-malic acid, L-(+)-tartaric acid, D-(-)-tartaric acid, and citric acid, were selected to measure the pH changes in aqueous HCA solutions after adding boric acid. The results showed that the pH values of the aqueous HCA solutions gradually decreased with an increase in the boric acid molar ratio, and the acidity coefficients when boric acid formed double-ligand complexes with HCAs were smaller than those of the single-ligand complexes. The more hydroxyl groups the HCA contained, the more types of complexes could be formed, and the greater the rate of change in the pH. The total rates of change in the pH of the HCA solutions were in the following order: citric acid > L-(-)-tartaric acid = D-(-)-tartaric acid > D-gluconic acid > (R)-(-)-mandelic acid > L-(-)-malic acid > D-(-)-lactic acid > glycolic acid. The composite catalyst of boric acid and tartaric acid had a high catalytic activity-the yield of methyl palmitate was 98%. After the reaction, the catalyst and methanol could be separated by standing stratification.

Adsorption of triclosan from aqueous solutions via novel metal–organic framework: Adsorption isotherms, kinetics, and optimization via Box-Behnken design

Utilizing Lanthanum/Palladium -Metal organic framework (La/Pd-MOF), this study sought to analyze the efficacy of removing triclosan (TCS) from aqueous solutions. Through compelling experimentation, we demonstrated that La/Pd-MOF is an effective adsorbent for eliminating TCS from water. Characterization of the material was conducted using SEM, XRD, BET analysis, and surface characterization to determine the point of zero charge. Through batch experiments, we investigated how pH levels impacted adsorption equilibrium. Fascinatingly, our results show that changes in solution pH drastically altered adsorption behavior. The effectiveness of TCS adsorption on La/Pd-MOF was thoroughly examined using kinetic models, adhering to the pseudo-second-order model. Furthermore, Langmuir isotherm model fitted the adsorption process accordingly. It was identified that a chemisorption process was involved in the overall process. To further customize the parameters like absorbent dosage, solution pH, temperature and time, Box-Behnken design (BBD) with Response Surface Methodology (RSM) were implemented. According to the instructions, the (ΔH°), (ΔS°), and (ΔG°) of TCS were endothermically and spontaneously extracted using La/Pd-MOF as an adsorbent. The synthesized La/Pd-MOF adsorbent exhibits remarkable render ability and cyclability for up to five cycles of adsorption–desorption. The effectiveness of the created adsorbent was evaluated as a proof of concept for cleaning wastewater samples at a lab scale. Study the mechanism of interaction between the La/Pd-MOF and TCS as it could be taking place through π-π interaction, pore filling, H-Bonding or electrostatic interaction. The La/Pd-MOF adsorbent provided a straightforward and efficient method for managing industrial effluent and water filtration. Our research indicates that our work is the first to describe how to remove TCS using La/Pd-MOF adsorbent from wastewater samples. The results showed that a maximum adsorption capacity of TCS onto La/Pd-MOF is obtained at a pH value of 6, which is 610.845 mg·g−1.

Highly Stable and Reusable 3D Graphene-Quinizarin Voltammetric pH Sensor

A simple pH sensor has been developed employing a 3D porous graphene framework blended with quinizarin. The performance of the fabricated sensor is tested via the square wave voltammetry technique by applying different buffer solutions and real samples. The peak potential of the designed electrode varies with the change in pH of solutions due to 2e−/2H+ transfer process of pH-dependent quinone/hydroquinone redox couple. For varying pH (1–13), the designed sensor has a sensitivity of 65.6 ± 0.4 mV/pH at 25 °C. Soil pH sensing is performed for different types of soil samples prepared using 1M KCl and 0.01M CaCl2 solutions with a potential shift of 63.5 ± 0.9 mV/pH and 57.9 ± 0.3 mV/pH, respectively. The 3D graphene-quinizarin pH sensing probe demonstrates negligible hysteresis (± 0.3 pH) and long-term stability (six months and more). In comparison to the commercial pH meter, the fabricated sensor shows a relative inaccuracy of less than 5%. Moreover, a single electrode could be used to detect the pH of multiple environments by mild rinsing with deionized water and is reusable for more than 500 cycles without significant potential drift. These low-cost and reusable pH-sensitive electrodes with linear Nernstian response are promising candidates for diverse pH-sensing applications.

Design and Properties of Natural Rosin-Based Phosphoester Functional Surfactants

As an important forestry biomass resource, rosin has a wide range of applications in medicine, adhesives, surfactants and other fields. Using natural dehydroabietic acid as a raw material, dehydroabietic acid-based phosphorus monoester (DPM) and diester (DPD) surfactants were designed and synthesized. The chemical structures and self-assembly properties were characterized by FT-IR, NMR and TEM, and the effects of pH on critical micelle concentration, γCMC, emulsifying properties, foam properties and micelle morphology were studied. The results showed that the CMC, γCMC value and aggregate morphology had certain pH responsiveness. The γCMC value under acidic conditions was smaller than γCMC under alkaline conditions, and the foaming performance and foam stability under acidic conditions were better than those under alkaline conditions. TEM micelle morphology studies have shown that DPM and DPD surfactants can self-assemble into rod-shaped and spherical micelle morphologies with a pH change in an aqueous solution. At the same pH, the foaming and emulsification properties of DPD were better than those of DPM. The best foaming and emulsification ability of DPD were 11.8 mL and 175 s, respectively. At the same time, the foaming ability of DPD is also affected by pH. DPD has excellent foaming properties in acidic conditions, but these disappeared in neutral conditions.

Removal of Congo Red from Wastewater Using ZnO/MgO Nanocomposites as Adsorbents: Equilibrium Isotherm Analyses, Kinetics and Thermodynamic Studies

One step polyacrylamide gel method was used to synthesize the ZnO/MgO adsorbents and the adsorption behavior with Congo red (CR) from wastewater was extensively investigated. Various advanced techniques were applied to confirm the ZnO/MgO adsorbents consist of Zn, C, Mg and O elements and do not contain any other impurity elements. With the increase of MgO content, the morphology of ZnO/MgO adsorbent changes from the agglomeration of large particles to evenly dispersed fine particles and then to icicle structure. Results demonstrated that the adsorption process of ZnO/MgO adsorbents was significantly affected by the change in initial dye solution pH, initial adsorbent dosage, contact time and reaction temperature. The optimum pH, adsorbent dosage, contact time and reaction temperature is 9.81, 2 g /L, 65 min and 293 K, respectively. The maximum adsorption capacity of ZnO/MgO (nZnO:nMgO = 8:2) adsorbents (295.138 mg/g) for the adsorption of CR dye was approximately double that of previous reports (125 mg/g). The adsorption equilibrium data are well fitted by the Freundlich and Langmuir isotherm models. Thermodynamic studies indicate that the adsorption process of ZnO/MgO adsorbents is an exothermic process. Based on the experimental and theoretical analysis, the adsorption mechanism for the ZnO/MgO adsorbents consisted of hydrogen bonding, n-π interaction and electrostatic interaction. The present work pioneers the potential application of ZnO/MgO adsorbents for the adsorption of CR dye and further provides experimental evidence for the synthesis of other adsorbents.

Hard tissue repairing potency of mesoporous borosilicate bioactive glass: An in vitro assessment

Complete repair of the fractured hard tissues remains medically challenging, wherein the bioactive glass with antibacterial characteristics can efficiently support the bone growth. Thus, mesoporous borosilicate bioactive glasses (MBGs) of composition xB2O3–(80-x)SiO2–15CaO2–5P2O5 (0≤x≤15 mol%) were prepared using the sol-gel unified evaporation-induced self-assembly (EISA) technique and characterized. In addition, in vitro bio-degradation and bioactivity potential of these MBGs were assessed by immersing them in the simulated body fluid (SBF) for different periods to measure the weight loss and solution pH change. XRD analysis of these glasses showed very weak crystallinity of calcium phosphate Ca3(PO4)2 (JCPDS 70-0364) and FESEM images confirmed their strong mesoporosity with smooth textures. The recorded nitrogen (N2) adsorption-desorption isotherms and hysteresis loops of the studied MBGs indicated their hexagonal crystalline symmetry. The highest pore area and pore volume were estimated to be 342 m2g−1 and 0.6052 cm3, respectively. FTIR spectra of glasses revealed prominent peaks at 1400 and 1500 cm−1 corresponded to the vibration modes of borate units, C-O-C and O-H on P123. With the increase of boron contents, the rate of glass dissolution was increased, indicating their fast bio-degradation essential for efficient osteointegration. In short, the proposed MBGs are asserted to be beneficial for the bio-medical implants coating.

Modeling EDTA-facilitated cadmium migration in high- and low-permeability systems using MODFLOW and RT3D

Cadmium (Cd) has impacted groundwater resources and can pose a serious threat to human health and the environment. Its fate in groundwater is complex and challenging to predict, as it is affected by adsorption to sediments, complexation with aqueous phase ligands, and variations in hydraulic conductivity. In this study, a 2D reactive transport model based on MODFLOW and RT3D is used to simulate published experimental results of cadmium migration without and with EDTA present in a flow cell containing high- and low-permeability zones (i.e., HPZs and LPZs). The model is then extended to conceptual flow cells with more complex LPZ configurations. Simulation results generally match the experimental data well, and analysis of experimental and simulated Cd effluent concentration profiles shows that EDTA enhances Cd removal from LPZs relative to water alone. Simulation results indicate that faster Cd removal is due to EDTA complexation with adsorbed Cd in LPZs, which enhances its solubilization and subsequent back diffusion. Lastly, simulation results show that with increasing LPZ heterogeneity more Cd is retained in flow cells, and EDTA is more effective in enhancing Cd removal relative to water alone; these results are attributed to more LPZ-HPZ interfaces that enhance Cd mass transfer into LPZs during contamination, and enhance EDTA mass transfer into LPZs to promote cleanup. Overall, the results highlight the promise of using EDTA to remove Cd from heterogeneous sites, but caution is advised due to model simplicity and lack of consideration of changes in solution pH, redox potential, or competing cations.

Dual fluorescent hollow silica nanofibers for in situ pH monitoring using an optical fiber.

This study reports a sensitive and robust pH sensor based on dual fluorescent doped hollow silica nanofibers (hSNFs) for in situ and real-time pH monitoring. Fluorescein isothiocyanate (FITC) and tris(2,2'-bipyridyl)dichlororuthenium(ii) hexahydrate (Ru(BPY)3) were chosen as a pH sensitive dye and reference dye, respectively. hSNFs were synthesized using a two-step method in a reverse micelle system and were shown to have an average length of 6.20 μm and average diameter of 410 nm. The peak intensity ratio of FITC/Ru(BPY)3 was used to calibrate to solution pH changes. An optical-fiber-based fluorescence detection system was developed that enabled feasible and highly efficient near-field fluorescence detection. The developed system enables fully automated fluorescence detection, where components including the light source, detector, and data acquisition unit are all controlled by a computer. The results show that the developed pH sensor works in a linear range of pH 4.0-9.0 with a fast response time of less than 10 s and minimal sample volume of 50 μL, and can be stored under dark conditions for one month without failure. In addition, the as-prepared hSNF-based pH sensors also have excellent long-term durability. Experimental results from ratiometric sensing confirm the high feasibility, accuracy, stability and simplicity of the dual fluorescent hSNF sensors for the detection of pH in real samples.

Impact of In Vitro Degradation on the Properties of Samples Produced by Additive Production from PLA/PHB-Based Material and Ceramics.

The present study deals with preparing a polymer-based material with incorporated ceramics and monitoring changes in properties after in vitro natural degradation. The developed material is a mixture of polymers of polylactic acid and polyhydroxybutyrate in a ratio of 85:15. Ceramic was incorporated into the prepared material, namely 10% hydroxyapatite and 10% tricalcium phosphate of the total volume. The material was processed into a filament form, and types of solid and porous samples were prepared using additive technology. These samples were immersed in three different solutions: physiological solution, phosphate-buffered saline, and Hanks' solution. Under constant laboratory conditions, changes in solution pH, material absorption, weight loss, changes in mechanical properties, and surface morphology were monitored for 170 days. The average value of the absorption of the solid sample was 7.07%, and the absorption of the porous samples was recorded at 8.33%, which means a difference of 1.26%. The least change in pH from the reference value of 7.4 was noted with the phosphate-buffered saline solution. Computed tomography was used to determine the cross-section of the samples. The obtained data were used to calculate the mechanical properties of materials after degradation. The elasticity modulus for both the full and porous samples degraded in Hanks' solution (524.53 ± 13.4 MPa) has the smallest deviation from the non-degraded reference sample (536.21 ± 22.69 MPa).

Elevated CO2 concentration induces changes in plant growth, transcriptome, and antioxidant activity in fennel (Foeniculum vulgare Mill.).

Fennel (Foeniculum vulgare Mill.) is widely used to produce natural bio-materials. Elevated CO2 (eCO2) concentrations in the atmosphere improve the net photosynthesis of plants. The aim of the present study was to investigate distinct changes in fennel growth characteristics and phytonutrient contents under different CO2 concentrations. The effects of 400 and 800 ppm concentrations on plant growth and antioxidant activity were observed under hydroponics. Plant growth was improved by eCO2 concentrations. We also observed diverse changes in nutrient solution (pH, electrical conductivity, and dissolved oxygen) and environmental factors (temperature and humidity) in greenhouse under light or dark conditions. Electrical conductivity increased under dark and eCO2 conditions, whereas the pH decreased. Additionally, we performed transcriptome analysis and identified CO2-responsive differentially expressed genes. In the 800 ppm group, genes involved in photosynthesis and Karrikin response were upregulated whereas those involved in syncytium formation were downregulated. Four upregulated differentially expressed genes involved in flavonoid biosynthesis and total flavonoid content were relatively increased under the 800 ppm CO2 condition. In contrast, antioxidant activity, including total phenolic content, scavenging activity, ferric ion reducing antioxidant power, and reducing power were decreased in fennel under relatively high eCO2 concentrations. Moreover, different light intensities of 12 or 24 lx did not affect the growth and antioxidant activity of fennel, suggesting eCO2 has a stronger effect on plant improvement than light intensity. The results of the present study enhance our understanding of the positive effects of CO2 on the growth and antioxidant activity of fennel.

Development of Bi2WO6 and Bi2O3 - ZnO heterostructure for enhanced photocatalytic mineralization of Bisphenol A.

Present study proposed the synthesis of mixed p-type and n-type nanocomposite heterostructures by co-precipitation method. The as-synthesized heterostructures were characterized through different characterization techniques. The as-synthesized Bi2WO6 and Bi2O3-ZnO heterostructures were tested as photocatalysts during the photodegradation of Bisphenol A (BPA). The Bi2O3-ZnO heterostructure nanocomposite was found to be a more effective photocatalyst than Bi2WO6. The effect of operating parameters including catalytic dose (0.02-0.15 gL-1), initial BPA concentration (5-20 mgL-1), temperature change (5-20 °C) and solution pH changes (4, 5, 7, and 8) were evaluated with Bi2O3-ZnO under UV-light irradiation by selecting a 300 W Xe lamp. More than 90% BPA was degraded with 0.15 gL-1 Bi2O3-ZnO, keeping 1.0 mM H2O2concentration fixed in 250 mL of reaction suspension. The HPLC and GC-MS were used to detect the reaction intermediates and final products. A plausible degradation pathway was proposed on the basis of the identification of reaction intermediates. Repeatability test analysis confirmed that the as-synthesized catalyst showed superb catalytic performance on its removal trend. The kinetics of degradation of BPA were well fitted by the power laws model. With the order of reaction being 0.6, 0.9, 1.2, and 1.3 for different operating parameters, i.e., catalyst dose, initial pH, temperature, and initial BPA concentration.

Development of bicarbonate buffer flow-through cell dissolution test and its application in prediction of in vivo performance of colon targeting tablets

The purpose of this study was to develop a bicarbonate buffer flow-through cell (FTC) dissolution test. Mesalazine colon targeting tablets of a generic development product (test formulation, TF; Mesalazine 400 mg tablet) and the original product (reference formulation, RF; Asacol® 400 mg tablet) were used as model formulations. A clinical bioequivalence (BE) study was conducted on 48 healthy male subjects under fasting conditions. The oral absorption time profiles were calculated by point-area deconvolution. The compendial paddle and FTC apparatus were used for dissolution tests. Bicarbonate or phosphate-citrate buffer solutions (McIlvaine buffer) were used as the dissolution media. A floating lid was used to maintain the pH value of the bicarbonate buffer solution in the vessel (paddle) or the reservoir (FTC). In the development of bicarbonate FTC method, the pH changes of bicarbonate buffer solution (pH 5.5–7.5; 5–50 mM bicarbonate) were evaluated. For the evaluation of colon targeting tablets, the dissolution profiles of TF and RF were measured at a pH of 7.5. The TF and RF formulations were exposed to 0.01 HCl (pH 2.0) for 2 h before pH 7.5. In the clinical BE study, drug dissolution started 4–8 h after oral administration and continued slowly more than 10 h. Both the area under the curve (AUC) and maximum plasma concentration (Cmax) of TF were approximately twice as high as those of RF. In the development of the bicarbonate FTC method, the pH change of the bicarbonate buffer solution was suppressed by the floating lid within ∆pH < 0.1 over 10 h. In the dissolution test of McIlvaine buffer solutions, TF and RF showed faster disintegration and higher dissolution than those observed in the clinical BE study. When using the paddle apparatus the dissolution profiles of TF and RF in both buffer solutions were not consistent with those of the clinical result. In bicarbonate FTC, the disintegration time, dissolution rate, and dissolution inequivalence between TF and RF were consistent with the results of the clinical BE study. In conclusion, the bicarbonate FTC method was constructed for the first time in this study. This method is simple and practically useful for predicting in vivo performance of colon targeting tablets during drug development.

Optical band gap enhancements of chemically synthesized α-Ni(OH)2 nanoparticles by a novel technique: Precipitator molarity variation.

Nickel hydroxide nanoparticles (NHNPs) are extremely important semiconducting materials for applications in energy storage and energy harvesting devices. This study uses a novel variation in molarity of the sodium hydroxide (NaOH) precipitator solution to enhance the direct optical band gap in the NHNPs chemically synthesized by using nickel nitrate hexahydrate (Ni(NO3 )2 ·6H2 O) as the precursor. The simple, energy benign chemical precipitation route involved the usage of 1 M (Ni(NO3 )2 ·6H2 O) solutions as the precursor and 0.4M, 0.6M, and 0.8M NaOH solutions as the precipitator solutions. The simple variation in precipitator molarity induces an increase in pH from about 6.9 to 7.5 of the reactant solution. As the molarity of the precursor solution does not change, the change in pH of the reactant solution is equivalent to the change in the pH of the precipitator solution. The NHNPs characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), dynamic light scattering (DLS), Fourier-transform infrared (FTIR) and ultraviolet-visible (UV-vis) techniques confirm a reduction of the nanocrystallite size from about 6.8 to 4.5nm with a concomitant enhancement in the direct optical band gap energy from about 2.64 to 2.74 eV. The possible mechanisms that could be operative behind obtaining microstructurally tuned (MT)-NHNPs and band gap engineering (BGE) of the MT-NHNPs are discussed from both theoretical and physical process perspectives. Further, the implications of these novel results for possible future applications are briefly touched upon. The reported results might be useful to assess the material as an active electrode to improve the performance of batteries.

Effect of Dietary Fiber on the Level of Free Hypoglycemic Agents in Vitro.

We studied the effect of dietary fibers (DFs) on the levels of free hypoglycemic agents in vitro, i.e., glimepiride and the biguanides buformin and metformin. The levels of free buformin and free metformin were not affected by mixtures of DFs, i.e., cellulose, chitosan, pectin (PE), and glucomannan (GM), in fluids of pH 1.2 and 6.8 (similar to the pH of the stomach and intestines, respectively). However, the free biguanide level was significantly reduced by mixing with PE or sodium alginate (AL), in water. The free glimepiride level was reduced in the mixture of AL, PE, and GM (in a solution with a pH of 6.8). The changes in aqueous AL solution pH seemed to reflect the free metformin levels. Therefore, the effects of DFs on free drug levels were dependent on drug type, hypoglycemic agent, and mixing solution. In this study, the oral regimen concentrations of the drug and DFs were used. Based on these results, it is important to consider the interactions between hypoglycemic agents and DFs.

Origins of the pH-Responsive Photoluminescence of Peptide-Functionalized Au Nanoclusters.

Ultrasmall peptide-protected gold nanoclusters are a promising class of bioresponsive material exhibiting pH-sensitive photoluminescence. We present a theoretical insight into the effect peptide-ligand environment has on pH-responsive fluorescence, with the aim of enhancing the rational design of gold nanoclusters for bioapplications. Employing a hybrid quantum/classical computational methodology, we systematically calculate deprotonation free energies of N-terminal cysteine amine groups in proximity to the inherently fluorescent core of Au25(Peptide)18 nanoclusters. We find that subtle changes in hexapeptide sequence alter the electrostatic environment and significantly shift the conventional N-terminal amine pKa expected for amino acids free-in-solution. Our findings provide an insight into how the deprotonation equilibrium of N-terminal amine and side chain carboxyl groups cooperatively respond to solution pH changes, explaining the experimentally observed, yet elusive, pH-responsive fluorescence of peptide-functionalized Au25 clusters.

Enhanced Fenton-like catalysis for pollutants removal via MOF-derived CoxFe3-xO4 membrane: Oxygen vacancy-mediated mechanism.

Traditional batch configuration is not sustainable due to catalyst leaching and ineffective recovery. Herein, a novel membrane-based catalyst with oxygen vacancies is developed, which assembled metal-organic-framework cobalt ferrite nanocrystals (MOF-d CoxFe3-xO4) on polyvinylidene fluoride membrane to activate peroxymonosulfate (PMS) for catalytic degradation of emerging pollutants. MOF-d CoxFe3-xO4 are synthesized by one-step pyrolysis using Co/Fe bimetallic organic frameworks (CoxFe3-x bi-MOF) with tunable cobalt content as a template (x/3-x represented the molar ratio of Co and Fe in MOF). Intriguingly, MOF-d Co1.75Fe1.25O4 membrane exhibits excellent PMS activation efficiency as indicated by 95.12% removal of the probe chemical (bisphenol A) at 0.5mM PMS (∼100Lm-2h-1at the loading of 10mg), which is significantly higher than the traditional Co1.75Fe1.25O4 suspension system (34.16%). Experimental results show that the membrane has excellent anti-interference ability to anions and dissolved organic matter, and can effectively degrade a variety of emerging pollutants, and its performance is not inhibited by the change of solution pH (3-9) or the long-term (20h) continuous flow operation. EPR and quenching experiments show that catalytic degradation is the result of the synergistic effect of radicals and non-radicals. The oxygen vacancy-mediated mechanism can explain the formation of active substances, and the formation of 1O2 plays an important role in the degradation of bisphenol A. This study provides a membrane-based strategy for effective and sustainable removal of emerging pollutants.

Highly Photostable and pH−Sensitive Nanosensors

Determination of pH values has a vital influence in many chemical and biological processes. To accurately determine pH values, we fabricated a highly photostable ratiometric fluorescent pH−sensitive nanosensor by staining the core of mesoporous silica nanoparticle with a rhodol dye and chemically labelling its outer shell with a rhodamine derivative dye. The two dyes possess opposite pH−responding directions, which increases the band of the signal change. There is a nine−fold change in fluorescence intensity ratios when the solution pH changes from 3.0 and 9.0. Meanwhile, the nanosensors displayed yellowish emission in low pH value, orange emission in mid pH value, and reddish emission in high pH value, which can be readily inspected by bare eyes. Last but not least, excellent photostability and reversibility features make the nanosensors useful for the continuous measuring of pH with high accuracy.