Neutral pH Conditions Research Articles

Janus Ga2SeTe and In2SeTe nanosheets: Excellent photocatalysts for hydrogen production under neutral pH

In the past few years, Janus nanosheets have attracted much interest according to their specific structure and considerable potential to address the energy and environmental issues. Herein, the electronic, optical and photocatalytic properties of two-dimensional Janus Ga2SeTe and In2SeTe have been studied using ab-initio computations based on the density functional theory. The obtained results show that these nanomaterials exhibit a semiconductor behavior with direct and moderate bandgaps using hybrid HSE06 functional. Subsequently, the understudied compounds present suitable optical conductivity, absorption, transmission and reflectivity for water splitting under the ultraviolet–visible light irradiation. Interestingly, the band edge positions of Janus Ga2SeTe and In2SeTe excellently straddle the redox potentials of water under neutral pH. Additionally, the free energy values for the formation of H2 from H adsorbed on the Ga2SeTe and In2SeTe compounds are respectively 1.304eV and 0.976eV at pH = 7. More excitingly, the present study proposes strain engineering approach to improve the photocatalytic performance of the Janus Ga2SeTe and In2SeTe monolayers. Specifically, the investigated semiconductors show more appropriate band edge alignment and better hydrogen evolution reaction activity under biaxial tensile strain, which fulfil the water splitting requirements at neutral pH conditions. Our findings conclude that the Janus Ga2SeTe and In2SeTe nanosheets are promising candidates for photocatalytic hydrogen production.

Efficient Hydrogen Production at pH 7 in Water with a Heterogeneous Electrocatalyst Based on a Neutral Dimeric Cobalt-Dithiolene Complex

The development of efficient hydrogen production technologies is fundamental for replacing fossil-fuel-based energies. As such, electrocatalysts derived from Earth-abundant metal complexes are appealing, and interesting performances have typically been disclosed under acidic conditions in organic solvents. However, their applicability under relevant pH-neutral conditions has been underexplored. Herein, we demonstrate that nonionic, dimeric cobalt-dithiolene complexes supported on a multiwalled carbon nanotube (MWCNT)/carbon paper (CP) electrode are powerful electrocatalysts for hydrogen production in aqueous media at pH 7. The high turnover numbers encountered (TON up to 50980) after long reaction times (up to 16 h) are explained by the increased electroactive cobalt concentration on the modified electrode, which is ca. 4 times higher than that of a state-of-the-art cobalt porphyrin electrocatalyst. These findings point out that immobilizing well-defined, multinuclear, low-cost metal complexes on carbon material is a promising strategy to design highly electroactive electrodes enabling production of green energies.

Molecular interactions between soybean glycinin (11S) and genistein using spectroscopic and in silico analyses

Interactions and binding mechanisms between soybean glycinin (11S) and genistein were investigated at near neutral pH (7.4) and ambient temperature using various spectroscopic techniques and molecular docking. Ultra-violet visible spectroscopy revealed non-covalent bonds were responsible for the stabilisation of the complex. Following complexation, minor reductions in the alpha helix and beta sheet content of the protein were confirmed by circular dichroism (CD) and infrared spectroscopy (FTIR). Fluorescence quenching and molecular docking predicted a 11S trimer and genistein complex with a 1:1 stoichiometric ratio, with the binding location predominantly on the interior portion of the protein, stabilised in majority by hydrogen bonds. Although binding was determined to be of moderate strength, secondary structure characterisation suggested that the structural components of the protein remained largely unchanged. This outcome indicates that the ligand can be accommodated in the interior of the 11S trimer, forming a stable complex within the present conditions of neutral pH and ambient temperature.

Different pKa Shifts of Internal GLU8 in Human β-Endorphin Amyloid Revealing a Coupling of Internal Ionization and Stepwise Fibril Disassembly.

As a functional amyloid, human β-endorphin amyloid fibril features a β-solenoid conformation and store peptide hormones within acidic secretory granules, which would be released into the blood through fibril disassembly when the cellular milieu pH increases from acidic to neutral level on exocytosis. To gain detailed atomic mechanism of β-endorphin amyloid fibrils' pH-responsive disassembly, we conduct constant pH molecular dynamics simulations to investigate the structural and dynamical properties of β-endorphin amyloid fibrils in experiencing the environmental pH changes. Our results demonstrate a clear pKa shift of the internal ionizable residue of GLU8, and this shift becomes even more pronounced when it is buried more deeply in the amyloid fibrils. The unusual pKa of GLU8 reveals that its protonation state changes from the protonated state in the acidic secretory granule to the deprotonated state in the neutral pH conditions in the blood, where the deprotonation of GLU8 leads to unfavorable interactions within the hydrophobic core of the amyloid and subsequent fibril disassembly. The different pKa shifts of GLU8 relative to its positions in the amyloid fibril indicate that the β-endorphin amyloid fibril disassembly is a stepwise process, accounting for the experimental observation that the disassembly always initiates from the outermost layer. This study reveals the critical role of the protonation state of GLU8 in amyloid fibrils' pH-responsive disassembly, and provides clear insights for understanding the structural transitions of amyloids in hormone secretion. This study also provides theoretical basis for designing pH-sensitive biological tools for specific use with precise positioning of ionizable residues into the hydrophobic interior of proteins.

Synergistic removal of sulfamethoxazole and dimethyl phthalate by five constructed wetland substrates

Frequent detection and joint toxicity of sulfonamides (SAs) and phthalate acid esters (PAEs) in water environment have caused serious health and safety problems that can be reduced by vertical flow constructed wetland (VFCW). However, it remains unclear what kind of substrate used in VFCW can synergistically remove SAs and PAEs. In this study, it was determined if biochar, zeolite, vermiculite, peat and sand synergistically removed sulfamethoxazole (SMX) and dimethyl phthalate (DMP) as representatives of SAs and PAEs by using batch and column experiments. The batch experiments showed that pseudo-second-order and intraparticle diffusion kinetics and Freundlich isotherm could better describe the synergistic adsorption of SMX and DMP on each substrate. SMX promoted hydrophobic interaction between DMP and each substrate so that low concentration DMP almost was adsorbed completely at neutral pH. Both neutral and alkaline pH conditions were favorable for synergistic adsorption of SMX and DMP on each substrate. The column experiments showed that removal of SMX or DMP in VFCW by substrate adsorption alone was limited with run time increasing, but SMX and DMP were effectively removed with run time increasing when loaded with simulated wastewater, SMX and DMP. The VFCW not only removed 94.7% SMX and 91.8% DMP after running 50 d, but also improved total nitrogen removal. In conclusion, these results strongly suggest that biochar, zeolite, vermiculite, peat and sand filled in VFCW can synergistically remove SMX and DMP.

Mechanistic insights into surface catalytic oxidation of fluoroquinolone antibiotics on sediment mackinawite

Fluoroquinolone antibiotics (FQs) have been widely detected in the sediments due to vast production and consumption. In this study, the transformation of FQs was investigated in the presence of sediment mackinawite (FeS) under ambient conditions. Moreover, the role of dissolved oxygen was evaluated for the enhanced degradation of FQs induced by FeS. Our results demonstrated that typical FQs (i.e., flumequine, enrofloxacin and ciprofloxacin) could be efficiently adsorbed and degraded by FeS under neutral pH conditions. As indicated by the results of electron paramagnetic resonance analysis (EPR) and free radicals quenching experiments, hydroxyl radical and superoxide radical anions were identified as the dominant reactive species responsible for FQs degradation. Based on the results of product analysis and theoretical calculation, the degradation of FQs mainly occurred at the piperazine ring and quinolone structure. Our results show that FQs could be efficiently removed by FeS, which benefits understanding the transformation of antibiotics in the sediments, and even sheds light on the remediation of organic pollutants contaminated soils.

A Highly Stable, Capacity Dense Carboxylate Viologen Anolyte towards Long‐Duration Energy Storage

AbstractAqueous organic redox flow batteries (AORFBs) have received increasing attention as an emergent battery technology for grid‐scale renewable energy storage. However, physicochemical properties of redox‐active organic electrolytes remain fine refinement to maximize their performance in RFBs. Herein, we report a carboxylate functionalized viologen derivative, N,N′‐dibutyrate‐4,4′‐bipyridinium, (CBu)2V, as a highly stable, high capacity anolyte material under near pH neutral conditions. (CBu)2V can achieve solubility of 2.1 M and display a reversible, kinetically fast reduction at −0.43 V vs NHE at pH 9. DFT studies revealed that the high solubility of (CBu)2V is attributed to its high molecular polarity while its negative reduction potential is benefitted from electron‐donating carboxylate groups. A 0.89 V (CBu)2V/(NH)4Fe(CN)6 AORFB demonstrated exceptional energy storage performance, specifically, 100 % capacity retention with a discharge energy density of 9.5 Wh L−1 for 1000 cycles, power densities of up to 85 mW cm−2, and an energy efficiency of 70 % at 60 mA cm−2. (CBu)2V not only represents the most capacity dense viologen with pendant ionic groups and also exhibits the longest (1200 hours or 50 days) and the most stable flow battery performance to date.

A Highly Stable, Capacity Dense Carboxylate Viologen Anolyte towards Long-Duration Energy Storage.

Aqueous organic redox flow batteries (AORFBs) have received increasing attention as an emergent battery technology for grid-scale renewable energy storage. However, physicochemical properties of redox-active organic electrolytes remain fine refinement to maximize their performance in RFBs. Herein, we report a carboxylate functionalized viologen derivative, N, N'-dibutyrate-4,4'-bipyridinium,(CBu)2V, as a highly stable, high capacity anolyte material under near pH neutral conditions.(CBu)2Vcan achieve more than 2.1 M solubility and display a reversible, kinetically fast reduction at -0.43 V vs NHE at pH 9.DFT studies revealed that the high solubility of(CBu)2Vis attributed to its high molecular polarity while its negative reduction potential is benefitted from electron-donating carboxylate groups. A 0.89 V (CBu)2V/(NH)4Fe(CN)6AORFB demonstrated exceptional energy storage performance, specifically, 100% capacity retention with a utilized energy density of 9.5 Wh/L for 1000 cycles, power densities of up to 85 mW/cm2, and an energy efficiency of 70% at 60 mA/cm2.(CBu)2Vnot only represents the most capacity dense viologen with pendant ionic groups and also exhibits the longest (1200 hours or 50 days), most stable flow battery performance to date.

MoS2 Quantum Dot Modified Electrode: An Efficient Probe for Electrochemical Detection of Hydrazine

The development of an effective sensor system that can detect carcinogenic hydrazine is of prime scientific interest for the protection of human health and the environment. In the present study, MoS2 quantum dots (QDs) with an average diameter of ~5 nm were synthesized using a facile one-step, bottom-up hydrothermal method using cysteine as reducing as well as capping agents. The presence of cysteine was evaluated by FTIR spectroscopy. The synthesized MoS2 QDs were applied to modify the conventional glassy carbon electrode (GCE) in order to detect hydrazine electrochemically in neutral pH conditions. In the cyclic voltammetry (CV) study, the MoS2 QDs-modified electrode revealed much better catalytic activities for hydrazine electro-oxidation compared to the bare GCE surface. The smaller size of the QDs with high surface area and the presence of carboxylic acid containing cysteine on the surface of the QDs enhanced the adsorption as well as the electrocatalytic activity. The amperometric response of MoS2-QD-modified GCE unveiled excellent electrocatalytic sensing properties towards neurotoxic hydrazine with a very high sensitivity of 990 μAmM−1cm−2 (R2 = 0.998), low LOD of 34.8 μM, and a broad linear range. Moreover, this high-sensitive, binder and conducting filler-free MoS2-QD-based sensing system is very promising in agile amperometric detection of neurotoxic hydrazine for environmental monitoring in industrial sectors.

The role of aggregation and ionization in the chemical instability of Amphotericin B in aqueous methanol

Amphotericin B (AmB) is a potent antimicrobial agent used in clinical practice. Nevertheless, the mechanism of its aqueous instability remains not yet fully understood, especially the role that its aggregation state plays in this process. Therefore, the current study used an aqueous methanol media to evaluate the AmB instability as a function of pH-, organic solvent- and concentration-dependent ionization and aggregation. To reach this goal, the aggregation status and instability were determined using UV–vis spectroscopy, LC-MS and HPLC. Moreover, not only the hydrolytic degradation products were identified by UV–vis spectroscopy and LC-MS, but also, the degradation rate constants were estimated by nonlinear regression. The results indicated that monomeric AmB was the predominant species under pH conditions, wherein the substrate was cationic (pH < 4) or anionic (pH > 9). On the other hand, aggregated AmB form was the predominant species for the zwitterionic substrate (at methanol concentration < 30 %(v/v)). Anionic substrate degraded by specific base-catalyzed lactone hydrolysis. Oxidation accounted for the loss of zwitterionic substrate. Aggregated zwitterionic AmB exhibited lower stability than monomeric zwitterionic AmB under neutral pH conditions. These studies are a step forward in comprehending the degradation kinetics of AmB in aqueous medium. In fact, along with our previous research on AmB instability in oils, it leads to a better understanding of the AmB stability in complex systems with an oil–water interface, such as disperse lipid systems.

Exploitation of expired cellulose biopolymers as hydrochars for capturing emerging contaminants from water.

Expired chemicals pose a potential environmental threat to humans and living organisms. Herein, we proposed a green approach whereby expired cellulose biopolymers were converted to hydrochar adsorbents and tested for removing the emerging pharmaceutical contaminants of fluoxetine hydrochloride and methylene blue from water. A thermally stable hydrochar was produced with an average particle size of 8.1 ± 1.94 nm and a mesoporous structure that exhibited a larger surface area than the expired cellulose by 6.1 times. The hydrochar was efficient in removing the two contaminants with efficiencies that reached above 90% under almost neutral pH conditions. Adsorption exhibited fast kinetics and regeneration of the adsorbent was successful. The adsorption mechanism was hypothesized in view of the Fourier Transform Infra-Red (FTIR) spectroscopy and pH effect measurements to be mainly electrostatic. A hydrochar/magnetite nanocomposite was also synthesized, and its adsorption behavior for both contaminants was tested and it revealed an enhanced percent removal relative to the bare hydrochar by 27.2% and 13.1% for FLX and MB, respectively. This work supports the strategies for zero waste management and the circular economy.

Influence of Soy Lecithin and Sodium Caseinate on The Stability and in vitro Bioaccessibility of Lycopene Nanodispersion.

Various approaches have been used to present functional lipids including lycopene in a palatable food form to consumers. However, being highly hydrophobic, lycopene is insoluble in aqueous systems and has a limited bioavailability in the body. Lycopene nanodispersion is expected to improve the properties of lycopene, but its stability and bioaccessibility are also affected by emulsifier type and environmental conditions such as pH, ionic strength and temperature. The influence of soy lecithin, sodium caseinate and soy lecithin/sodium caseinate at 1:1 ratio on the physicochemical properties and stability of lycopene nanodispersion prepared using the emulsification-evaporation methods before and after treatment at different pH, ionic strength and temperature were investigated. The in vitro bioaccessibility of the nanodispersions was also studied. Under neutral pH conditions, nanodispersion stabilized with soy lecithin had the highest physical stability and the smallest particle size (78 nm), the lowest polydispersity index (PDI) value (0.180) and highest zeta potential (-64 mV) but the lowest lycopene concentration (1.826 mg/100 mL). Conversely, nanodispersion stabilized with sodium caseinate had the lowest physical stability. Combining the soy lecithin with sodium caseinate at 1:1 ratio resulted in a physically stable lycopene nanodispersion with the highest lycopene concentration (2.656 mg/100 mL). The lycopene nanodispersion produced by soy lecithin also had high physical stability under different pH range (pH=2-8) where the particle size, PDI and zeta potential remained fairly consistent. The nanodispersion containing sodium caseinate was unstable and droplet aggregation occurred when the pH was reduced close to the isoelectric point of sodium caseinate (pH=4-5). The particle size and PDI value of nanodispersion stabilized with soy lecithin and sodium caseinate mixture increased sharply when the NaCl concentration increased above 100 mM, while the soy lecithin and sodium caseinate counterparts were more stable. All of the nanodispersions showed good stability with respect to temperature changes (30-100 °C) except for the one stabilized by sodium caseinate, which exhibited an increased particle size when heated to above 60 °C. The combination of soy lecithin and sodium caseinate was found to increase the bioaccessibility of the lycopene nanodispersion. The physicochemical properties, stability and extent of the lycopene nanodispersion digestion highly depend on the emulsifier type. Producing a nanodispersion is considered one of the best ways to overcome the poor water solubility, stability and bioavailability issues of lycopene. Currently, studies related to lycopene-fortified delivery systems, particularly in the form of nanodispersion, are still limited. The information obtained on the physicochemical properties, stability and bioaccessibility of lycopene nanodispersion is useful for the development of an effective delivery system for various functional lipids.

Environmental risk assessment of the contamination of river water and sediments from the Bor mining area, East Serbia―Secondary Cu enrichment at the reservoir site

AbstractThe study area is within the Bor copper mining region, Eastern Serbia, where wastewaters from the Bor metallurgical/smelting facilities have caused serious copper (Cu) and arsenic (As) contamination to the Timok river system. The operating conditions at smelting facilities control the pH of the river waters, resulting in highly acidic waters in 2019 than 2015. This study compares the mobility of Cu and As and risk assessment of river water contamination during both years as well as assessing the risks of riverbed sediments contamination and investigating the origins of Cu and As pollution. In the river system, As generally existed as a particulate species in the entire study area during both years and was widely removed from river waters by sorption onto the hydrous ferric oxides (HFO), whereas dissolved Cu was removed from river waters only at neutral pH conditions with hydrous aluminum oxides (HAO) and HFO at the downstream reservoir site of Timok River. Despite the similarity in Cu mobility during both years, the lower pH of river waters in 2019 than 2015 enabled dissolved Cu species to be transported farther downstream, resulting in a higher level of river water pollution. The contamination factor (CF), used to estimate levels of sediment pollution, had higher values for Cu and As compared to Zn, Pb, Co, and Ni. The CF values of Cu were the highest in sediments near the Bor metallurgical/smelting facilities and at downstream reservoir site, whereas the CF values of As were generally high in the entire research field. Additionally, the ecological risk potential (Er) values of Cu were the highest in sediments of the Bor River and Timok River, reflecting an enrichment of Cu at these sites. Finally, a clarification on the origin of Cu pollution and risks of mobilization was inferred from the sequential extraction test. The predominant Cu species in sediments of the upstream region were oxidizable and residual, hosted by copper sulfides originating from the flotation tailings, suggesting a relatively low risk of Cu release from these sediments. However, at the downstream site (especially reservoir sediments), the contribution of acid‐soluble Cu was 34.8%, suggesting a higher risk of Cu release. The highest contributions of acid‐soluble and reducible Cu (18%) at the reservoir site were promoted by the effective settlement of Cu‐sorbing HAO and HFO. The Cu contents of these two fractions were 0.86 wt%, almost three times higher than that of Cu ore in Veliki Krivelj open pit mine.

Low density lipoprotein-pectin complexes stabilized high internal phase pickering emulsions: The effects of pH conditions and mass ratios

The present work aimed to explore the feasibility of using egg yolk low density lipoproteins (LDL) as naturally occurring nanoparticles to prepare high internal phase Pickering emulsions (HIPEs), and to understand the role of pectin (PE) as a natural food thickener in improving the emulsifying stability to prepare HIPEs. Colloidal complexes were formed spontaneously via electrostatic interactions upon mixing PE and LDL at acidic pH condition. The colloidal characteristics of LDL-PE complexes were studied by dynamic light scattering method, Fourier transform infrared spectroscopy and viscosity measurements, as well as interfacial activities. Lastly, the capability of complexes as a stabilizer to prepare HIPEs was then comprehensively investigated as functions of pH conditions and mass ratios of LDL and PE. The results indicated that the particle sizes and surface activities of LDL-PE complexes were highly dependent on the electrostatic interactions. The interactions between LDL and PE slightly reduced at neutral pH conditions or higher concentrations of PE, which were more favorable to form stable particles with smaller size and higher surface activity, and thus greater stability of HIPEs. Although the interfacial tensions of LDL increased with the existence of PE, the stability of LDL-PE stabilized HIPEs (LP-HIPEs) was greatly enhanced compared with the free LDL stabilized ones. LDL and PE formed non-covalent network among the emulsion droplets and the oil-water interface of HIPEs, inducing stable gel structure. Droplet size analysis and morphological observation under optical microscopes together with digital photos revealed the homogenous emulsion droplets in a strong gel geometry. Gel-like elastic network structure was confirmed by rheological measurements, and the thick coating layer of LDL-PE complexes on the oil-water interface was further visualized by confocal laser scanning microscope. Our findings are innovative and offer new opportunities to prepare HIPEs from all natural ingredients for future applications in the food industry. • Low density lipoprotein-pectin (LDL-PE) complexes were able to stabilize HIPEs. • Pectin played critical roles in the formation of stable gel-like structure in HIPEs. • Rheological data and microscopical images confirmed the strong gel network. • The HIPEs showed exceptional stability in centrifugation and long-term storage tests. • LDL-PE exhibited superior emulsifying and stabilization capability than LDL alone.

Geological and hypogene mineralization characteristics of the hematite‐rich Pelusa IOCG prospect, Antofagasta Region, Northern Chile

AbstractThe Japón, Tailandia and China Sur deposits in the Pelusa mineralized area correspond to a hematite‐dominant IOCG clan within the coastal Cordillera in the Antofagasta Region, Northern Chile, and their mineralization occurs in basaltic to andesitic volcanic rocks of the Jurassic La Negra Formation. In addition to geological and mineralogical descriptions, bulk chemistry of the host rocks, microthermometric and sulfur isotropic analyses were performed to elucidate ore‐forming characteristics of the three orebodies. Chemical data of the host rocks indicate a subalkaline calc‐alkaline affinity with enrichment of the incompatible LILEs, displaying a typical pattern of igneous rocks formed in subduction zones as a general characteristic of the Jurassic‐Lower Cretaceous magmatic arc. Chalcopyrite is the predominant hypogene copper mineral, that variously occurs as veinlets, disseminations and breccia matrix. Fluid inclusions data indicate formation temperatures of the hypogene mineralization ranging mostly from 186 to 377°C, with a high‐salinity range of 30.1 and 45.0 wt% NaCl. The sulfur isotopic ratios (δ34SCDT) of pyrite and chalcopyrite present a narrow range of values from −10.6 to −7.5‰. The negative values in the limited range imply that sulfide minerals of the Pelusa area were formed under a relatively oxidizing and/or neutral pH condition, compared with other Chilean IOCG deposits.

Coprinopsis cinerea Galectin CGL1 Induces Apoptosis and Inhibits Tumor Growth in Colorectal Cancer Cells.

Mushroom galectins are promising anticancer agents for their low IC50 values against cancer cells in vitro. In this study, two Coprinopsis cinerea galectins, CGL1 and CGL2, were heterologously expressed, and their biochemistry properties and anticancer effects were evaluated. The purified galectins were thermostable at neutral pH conditions. They both existed as tetramers and shared a high affinity towards lactose. CGL1 and CGL2 strongly inhibited the cell viability of many cancer cell lines, including three colorectal cancer cells, in a dose-dependent manner by inducing mitochondria-mediated caspase-dependent apoptosis. Furthermore, CGL1 exhibited higher apoptosis-inducing ability and cytotoxicity than CGL2. In vivo cell viability experiments based on two xenograft mouse models showed that CGL1 had a more substantial inhibitory effect than CGL2 on HCT116 tumor growth (p &lt; 0.0001), whereas only CGL1 inhibited DLD1 tumor growth (p &lt; 0.01). This is the first study to evaluate the anti-colorectal cancer effect of mushroom lectins in vivo, and our results showed that CGL1 is a potent agent for colorectal cancer treatment.

Aluminum-based electrocoagulation for residual fluoride removal during per- and polyfluoroalkyl substances (PFASs) wastewater treatment

The residual fluorion (F–) generated during per- and polyfluoroalkyl substances (PFASs) treatment presents a new environmental burden, while minimum attention has been redirected to its removal. In this study, Al-based electrocoagulation (EC) technique was optimized to effectively remove the residual F– during PFASs wastewater treatment. At EC’s optimal operating conditions, it can achieve over 81.7 % removal efficiency within 30 min. Furthermore, EC exhibited a stable performance on removing F– across a wide range of pH (3–11), and could form stable flocs under neutral pH conditions. The in-depth characterization of flocs has revealed the dynamic change of Al-F species along the EC process, and removal mechanisms were proved to be a combination of complexation, ion exchange, hydrogen bonding and precipitation. In addition, the optimized EC showed stable removal efficiency of F– with the co-existence of multiple PFASs. Hence, we have effectively removed the residual F– during PFASs wastewater treatment, and provide new insights to better understand the defluorination mechanisms in the EC process.

PH-Responsive Metal-Organic Framework Thin Film for Drug Delivery.

In this work, surface-supportive MIL-88B(Fe) was explored as a pH-stimuli thin film to release ibuprofen as a model drug. We used surface plasmon resonance microscopy to study the pH-responsive behaviors of MIL-88B(Fe) film in real time. A dissociation constant of (6.10 ± 0.86) × 10-3 s-1 was measured for the MIL-88B(Fe) film in an acidic condition (pH 6.3), which is about 10 times higher than the dissociation of the same film in a neutral pH condition. MIL-88B(Fe) films are also capable of loading around 6.0 μg/cm2 of ibuprofen, which was measured using a quartz crystal microbalance (QCM). Drug release profiles were compared in both acidic and neutral pH conditions (pH 6.3 and 7.4) using a QCM cell to model the drug release in healthy body systems and those containing inflammatory tissues or cancerous tumors. It was found that the amount of drug released in acidic environments had been significantly higher compared to that in a neutral system within 55 h of testing time. The pH-sensitive chemical bond breaking between Fe3+ and the carboxylate ligands is the leading cause of drug release in acidic conditions. This work exhibits the potential of using MOF thin films as pH-triggered drug delivery systems.

Improving Alkali Polymer Flooding Economics by Capitalizing on Polymer Solution Property Evolution at High pH

Summary Alkali polymer (AP) flooding is a promising enhanced oil recovery (EOR) method to increase oil recovery from reactive oils. It is essential to carefully select the alkali and polymer type and concentration to optimize incremental oil recovery. In addition to the conventional laboratory tests for polymer flooding, the effects of the high pH on the polymer and its evolving properties over time need to be investigated. Consideration of near-wellbore and reservoir effects is key in designing the process. We are showing how understanding and taking advantage of the polymer performance in a high pH environment allow for cost reduction and increase in injectivity and incremental oil recovery for AP projects. The polymer performance was evaluated for AP flooding of the Matzen field (Austria). Evaluations included changes in polymer rheology during aging at high pH conditions, phase behavior tests, and single-/two-phase corefloods with aged and nonaged polymer solutions. In addition, adsorption of the aged polymer and interfacial tension (IFT) were measured. The aging was studied in anaerobic conditions at reservoir temperature and through an accelerated method at elevated temperatures. The accelerated method developed earlier for neutral pH range provides a possibility to run aging at elevated temperatures in a short time frame and transfer the data to reservoir temperature to give information on the long-term performance. The transfer takes place through a conversion factor derived from the first-order kinetics of acrylamide hydrolysis in pH 6–8. In the present work, the applicability of the accelerated method is evaluated for elevated pH by determining the degree of polymer hydrolysis over time via nuclear magnetic resonance and linking it to viscosity performance at various temperatures. The AP conditions in the Matzen AP flooding project (pH &amp;gt; 10) lead to an increased initial rate of polymer hydrolysis of the tested hydrolyzed polyacrylamide (HPAM) by a factor of 100 compared to hydrolysis at a neutral pH level. This resulted in a rapid increase in a polymer solution viscosity of 160% compared with initial conditions within days at a reservoir temperature of 49°C, after which the viscosity leveled off. Accelerated aging experiments at higher temperatures predict long-term stability of the increased viscosity level for several years. Single-phase injection test in a representative core confirmed the performance of the aged solution compared to a nonaged solution at the same polymer concentration. The retention of polymers is reduced in AP conditions compared with traditional neutral pH conditions, 19 vs. 48 µg/g in the static adsorption test, respectively. Two-phase coreflood tests showed increased polymer viscosity at reservoir conditions. The displacement efficiency of the aged and nonaged polymer solution was similar, confirming the potential for cost savings using lower polymer concentration. This is leading to an improved injectivity and makes use of the increased polymer viscosity down in the reservoir through hydrolysis. The current work combines multiple aspects that should be considered in the proper planning of AP projects—not only improvements in polymer viscosity performance due to water softening but also long-term effects due to increased pH. Additionally, these aspects are combined with changes in adsorption properties. The results show that the design of AP projects will benefit from the holistic approach and understanding the changes in polymer rheology with time. The costs of AP projects can be reduced owing to the lower required polymer concentrations for the same displacement efficiency and reduced retention of polymer. An efficient design of AP projects takes good injectivity of nonaged polymers and the aging of the polymer solutions in alkali into account. Overall, we aim to reduce the polymer concentration—which is a key cost driver—compared with a nonaged application. We show that for AP effects, these effects should be evaluated to improve the economics.

Photocatalytic Cleavage of Trityl Protected Thiols and Alcohols

AbstractWe report the visible light photocatalytic cleavage of trityl thioethers or ethers under pH-neutral conditions. The method results in the formation of the respective symmetrical disulfides and alcohols in moderate to excellent yield. The protocol only requires the addition of a suitable photocatalyst and light rendering it orthogonal to several functionalities, including acid labile protective groups. The same conditions can be used to directly convert trityl-protected thiols into unsymmetrical disulfides or selenosulfides, and to cleave trityl resins in solid phase organic synthesis.