Hydrolytic Stability Research Articles

Study on hydrolytic stability constant of U(IV) by titration

Study on hydrolytic stability constant of U(IV) by titration

A synthetic strategy for the preparation of alkoxy‐functionalized bis‐1,2,4‐triazinyl‐2,6‐pyridines

AbstractHeteroaryl‐1,2,4‐triazine complexants are commonly utilized in separation science for the selective chelation of minor An from Ln in simulated high‐level waste. To facilitate access to relevant chemical entities for hypothesis‐driven inquiry toward improved separations performance, a synthetic method to construct various alkoxy‐complexant derivatives was required. In this work, a convergent synthetic strategy for the production of 3,3′‐ and 4,4′‐tetraalkoxy‐bis‐1,2,4‐triazinyl‐2,6‐pyridines from readily available starting materials via a dealkylation/alkylation/condensation approach is described. Synthetic method development, substrate scope, preliminary solubility, and hydrolytic stability data in various process‐relevant diluents are reported herein.

A comprehensive study on the identification and characterization of degradation products of lipoglycopeptide Dalbavancin using LC and LC-HRMS/MS.

Dalbavancin is the second-generation approved semisynthetic lipoglycopeptide by the United States Food and Drug Administration (USFDA) for the treatment of acute bacterial skin and skin-structure infections. Unlike other lipoglycopeptides, the stability behavior of Dalbavancin was least explored, which is a prerequisite. The current study endeavors to elucidate the oxidative and hydrolytic stability behavior of Dalbavancin by exposing the drug to oxidative, acidic, and basic stress conditions. A simple liquid chromatography (LC) method was developed, where significant resolution between Dalbavancin, its homologs, and the generated degradation products was achieved. Seven degradation products were identified under acidic, basic, and oxidative stress conditions. Using liquid chromatography and high-resolution mass spectrometry (LC-HRMS), MS/MS studies, the generated degradation products were identified and characterized. Formation of isomeric degradation products was identified especially upon exposure to basic stress conditions. The mechanistic fragmentation pathway for the seven degradation products was established, and the chemical structure for the identified degradation products was elucidated. The results strongly suggest that Dalbavancin is highly susceptible to degradation under oxidative and hydrolytic stress conditions. This study provides insights into the hydrolytic and oxidative stability of Dalbavancin, which can be employed during drug development and discovery in synthesizing relatively stable analogs.

Preparation of Nonlinear Structure Poly(glycolic acid) with High Toughness, Excellent Hydrolysis Stability, and Foaming Performance

Preparation of Nonlinear Structure Poly(glycolic acid) with High Toughness, Excellent Hydrolysis Stability, and Foaming Performance

Design and development of a chitosan-based nasal powder of dimethyl fumarate-cyclodextrin binary systems aimed at nose-to-brain administration. A stability study

The nasal administration route has been studied for the delivery of active molecules directed to the Central Nervous System, thanks to the anatomical connection between the nasal cavity and the brain.Dimethyl fumarate is used to treat relapsing-remitting multiple sclerosis, with a role as an immunomodulator towards T- T-cells and a cytoprotector towards neurons and glial cells. Its use in therapy is hindered by its low aqueous solubility, and low stability, due to hydrolysis and sublimation at room temperature. To overcome this limitation, in this study we evaluated the feasibility of using two amorphous β-cyclodextrin derivatives, namely hydroxypropyl β-cyclodextrin and methyl β-cyclodextrin, to obtain a nasally administrable powder with a view to nose-to-brain administration.Initially, the interaction product was studied using different analytical methods (differential scanning calorimetry, Fourier transform infrared spectroscopy and powder X-ray diffraction) to detect the occurrence of binary product formation, while phase solubility analysis was used to probe the complexation in solution.The dimethyl fumarate-cyclodextrin binary product showing best solubility and stability properties was subsequently used in the development of a chitosan-based mucoadhesive nasally administrable powder comparing different preparative methods. The best performance in terms of both hydrolytic stability and DMF recovery was achieved by the powder obtained via freeze-drying.

Anchoring groups for ordered and highly stable monomolecular films on naturally oxidized aluminum – phosphonate versus carboxylate

Modification of metal oxide surfaces by self-assembled monolayers (SAMs) is attracting growing attention. Carboxylic (CA) and phosphonic (PA) acids are most popular anchoring groups in this context, applied to create hydrophobic coatings, biosensors, and organic field-effect transistors. The efficiency of these devices is crucially affected by the structural quality and stability of the SAM. In this context, we studied the effect of the preparation procedure (solvent, incubation time, and temperature) on the quality of PA SAMs on naturally oxidized aluminum. We demonstrate formation of PA SAMs matching structural quality of archetypical alkanethiols on gold. Next, we compare their stability with analogous CA SAMs. Our data show that PA SAMs not only exhibit much higher hydrolytic stability but are also capable to protect aluminum substrate from oxidation and degradation. Importantly, even small improvement of the PA SAMs quality, translates into enormous increase of their hydrolytic stability crucial for majority of applications. Finally, we demonstrate that the thermal stability of PA on oxidized aluminum is by ∼250 K higher than CA SAMs, and by ∼200 K higher than for thiols on gold, which makes PA SAMs an excellent candidate for organic electronics, where overheating problems and high-temperature fabrication procedures are common issues.

Low density methacrylated pea, corn, and tapioca starch covalent cryogels with excellent elasticity and water/oil absorption capacity

Porous starch materials are promising in several applications as renewable natural biomaterials. This study reports an approach combining methacrylation of starch and chemical crosslinked cryogelation to fabricate highly elastic macroporous starch (ST-MA) cryogels with impressed water/oil absorption capacity and wet thermal stability among starch based porous materials. Five different types of starch, including pea, normal corn, high amylose corn, tapioca, and waxy maize starch with different amylose content, have been studied. The methacrylation degree is not related with amylose content. All cryogels exhibited excellent compressive elasticity enduring 90 % deformation without failure and good robustness in cyclic tests. The ST-MA cryogels from pea starch exhibited the highest Young's modulus and compressive strength among five types of starch. These covalent cryogels exhibit high wet-thermal stability and enzymatic hydrolysis stability, while still are biodegradable. The dry ST-MA sponges (2 wt%) showed outstanding liquid absorption capacity, absorbing ~40 folds (g/g) of water or ~ 36 folds (g/g) of oil respectively. All types of starch have similar liquid absorption performance. This study provides a universal approach to fabricate highly elastic covalent starch macroporous materials with impressed liquid absorption capacity and outstanding stability, especially wet-thermal stability, and may expand their applications.

Effect of Ce and La doping on photocatalytic and structural properties of the SrO-Bi2O3 system formed on the surface of silicate carrier

This work investigates the impact of doping bismuth photocatalysts based on the SrO-Bi2O3 system with rare-earth elements (La and Ce) as coatings. The authors have developed a method to create photocatalytic coatings on a silicate carrier, which enables the doping of coatings during their formation. The study shows that this method is effective for doping coatings. The addition of 1 to 5% La or Ce controls the light absorption efficiency of the materials in the visible region of the spectrum as well as their hydrolytic stability. The effect of dopants on the efficiency of coatings in the photocatalytic degradation of methylene blue, formic acid, ethylene glycol, and nitrite ions was investigated, and the effect of La and Ce on the structure of the resulting materials was demonstrated. It was found that the optimum content of the doping element Ce is 3%, at. which increases the degradation of pollutants from 1.7 to 15.7 times.

A new green approach to synthesizing MIP-202@porous silica microspheres for positional isomer/enantiomer/hydrophilic separation

Metal-organic frameworks (MOFs) with superior physicochemical properties have great potential for applications in chromatographic separation. However, currently popular methods for the synthesis of MOF-based silica composite materials usually require the use of harmful organic solvents and long-term high-temperature sealing reactions. In order to respond to the needs of green chromatography, it is urgent to develop a new green organic-solvent-free strategy for the synthesis of MOF@SiO2 composites. MIP-202 is a zirconium-MOF constructed from zirconium ion and L-aspartic acid, which features green synthesis as well as good hydrolytic stability and chemical stability. In this paper, SiO2-NH2 was first prepared in a hydrophilic deep eutectic solvent, and then an amino acid-based MOF material (MIP-202) was modified on the surface of the SiO2-NH2 in an aqueous solution to obtain a MIP-202@SiO2 composite material. The multi-mode separation performance of MIP-202@SiO2 as a promising liquid chromatographic stationary phase was particularly evaluated and the separation mechanisms were discussed. The MIP-202@SiO2 column exhibited excellent separation ability for aromatic positional isomers. In addition, chiral enantiomers and hydrophilic analytes were also satisfactorily detected and separated. This work provides a new approach for the facile synthesis of MOF-based liquid chromatographic separation material by using green deep eutectic solvent and water as the reaction media.

Chromatographic and Thermal Characteristics, and Hydrolytic and Oxidative Stability of Commercial Pomegranate Seed Oil.

The current investigations were aimed at the determination of the hydrolytic and oxidative stability of commercial pomegranate seed oils provided by four different producers, and to assess the oils' primary quality parameters. During storage, many changes occur in oils that can significantly affect their quality. The oils were tested for acid and peroxide values, fatty acid profile, and their distribution between the sn-1,3 and sn-2 positions of triacylglycerols. The oxidative stability was also determined, and melting curves were plotted for the oils. The analyzed oils were stored for one month in a dark place at refrigerator temperature. Based on the obtained results, it was found that the acid values for most oils did not exceed the permissible level determined by the Codex Alimentarius. However, in all oils, the peroxide value exceeded the permissible level set by the standard EN ISO 3960:2017-03 and the Codex Alimentarius after the one-month storage period. The examined pomegranate seed oils were found to be valuable sources of polyunsaturated fatty acids, especially punicic acid, which was the most abundant fatty acid present in these oils. In all analyzed oils, linoleic acid predominated in the sn-2 position of the triacylglycerols. Pomegranate seed oils did not exhibit good oxidative stability, as the oxidation induction times for all tested oils were very short. The storage period significantly affected the content of the primary oxidation products and oxidative stability of the oils.

Synergistic enhancement of hydrophobic dental adhesives: autonomous strengthening, polymerization kinetics, and hydrolytic resistance

The leading cause of composite restoration failure is recurrent marginal decay. The margin between the composite and tooth is initially sealed by a low-viscosity adhesive, but chemical, physical, and mechanical stresses work synergistically and simultaneously to degrade the adhesive, destroying the interfacial seal and providing an ideal environment for bacteria to proliferate. Our group has been developing self-strengthening adhesives with improved chemical and mechanical characteristics. This paper reports a self-strengthening adhesive formulation that resists hydrolysis-mediated degradation by providing intrinsic reinforcement of the polymer network through synergistic stimulation of free-radical polymerization, sol-gel reaction, and hydrophobicity. Hydrophobic resin formulation (NE1) was developed using HEMA/BisGMA 28/55w/w and 15 wt% MPS. Control (NC1) contained HEMA/BisGMA 28/55 w/w and 15 wt% MES. The polymerization kinetics, water sorption, leachates, and dynamic mechanical properties of the resin samples were investigated. The NC1 and NE1 samples showed comparable polymerization kinetics, degrees of conversion and water sorption. In contrast, NC1 showed significantly higher levels of HEMA and BisGMA leachate, indicating faster degradation in ethanol. At day 3, cumulative HEMA leachate for NC1 was ten times greater than NE1 (p < 0.05). Dynamic mechanical properties were measured at 37 and 70°C in both dry and wet conditions. Under dry conditions, the storage moduli of NC1 and NE1 were comparable and the glass transition temperature (Tg) of NC1 was statistically significantly lower (p < 0.001) than NE1. Under wet conditions, the storage modulus of NC1 was lower than NE1 and at 70°C there was a threefold difference in storage modulus. At this temperature and under wet conditions, the storage modulus of NC1 is statistically significantly lower (p < 0.001) than NE1. The results indicated that in the wet environment, NE1 provided lower chain mobility, higher crosslink density, and more hydrogen bonds. The newly formulated methacrylate-based adhesive capitalizes on free-radical polymerization, sol-gel reactions, and hydrophobicity to provide enhanced mechanical properties at elevated temperatures in wet environments and hydrolytic stability under aggressive aging conditions.

Computationally guided synthesis of a hierarchical [4[2+3]+6] porous organic ‘cage of cages’

Here we report a two-step, hierarchical synthesis that assembles a trigonal prismatic organic cage into a more symmetric, higher-order tetrahedral cage, or ‘cage of cages’. Both the preformed [2+3] trigonal prismatic cage building blocks and the resultant tetrahedral [4[2+3]+6]cage molecule are constructed using ether bridges. This strategy affords the [4[2+3]+6]cage molecule excellent hydrolytic stability that is not a feature of more common dynamic cage linkers, such as imines. Despite its relatively high molar mass (3,001 g mol−1), [4[2+3]+6]cage exhibits good solubility and crystallizes into a porous superstructure with a surface area of 1,056 m2 g−1. By contrast, the [2+3] building block is not porous. The [4[2+3]+6]cage molecule shows high CO2 and SF6 uptakes due to its polar skeleton. The preference for the [4[2+3]+6]cage molecule over other cage products can be predicted by computational modelling, as can its porous crystal packing, suggesting a broader design strategy for the hierarchical assembly of organic cages with synthetically engineered functions.

Preparation and Characterization of SPEEK–PVA Blend Membrane Additives with Colloidal Silica for Proton Exchange Membrane Fuel Cell

An inexpensive membrane with high proton conductivity and high fuel cell performance, which can be an alternative to Nafion for PEMFC (Proton exchange membrane fuel cell), will overcome the obstacle to widespread commercialization of fuel cells due to high cost. For this purpose, SPEEK (sulfonated polyether ether ketone)-PVA (polyvinyl alcohol) blend membranes with colloidal silica additives were synthesized in this study. Ludox AS-40 was used as the colloidal silica source and the blend membrane was prepared by solution casting method. Water uptake capacity, swelling property, size change, dynamic mechanical analysis, ion exchange capacity, AC impedance analysis, hydrolytic and oxidative stability experiments of the synthesized Ludox additives blend membranes for fuel cell application were carried out, and the membranes were also characterized by FTIR (Fourier transform infrared) analysis. While the water uptake capacities of SPEEK/PVA membranes containing 1% Ludox, 5% Ludox, and 10% Ludox at room temperature were found to be 14.08%, 14.84%, and 16.6%, respectively, the water uptake capacities at 80oC increased to 14.73%, 15.17%, and 17.11%. The proton conductivities of 1% Ludox, 5% Ludox and 10% Ludox doped SPEEK/PVA membranes at 80oC were 0.25 S/cm, 0.56 S/cm, and 0.65 S/cm, respectively. Similarly, ion exchange capacities were determined to be 1.41 meq/g, 1.63 meq/g, and 1.71 meq/g, respectively. All Ludox-added membranes exhibited excellent hydrolytic stability, retaining approximately 88% of their mass after 650 h. In addition, in oxidative stability experiments carried out in 4 ppm Fe+ 2 at 80oC, the 10% Ludox-added membrane exhibited the highest weight loss of 88.8% at the end of 24 h, while the 5% Ludox-additive membrane retained 91.6% of its total weight. Considering the proton conductivity and longevity tests of the synthesized membranes, they are thought to be promising structures.Graphical

Boosting catalytic hydrolysis of carbonyl sulfide over K+ modified CeO2 nanospheres at low-temperature

Carbonyl sulfide (COS) as one of typical atmospheric sulfur-containing pollutants widely emitted from various industrial processes, which has a significant impact on human health and environmental safety. Currently, developing highly efficient catalysts to eliminate COS is of great significance for both fundamental catalytic research and actual industrial application. Here we report a series of K+ doping spherical cerium oxide (CeO2-S) that showing promote activity for catalytic hydrolysis of COS. The research results demonstrated that the K+-doped CeO2-S formed more Ce3+ and oxygen vacancies than CeO2-S. The hydrolysis activity and stability of CeO2-S for COS were significantly improved by the introduction of K+. Among them, the 0.2 K/CeO2-S showed the optimal performance. Further in-situ DRIFTS results revealed that a slight increase in alkalinity could enhanced the activation of H2O over 0.2 K/CeO2-S, and the generated surface active hydroxyl groups reacted with adsorbed COS to produce the intermediate species (HSCO2-), leading to the formation of H2S and CO2. The catalysts prepared in this paper exhibited promoted activity with low-temperature and high stability for COS hydrolysis, which is beneficial for practical industrial scale-up applications and provides novel insights into designing efficacious catalysts with efficient low-temperature activity and superior stability for removing COS.

Proton exchange membranes based on sulfonated polybutylene fumarate: Preparation and characterization

AbstractBased on a novel unsaturated polyester, polybutylene fumarate (PBF), a series of sulfonated proton exchange membranes were prepared and characterized for direct methanol fuel cell application. In this work, PBF underwent sulfonation at different degrees, and the optimum degree of sulfonation (DS) was identified by assessing the hydrolytic stability. In the second step, an effective strategy to enhance the membranes' proton conductivity was adopted by the addition of the 2‐(1H‐Imidazol‐2‐yl) acetic acid (Im‐COOH) compound as a proton‐conducting agent to the sulfonated PBF (SPBF) matrix with the optimum DS. The results unveiled significant alterations in the physicochemical properties of PBF due to sulfonation, including an elevation in water uptake and the glass transition temperature (Tg), accompanied by the disappearance of the crystallinity within SPBF. In terms of electrochemical characteristics, the SPBF‐17.5 PEM demonstrated a proton conductivity of 3.36 × 10−3 S cm−1 and a methanol permeability of 1.068 × 10−7 cm2 s−1, yielding a selectivity of approximately 31,460 S s cm−3. Furthermore, the attractive interactions between SO3H and NH groups further elevated proton conductivity to 4.12 × 10−3 S cm−1, accompanied by a decrease in methanol permeability to 0.942 × 10−7 cm2 s−1, enhancing the selectivity parameter to 43,736 S s cm−3.

Fluorogenic Chemical Probes for Wash-free Imaging of Cell Membrane Damage in Ferroptosis, Necrosis, and Axon Injury.

Selectively labeling cells with damaged membranes is needed not only for identifying dead cells in culture, but also for imaging membrane barrier dysfunction in pathologies in vivo. Most membrane permeability stains are permanently colored or fluorescent dyes that need washing to remove their non-uptaken extracellular background and reach good image contrast. Others are DNA-binding environment-dependent fluorophores, which lack design modularity, have potential toxicity, and can only detect permeabilization of cell volumes containing a nucleus (i.e., cannot delineate damaged volumes in vivo nor image non-nucleated cell types or compartments). Here, we develop modular fluorogenic probes that reveal the whole cytosolic volume of damaged cells, with near-zero background fluorescence so that no washing is needed. We identify a specific disulfonated fluorogenic probe type that only enters cells with damaged membranes, then is enzymatically activated and marks them. The esterase probe MDG1 is a reliable tool to reveal live cells that have been permeabilized by biological, biochemical, or physical membrane damage, and it can be used in multicolor microscopy. We confirm the modularity of this approach by also adapting it for improved hydrolytic stability, as the redox probe MDG2. We conclude by showing the unique performance of MDG probes in revealing axonal membrane damage (which DNA fluorogens cannot achieve) and in discriminating damage on a cell-by-cell basis in embryos in vivo. The MDG design thus provides powerful modular tools for wash-free in vivo imaging of membrane damage, and indicates how designs may be adapted for selective delivery of drug cargoes to these damaged cells: offering an outlook from selective diagnosis toward therapy of membrane-compromised cells in disease.

Exploring the coordination chemistry of ruthenium complexes with lysozymes: structural and in-solution studies.

This study presents a comprehensive structural analysis of the adducts formed upon the reaction of two Ru(III) complexes [HIsq][trans-RuIIICl4(dmso)(Isq)] (1) and [H2Ind][trans-RuIIICl4(dmso)(HInd)] (2) (where HInd-indazole, Isq-isoquinoline, analogs of NAMI-A) and two Ru(II) complexes, cis-[RuCl2(dmso)4] (c) and trans-[RuCl2(dmso)4] (t), with hen-egg white lysozyme (HEWL). Additionally, the crystal structure of an adduct of human lysozyme (HL) with ruthenium complex, [H2Ind][trans-RuCl4(dmso)(HInd)] was solved. X-ray crystallographic data analysis revealed that all studied Ru complexes, regardless of coordination surroundings and metal center charge, coordinate to the same amino acids (His15, Arg14, and Asp101) of HEWL, losing most of their original ligands. In the case of the 2-HL adduct, two distinct metalation sites: (i) Arg107, Arg113 and (ii) Gln127, Gln129, were identified. Crystallographic data were supported by studies of the interaction of 1 and 2 with HEWL in an aqueous solution. Hydrolytic stability studies revealed that both complexes 1 and 2 liberate the N-heterocyclic ligand under crystallization-like conditions (pH 4.5) as well as under physiological pH conditions, and this process is not significantly affected by the presence of HEWL. A comparative examination of nine crystal structures of Ru complexes with lysozyme, obtained through soaking and co-crystallization experiments, together with in-solution studies of the interaction between 1 and 2 with HEWL, indicates that the hydrolytic release of the N-heterocyclic ligand is one of the critical factors in the interaction between Ru complexes and lysozyme. This understanding is crucial in shedding light on the tendency of Ru complexes to target diverse metalation sites during the formation and in the final forms of the adducts with proteins.

Crown aldoxime ethers: Their synthesis, structure, acid-catalyzed/photo-induced isomerization and adjustable guest binding

A series of novel crown aldoxime ethers were synthesized, demonstrating notable thermal and hydrolysis stability. The showcased acid-catalyzed and photo-induced cis/trans isomerization, which enables orthogonal control over both guest complexation and the chiroptical effects of these crown aldoxime ethers, manifesting a regulation of complexation through isomerization at binding heteroatoms.

Properties of APTES-Modified CNC Films.

Sulfated cellulose nanocrystals' (CNCs') facile aqueous dispersibility enables producing films, fibers, and other materials using only water as a solvent but prevents using sulfated CNCs in applications that require water immersion. We report that modifying CNCs with 3-aminopropyl-triethoxysilane (APTES) via a simple, single-pot reaction scheme dramatically improves the hydrolytic stability of CNC films. The effects of APTES modification on CNCs' properties were studied using attenuated total reflectance Fourier transform infrared spectroscopy, atomic force and optical microscopy, thermogravimetric analysis, dynamic light scattering, and ultimate analysis. Substituting a mere 12.6% of the CNCs' available hydroxyl groups with APTES dramatically increased the hydrolytic stability of shear cast films while only having minor impacts on their mechanical properties. In addition, quartz crystal microbalance with dissipation monitoring (QCMD) and multiparametric surface plasmon resonance (MP-SPR) studies showed that the CNC-APTES films also had a greater irreversible binding with carbofuran, a pesticide and emerging contaminant. These results highlight that APTES modification is a promising method for increasing the utility of sulfated CNCs in sensors, adsorbents, and other applications requiring water immersion.

Improvements in Hydrolytic Stability of Alkali-Activated Mine Tailings via Addition of Sodium Silicate Activator.

Over 14 billion tons of mine tailings are produced throughout the world each year, and this type of waste is generally stored onsite indefinitely. Alkali activation is a promising strategy for the reuse of mine tailings to produce construction materials, converting this waste stream into a value-added product. One major problem with alkali-activated mine tailings is their low durability in water (i.e., low hydrolytic stability). In this article, the influence of a mixed sodium hydroxide/sodium silicate alkali activator on the compressive strength, hydrolytic stability, and microstructure of alkali-activated materials (AAMs) were systematically investigated. XRD, FTIR, NMR, and NAD were used to investigate microstructural changes, and a water immersion test was used to show improvements in hydrolytic stability. For gold mine tailings activated with pure sodium hydroxide, the compressive strength was 15 MPa and a seven-day water immersion test caused a strength loss of 70%. With an addition of 1 M sodium silicate in the activator, the AAMs achieved a compressive strength of over 30 MPa and strength loss of only 45%. This paper proposes a mechanism explaining why the strength and hydrolytic stability of AAMs are dependent on the dosage of soluble silicate. A high dosage of sodium silicate inhibits the depolymerization of the source material, which results in a sample with less amorphous aluminosilicate gel and, therefore, lower hydrolytic stability.