Hydrolytic Behavior Research Articles

Effect of carbodiimides on the compatibility and hydrolytic behavior of PLA/PBAT blends

Blends of polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) have great potential to replace conventional polyolefin and polyester materials. However, poor compatibility and fast degradation rate limit its development. In this paper, the effects of two monomer-type carbodiimides and one polymerized carbodiimide on the crystalline, thermal stability, hydrolysis properties, and mechanical properties of PLA/PBAT blends are investigated by Fourier transform infrared spectroscopy, scanning electron microscope, differential scanning calorimetry, thermogravimetric analysis, gel permeation chromatography, melt mass-flow rate, terminal carboxyl content, tensile properties, and rotational torque. It is found that all the three carbodiimide additives can improve the compatibility and enhance the mechanical, processing, and thermal stability properties of PLA/PBAT blends except for their reduced crystallization performance. Moreover, regarding the hydrolysis properties, the two monomeric carbodiimides exhibit little effect on the hydrolysis of PLA/PBAT blends, even accelerating the degradation rate under alkaline conditions. However, the antihydrolysis effect of polycarbodiimide is remarkable, which effectively improves the compatibility and antihydrolysis properties of PLA/PBAT blends.

Arc-shaped air layer bioinspired by ginkgo nut to resist high humidity environment for PET fabrics

Developing simple processes and significant effect modification method for polyester (PET) fabrics to resist hygrothermal aging is a formidable challenge. In this study, inspired by the silver mirror phenomenon of natural ginkgo nut, we utilized the pea pod-shaped nanoparticles that zinc oxide (ZnO) was encapsulated in polyhedral oligomeric silsesquioxane (ZnO@POSS), and polydimethylsiloxane (PDMS) to construct stabilized arc-shaped air layer on the PET fabric surface to resist high humidity environment. The round belly structures of pea pod-shaped ZnO@POSS and interlaced physical networks assisted by PDMS on the PET fabrics surface served as the crucial roles to capture and retain air, resulting in the capacity of the arc-shaped air layer was significantly larger than other microstructures underwater. The water vapor was prevented from entering the fabric interstices that the self-catalytic hydrolysis behavior of PET macromolecular chains was efficiently restrained, and the strength retention of PET fabric was significantly improved from 45 % to 89 % after accelerated hygrothermal aging test (60 °C, 80 % RH, 600 h). This work represents a simple and effective approach to improve the durability for PET fabrics in high humidity environments.

Study on the effect of multi-factor compound action on long-term tensile performance of GFRP composite pipe and life prediction analysis

In this work, the glass fiber reinforced plastic (GFRP) composite pipes used as sewerage pipes in oil and gas field environments were studied. The accelerated aging experiments were carried out under the simulated environments of three typical oil field media which including circulating air, simulated produced water and standard simulated oil. Scanning electron microscopy (SEM) was adopted to observe the microscopic morphology of the aged GFRP tubes under the three conditions. The microstructural characteristics of the aged tubes and the evolution process of internal defects were also analyzed and evaluated in combination with micro-CT technology. The attenuation pattern of the hoop tensile strength of the aged pipes was measured via the separation disk method, and the service life prediction was carried out based on the Arrhenius theory with the hoop strength as the life index. The results show that the accumulation of aging time and continuous heat input will aggravate the expansion of internal pores and cause the aggregation of small-volume defects into large-volume defects. Especially in the simulated oil environment, which has the highest sensitivity to defects. The maximum porosity reaching 1.5 % and the maximum volume of individual defects exceeding 106 μm3 after aging for 4000 h at 95 °C. The thermal aging process under the three environmental conditions had similar aging characteristics, and interfacial damage of the glass fibers was observed in all of them. The variability of hydrothermal aging is related to the hydrolytic behavior of the glass fibers, which is associated with the progressive dissolution damage of the SiO2 network in the glass fibers, as well as the breaking of silane bonds. Thus, the hydrothermal environment had the most significant effect on the hoop tensile strength decay. Ultimately, 75 % strength retention was taken as the end-of-life indicator. The predicted service life based on the Arrhenius model for the three environments of thermo-oxygen, hydrothermal and simulated oil were 23.5, 23.1 and 28.5 years at 20 °C, and 12.2, 4.9 and 10.3 years at 40 °C, respectively.

An improved coking model for simulating reactive transport phenomena and coking behavior in sucrose hydrolysis

Levulinic acid (LA) holds great significance as a biomass platform chemical in the production of bio-aviation fuel and the utilization of bioenergy. Heterogeneous acid-catalyzed polysaccharide hydrolysis has emerged as a promising method for LA production. Understanding the coupling mechanisms of the physicochemical processes are fundamentally important to optimize the reaction system. In this work, a pore-scale multicomponent reactive transport model based on lattice Boltzmann method was developed to simulate the hydrolysis of sucrose. Considering the significant effect of active sites distribution density on coking formation, an improved coking model was proposed. Systematic investigations of reactive transport and coking behavior were conducted. Simulation results demonstrated that, initial sucrose concentration had a substantial impact on the coking rate of catalyst, when sucrose concentration exceeded 250 mmol/L, the catalyst became fully deactivated before complete hydrolysis of reactant occurred. Furthermore, a marginal benefit was found for the synergistic effect of protons in solution and solid catalysts on sucrose hydrolysis, when proton concentration reached the marginal value of 0.12 mol/L, further increases in proton concentration resulted in only marginal improvements in reaction efficiency. This work underscores the importance of the catalyst morphological character engineering and processes controlled for enhancing overall performance in LA production.

Improved recyclability of the superbase ionic liquid [MTBNH][AcO] used in the lyocell fiber spinning process

In the research of new solvents for cellulose dissolution for textile fiber production, some ionic liquids offer high dissolving capacities making them attractive solvents for lyocell processes. One especially interesting group is superbase carboxylates. However, despite their excellent pulp dissolving abilities and good spinnability properties in a lyocell process, they have been lacking hydrolytic stability, which hinders their recyclability. In this article, a new type of superbase-based ionic liquid, [MTBNH][AcO], is aimed to provide higher hydrolytic stability than its structural relative predecessors. For evaluation of the hydrolysis behavior of [MTBNH][AcO], we have tested the ionic liquid in two sets of recycling experiments. The “blank-experiments” were applied to investigate hydrolytic behavior without the presence of pulp. These values were compared with the results from spinning trials with pulp. It was found that this new ionic liquid is not only more stable than its predecessor [MTBDH][AcO] in terms of hydrolysis but can also dissolve and spin cellulose at lower temperatures. The spun fibers were tested for their textile-physical properties and their performance was comparable to other lyocell fibers.

The Hydrolysis Behavior of Antimony Trichloride and Phase Transformation Mechanism of Hydrolysates with the Effect of Arsenic

The Hydrolysis Behavior of Antimony Trichloride and Phase Transformation Mechanism of Hydrolysates with the Effect of Arsenic

New insights into the destabilization of fat globules in ultra-instantaneous UHT milk induced by added plasmin: Molecular mechanisms and the effect of membrane structure on plasmin action

Residual plasmin activity in whole ultra-instantaneous UHT (UI-UHT) milk causes rapid fat rise during storage, seriously affecting consumers' purchase intentions. In this work, the molecular mechanisms underlying fat destabilization in whole UI-UHT milk by added plasmin were investigated based on the hydrolysis behavior of interfacial proteins. By using SDS-PAGE and peptidomic analysis, we found that the hydrolysis of interfacial proteins by plasmin led to a decrease in the amount and coverage of interfacial proteins and an increase in zeta-potential value, causing the flocculation and coalescence of fat globules. Moreover, the hydrolysis pattern varied in different categories of interfacial proteins by plasmin. In total, 125 peptides in all samples were identified. Plasmin tended to hydrolyze most major milk fat globule membrane (MFGM) proteins into protein fragments (>10 kDa) rather than peptides (<10 kDa). In contrast, peptides derived from caseins were more preferentially identified within a relatively short incubation time. It was the co-hydrolysis of caseins and some major MFGM proteins as anchors that destroyed the stability of MFGM. Furthermore, studies on the effect of trilayer membrane structure remaining at the interface on the hydrolysis rate of major MFGM proteins by plasmin revealed that ADPH and BTN were very sensitive to plasmin action, while PAS 7 was very resistant to plasmin action. Overall, membrane structure reduced the susceptibility of some major MFGM proteins to plasmin and provided protective effects. Therefore, this study provided important insights into the hydrolysis behavior of interfacial proteins in whole UI-UHT milk induced by plasmin.

Hydrolytic degradation behaviors of polylactides/poly(propylene carbonate blends: Monolayers and bulk films

The study investigates the hydrolytic degradation behaviors of blends comprising polylactides (PLA) and poly(propylene carbonate) (PPC) in the form of monolayers and bulk films. PLA is a biodegradable polymer widely used in various applications, while PPC offers unique properties, making it a promising candidate for blend formulations. The research explores the degradation kinetics and mechanical properties under controlled hydrolysis conditions. The finding focuses on the compatibility of PLA and PPC, their degradation mechanisms, and the impact of blend composition on degradation rates. Understanding the hydrolytic behavior of these blends is crucial for designing eco-friendly materials with tailored degradation profiles for diverse applications.

Tuning multiple enzyme-like activities by metal doping for identification and quantitation of antioxidants in cosmetics

Inspired by the hydrolysis behaviors of skin cells, we exquisitely designed and synthesized a class of hydrolase mimics to develop an analytical method that can both identify and quantity antioxidant components in skin-whitening cosmetics, including ascorbic acid (AA) and its glycoside and phosphate derivatives. A series of ultra-thin Cu1-xMnxO2 or Fe1-yMnyO2 with rich acid-base pairs were prepared via chemical deposition and in-situ CuI/FeII self-assembly. H218O and D216O isotopic labeling studies and density function theory (DFT) calculations were adopted to analyze the cleaving sites of ascorbyl phosphate (AAL)/ascorbyl glucoside (AAP) and confirm that H2O was involved in the new bonds. In-situ DRIFT NH3-IR and −TPD further confirmed that the Fe- or Cu-substitution could increase the quantity and strength of Brønsted and Lewis acid sites. A cascade catalytic fluorescence sensor was designed for selective recognition or quantification of AA and its derivatives, which presents ultra-high-precision (≤2.5 %), stability, and selectivity in testing the target ingredients of five cosmetics from the market. Our nanozymes exhibit higher catalytic efficiency of 17.1 s−1 for AA, 8.42 s−1 for AAL, and 3.32 s−1 for AAP, which are 5.6 ∼ 32.8-fold higher than those of their mimic proteases. This work provides a controllable methodology to design hydrolytic nanozymes, which sheds light on biomimetic engineering and paves the way for breakthroughs in cosmetics industrial applications in the future.

Metal-modified CeO2 nanobelts for catalytic oxidation of ethyl acetate: Roles of surface lattice oxygen and hydrolysis behaviors

Based on the comparison of three counterparts [Mg-, Al- and Cu-modified CeO2 nanobelts], it is illustrated that the low-temperature hydrolysis of ethyl acetate (EA) rapidly occurs and the removal of absorbed hydrolyzates (mainly acetates) is considered the rate-determining step. As the temperature increases, the escape of surface lattice oxygen (Os-latt) breaks through the shield of hydrolyzates and promotes the deep oxidation of intermediate products. Additionally, the activated Os-latt also facilitates the C-O bond cleavage in EA by nucleophilic attack. Due to the Os-latt escape, surface metal ions achieve more unsaturated coordinations to absorb the CH3COO– species, leading to competitive adsorption between O2 and hydrolyzates. The Cu modification strengthens the coordination adsorption of CH3COO– species, and the Al modification exhibits a low Os-latt mobility. These factors all contribute to a strong adsorption or accumulation of surface hydrolyzates. Therefore, a favorable ester hydrolysis-oxidation process over CeO2-based catalysts depends not only on excellent Os-latt mobility but also the suitable adsorption capacity of hydrolyzates, such as Mg modification.

Construction of Poly(butylene succinate)-Grafted Graphene Bionanocomposites: Intercalation Structure, Synergistic Thermal–Oxidative Stabilization Effect, and Hydrolytic Behavior

Construction of Poly(butylene succinate)-Grafted Graphene Bionanocomposites: Intercalation Structure, Synergistic Thermal–Oxidative Stabilization Effect, and Hydrolytic Behavior

Environmental Evaluation on Toxicity, Toxic Mechanism, and Hydrolysis Behavior of Potential Acethydrazide Fungicide Candidates.

The evaluation of toxicity and environmental behavior of bioactive lead molecules is helpful in providing theoretical support for the development of agrochemicals, in line with the sustainable development of the ecological environment. In previous work, some acethydrazide structures have been demonstrated to exhibit excellent and broad-spectrum fungicidal activity; however, its environmental compatibility needs to be further elucidated if it is to be identified as a potential fungicide. In this project, the toxicity of fungicidal acethydrazide lead compounds F51, F58, F72, and F75 to zebrafish was determined at 10 μg mL-1 and 1 μg mL-1. Subsequently, the toxic mechanism of compound F58 was preliminarily explored by histologic section and TEM observations, which revealed that the gallbladder volume of common carp treated with compound F58 increased, accompanied by a deepened bile color, damaged plasma membrane, and atrophied mitochondria in gallbladder cells. Approximately, F58-treated hepatocytes exhibited cytoplasmic heterogeneity, with partial cellular vacuolation and mitochondrial membrane rupture. Metabolomics analysis further indicated that differential metabolites were enriched in the bile formation-associated steroid biosynthesis, primary bile acid biosynthesis, and taurine and hypotaurine metabolism pathways, as well as in the membrane function-related glycerophospholipid metabolism, linolenic acid metabolism, α-linolenic acid metabolism, and arachidonic acid metabolism pathways, suggesting that the acethydrazide F58 may have acute liver toxicity to common carp. Finally, the hydrolysis dynamics of F58 was investigated, with the obtained half-life of 5.82 days. The above results provide important guiding significance for the development of new green fungicides.

Modelling and dynamic simulation to produce fermentable sugars from lignocellulosic substrates through dilute acid hydrolysis

AbstractThis research paper presents a comprehensive investigation aimed at enhancing the 2G bioethanol production process through the implementation of a dynamic process simulator. The simulator, developed using the Julia programming language, enables the prediction of acid hydrolysis behaviour by manipulating critical variables, including liquid–solid ratio (LSR), acid concentration (CA), and processing time (t). Through meticulous simulations and subsequent experimental validation, optimal operating conditions were revealed, with an H2SO4 concentration of 2% v/v, a LSR of 4% v/w, and 60‐min processing time at 121.1°C. This configuration led to remarkable outcomes, including a xylose concentration of 47.45 g L−1 and an 87.4% hemicellulose removal percentage. Moreover, the simulator unveiled the adverse influence of low LSR values on xylose production and the generation of degradation products. The recalibration of kinetic parameters, guided by experimental data, further fine‐tuned the simulator's predictive accuracy. Overall, this study underscores the potential of the simulator in optimizing various raw materials and presents a promising avenue for advancing 2G bioethanol industry practices.

Hydrolysis behavior and mechanistic insights of CaMg2InX (X = 0.1, 0.3, 0.5, 0.7) ternary alloy for sustainable hydrogen production

The hydrolysis behavior of CaMg2In0.1, CaMg2In0.3, CaMg2In0.5, and CaMg2In0.7 ternary alloys in an MgCl2 solution following casting and hydrogenation were investigated. The hydrolysis mechanism of these alloys is elucidated through an analysis of microstructure, phase composition, and kinetics before and after hydrolysis. The nucleation-growth Avrami model is employed to accurately model the hydrolysis kinetics, revealing improved hydrolysis yields and reaction rates following hydrogenation. Notably, CaMg2In0.1 has demonstrated exceptional hydrolysis characteristics, exhibiting a yield of 1140 mL/g, an initial hydrolysis rate of 113 mL/g·s, and an activation energy of 24.3 ± 1.7 kJ·mol−1. The yield of H-CaMg2In0.1 further escalates to 1800 mL/g with a rate of 221 mL/g·s, attributed to the formation of Ca4Mg3H14 and In phases subsequent to the hydrogenation of In2Ca and Mg3In phases in the alloy. These newly formed phases act as catalysts and actively participate in the hydrolysis process, providing active sites for hydrogen production, thus enhancing hydrolysis yields and kinetics. It is observed that with increasing In content, the order of hydrolysis performance of the alloy is as follows: CaMg2In0.1 > CaMg2In0.3 > CaMg2In0.5 > CaMg2In0.7, consistent with the trend after hydrogenation. These findings indicate that the addition of In significantly enhances the hydrolysis performance of CaMg2 alloys, offering a promising strategy for preparing magnesium-based alloys with high yields and favorable kinetic properties.

Molecular structure regulation of functional polylactic acid based on chain expansion reaction and its improved hydrolysis resistance

AbstractIn this work, the functional polylactic acid (PLA) was synthesized using epoxy chain extender (ADR) as a chain extender agent through melt blending method. The effects of ADR content on the molecular structure, thermal properties, and tensile properties of the functional PLA were investigated. Meanwhile, the hydrolytic behavior of the PLA/ADR materials at different hydrolysis temperatures was explored. It was found that ADR effectively regulated the molecular structure of PLA in the molten state and significantly increased the relative molecular weight, storage modulus, and complex viscosity of PLA. In addition, the Cole‐Cole diagram results suggested the branched structure of PLA chain expansion systems. Based on mechanical property tests, it was noted that the addition of ADR made the molecular chain form a micro‐crosslinked structure. Additionally, the mass loss rate of PLA/1.6ADR (the dosage of ADR was 1.6 wt%) was 14.75% after 14 weeks of hydrolysis under hydrolysis conditions at 58°C, while that of pure PLA was 25.89%. Moreover, the functional PLA/ADR materials exhibited significantly slower decrease rates in molecular weight, melting temperature, and tensile strength, and still maintained intact morphology after 14 weeks of hydrolysis compared to pure PLA. Therefore, the molecular structure of PLA is effectively regulated by ADR, which greatly enhances the hydrolysis resistance and further promotes the range of application of PLA.

Understanding of ammonium salts under-deposit corrosion: Electrochemical and AIMD investigations

In-situ electrochemical experiments and ab initio molecular dynamics (AIMD) simulations are combined to investigate the under-deposit corrosion and hygroscopicity of ammonium salts on SAE 1020 steel interdigital electrodes. The findings indicate that the hygroscopicity of ammonium salts influences the evolution of the interface and the accumulation of the product film. The corresponding simulations reveal that the hydrolysis of NH4+ leads to the generation of a proton transfer chain, resulting in an elevation of H+ concentration. This hydrolysis behavior is effectively catalyzed on the Fe(1 0 0) surface, promoting the occurrence of anodic adsorption and cathodic hydrogen evolution reaction, thereby inducing corrosion.

The pretreatment and enzymatic hydrolysis behaviors of lignocellulosic biomass (oak and larch) based on structural changes in its lignin-carbohydrate complex

This study investigated the structural changes in oak and larch lignin-carbohydrate complexes (LCCs) during hydrothermal treatment and enzymatic hydrolysis. Hydrothermal treatment caused hemicellulose degradation (degradation rate at 170 ℃: larch 19.40%; oak, 22.26%). The LCC1 (glucan-lignin) fraction was the highest in the raw material of both biomasses. The LCC3 (xylan-lignin) and LCC2 (glucomannan-lignin) fractions were high in oak and larch, respectively; these fractions decreased as the hydrothermal treatment temperature increased (owing to hemicellulose degradation). Both biomasses had phenyl glycoside, benzyl ether (BE), and γ-ester (Est) linkages. The BE and Est linkages decreased as the hydrothermal treatment temperature increased; the Est linkages decrease was more significantly in oak than in larch. The efficiency of enzymatic hydrolysis was higher in oak than that in larch and increased as the hydrothermal treatment temperature increased. Furthermore, enzyme adsorption on the LCC1 sensor was higher in oak than in larch. The chemical compositions and LCC linkages of the biomass were changed by the hydrothermal treatment, which affected the efficiency of enzymatic hydrolysis. Moreover, the efficiency of enzymatic hydrolysis was higher for oak than for larch because of the difference hemicellulose and cellulose contents and LCC linkages.

Reaction contest: hydrolysis versus intramolecular cyclisation reaction in alkyl squaramate esters.

The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly basic neighboring group participation (NGP) substitutions, remain stable up to pH 9. Their hydrolysis rate (k OH ≈ 10-1 M-1 s-1) is 1000 times faster than that of squaramides, following a second-order rate law. Squaramate esters functionalized with basic NGP groups, such as amines, display a pH-dependent hydrolysis rate due to anchimeric assistance of the terminal amino group, reducing stability to pH 5. However, when the squaramate ester has a terminal nucleophilic group in the γ position of the alkyl chain, it undergoes rapid intramolecular cyclization, forming cyclic squaramides.

Screening of oxidative behavior in catalytic amyloid assemblies.

Once considered a thermodynamic minimum of the protein fold or as simply by-products of a misfolding process, amyloids are increasingly showing remarkable potential for promoting enzyme-like catalysis. Recent studies have demonstrated a diverse range of catalytic behaviors that amyloids can promote way beyond the hydrolytic behaviors originally reported. We and others have demonstrated the strong propensity of catalytic amyloids to facilitate redox reactions both in the presence and in the absence of metal cofactors. Here, we present a detailed protocol for measuring the oxidative ability of supramolecular peptide assemblies.

Comparative analysis of self-cure and dual cure-dental composites on their physico-mechanical behaviour.

Clinical practitioners may have become familiar with the rapid transformation of dental composites. However, they may not scientifically understand the factors influencing the mechanical and physical properties. Scientific knowledge of filler-resin interaction can significantly improve clinical understanding of resin composites. Several independent studies have examined the mechanical and physico-mechanical properties of dental resin composites; however, no comprehensive study has examined the influence of fillers and resin materials on the physico-mechanical properties of both self-cure and dual-cure composites. This study performed investigations on the physico-mechanical behaviour of four commercially available dual-cure dental composites (Bioactive, Fill Up!, Surefil One, Cention N) and two commercially available self-cure dental composites (Stela Capsule and Stela Automix). Test specimens for flexural and compressive strength, microhardness, fracture toughness, and hydrolytic behaviour were prepared and tested as per respective standards. The data sets were statistically analysed using one-way ANOVA and Tukey's post-hoc comparison. There was a substantial variation in flexural strength and modulus values in this study, ranging from 32.0 to 113.4 MPa and 2.36 to 12.07 GPa, respectively. Similarly, there were significant differences in compressive strength between the materials in this study, ranging from 119.3 to 223.5 MPa. The highest fracture toughness value was found to be 1.41 MPa.m0.5, while the lowest value was 0.43 MPa.m0.5. Variations in surface microhardness were significant (24.11-68.0 N/mm2), which correlated with the filler content. Water sorption and solubility demonstrated high variations among materials, with Surefil One exceeding ISO 4049 thresholds significantly. A linear correlation can be established between surface microhardness (HV) and flexural and compressive moduli, as well as filler content (wt.%). However, both flexural and compressive strengths are impacted by the resin's constituent monomers and the resin-filler matrix's cross-linking capability. Additionally, factors such as filler size, shape, and the cross-linking ability of the resin-filler matrix play a crucial role in fracture toughness and the propagation of cracks within the restoration. Also, resin monomers and filler particle size affect the hydrolytic degradation characteristics of composites, which can also affect their mechanical properties. © 2023 Australian Dental Association.