Reaction Products Research Articles

Synthesis of the O antigen repeating units of Escherichia coli serotypes O117 and O107

Abstract Escherichia coli serotype O117 (ECO117) are pathogenic bacteria that produce Shiga toxin. Repeating units of the O antigen of ECO117 have the pentasaccharide structure [4-D-GalNAcβ1-3-L-Rhaα1-4-D-Glcα1-4-D-Galβ1-3-D-GalNAcα1-]n. The related non-pathogenic serotype (ECO107) contains a GlcNAc residue instead of Glc in the repeating unit, and the biosynthetic enzymes involved are almost identical. We assembled these repeating units based on GalNAcα-diphosphate-phenylundecyl (GalNAcα-PP-PhU), an analog of the natural intermediate GalNAc-diphosphate-undecaprenyl. We previously characterized α1,4-Glc-transferase WclY from ECO117 that transfers the Glc residue to Galβ1–3GalNAcα-PP-PhU and showed that Arg194Cys mutants of WclY are active α1,4-GlcNAc-transferases. In this work, the reaction products of WclY were used as acceptor substrates for the final enzymes in pathway, L-Rha-transferase WclX, and GalNAc-transferase WclW, demonstrating a complete synthesis of the ECO117 and O107 repeating units. WclX transfers L-Rha with high specificity for the WclY enzyme product as the acceptor and for TDP-L-Rha as the donor substrate. A number of highly conserved sequence motifs were identified (DDGSxD, DxDD, and YR). Mutational analysis revealed several Asp residues are essential for the catalysis of L-Rha transfer, while mutations of Asp44 and R212 substantially reduced the activity of WclX. WclW is a GT2 enzyme specific for UDP-GalNAc but with broad specificity for the acceptor substrate. Using L-Rhaα-p-nitrophenyl as an acceptor for WclW, the reaction product was analyzed by NMR demonstrating that GalNAc was transferred in a β1–3 linkage to L-Rha. The in vitro synthesis of the repeating units allows the production of vaccine candidates and identifies potential targets for inhibition of O antigen biosynthesis.

Sponge-shaped Au nanoparticles: a stand-alone metallic photocatalyst for driving the light-induced CO2 reduction reaction

Coinage metal nanoparticles (NPs) enable plasmonic catalysis by generating hot carriers that drive chemical reactions. Making NPs porous enhances the adsorption of reactant molecules. We present a dewetting and dealloying strategy to fabricate porous gold nanoparticles (Au-Sponge) and compare their CO2 photoreduction activity with respect to the conventional gold nanoisland (Au-Island) morphology. Porous gold nanoparticles exhibit an unusually broad and red-shifted plasmon resonance which is in agreement with the results of finite difference time domain (FDTD) simulations. The key insight of this work is that the multi-step reduction of CO2 driven by short-lived hot carriers generated by the d → s interband transition proceeds extremely quickly as evidenced by the generation of methane. A 3.8-fold enhancement in the photocatalytic performance is observed for the Au-Sponge in comparison to the Au-Island. Electrochemical cyclic voltammetry measurements confirm the 2.5-fold increase in the surface area and roughness factor of the Au-Sponge sample due to its porous nature. Our results indicate that the product yield is limited by the amount of surface adsorbates i.e. reactant-limited. Isotope-labeled mass spectrometry using 13CO2 was used to confirm that the reaction product (13CH4) originated from CO2 photoreduction. We present the plasmon-mediated photocatalytic transformation of 4-aminothiophenol (PATP) into p,p'-dimercaptoazobenzene (DMAB) using Au-Sponge and Au-Island samples.

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments

A series of new RS−, RS−CH2− and R2N−CH2-functionalized сatechols with heterocyclic fragments such as 1,3,4-oxadiazole, 1,2,4-triazole, thiazole, or pyridine were synthesized by the reaction of 3,5-di-tert-butyl-o-benzoquinone or 3,5-di-tert-butyl-6-methoxymethylcatechol with different heterocyclic thiols. The S-functionalized catechols were prepared by the Michael reaction from 3,5-di-tert-butyl-o-benzoquinone and the corresponding thiols. The starting reagents such as substituted 1,3,4-oxadiazole-2-thiols and 4H-triazole-3-thiols are characterized by thiol–thione tautomerism, therefore their reactions with 3,5-di-tert-butyl-6-methoxymethylcatechol can proceed at the sulfur or nitrogen atom. In the case of mercapto-derivatives of thiazole or pyridine, this process leads to the formation of the corresponding thioethers with a methylene linker. At the same time, thiolated 1,3,4-oxadiazole or 1,2,4-triazole undergo alkylation at the nitrogen atom in the reaction with 3,5-di-tert-butyl-6-methoxymethylcatechol to form the corresponding thiones. The yield of reaction products ranges from 42 to 80%. The crystal structures of catechols with 3-nitropyridine or 1,3,4-oxadiazole-2(3H)-thione moieties were established by single-crystal X-ray analysis. The possibility of forming intra- and intermolecular hydrogen bonds has been established for these compounds. The electrochemical behavior of the studied compounds is influenced by several factors: the nature of the heterocycle and its substituents, the presence of a sulfur atom in the catechol ring, or a thione group in the heterocyclic core. The radical scavenging activity and antioxidant properties were determined using the reaction with synthetic radicals, the cupric reducing antioxidant capacity assay, the inhibition process of superoxide radical anion formation by xanthine oxidase, and the process of lipid peroxidation of rat liver (Wistar) homogenates in vitro.

Effect of electrolyte level on performance and mass transfer of non-aqueous lithium-oxygen battery

To accurately reveal the effect of electrolyte content on mass transfer within lithium-oxygen batteries and their discharge performance, this study utilizes computed tomography(CT) scanning technology and digital reconstruction methods to construct a geometric model of the lithium-oxygen battery cathode that is equivalent to the actual one. Based on the fundamental principles of mass transfer, fluid dynamics, and electrochemistry, a two-dimensional model for the discharge process of lithium-oxygen batteries is established. This model facilitates analysis of various parameters and their influencing factors, including the distribution of reaction products, pore structure, oxygen concentration distribution, battery performance, and overpotential, within the lithium-oxygen battery cathode. The research findings indicate that the deposition of reaction products alters the cathode structure and material transport; lower discharge current density and higher electrolyte levels are conducive to the dispersed deposition of reaction products, thereby reducing the deposition's resistance to internal mass transfer in the cathode.

Development and Validation of the MAST ISOPLEX® VTEC Kit for Simultaneous Detection of Shiga Toxin/Verotoxin 1 and 2 (stx1/vt1 and stx2/vt2) with Inhibition Control (IC) in a Rapid Loop-Mediated Isothermal Amplification (LAMP) Multiplex Assay

Loop-mediated isothermal amplification (LAMP) is a cost-effective, rapid, and highly specific method of replicating nucleic acids. Adding multiple targets into a single LAMP assay to create a multiplex format is highly desirable for clinical applications but has been challenging due to a need to develop specific detection techniques and strict primer design criteria. This study describes the evaluation of a rapid triplex LAMP assay, MAST ISOPLEX® VTEC, for the simultaneous detection of Shiga toxin/verotoxin 1 and 2 (stx1/vt1 and stx2/vt2) genes in verotoxigenic Escherichia coli (E. coli) (VTEC) isolates with inhibition control (IC) synthetic DNA using a single fluorophore–oligonucleotide probe, MAST ISOPLEX® Probes, integrated into the primer set of each target. MAST ISOPLEX® Probes used in the MAST ISOPLEX® VTEC kit produce fluorescent signals as they integrate with reaction products specific to each target, allowing tracking of multiple amplifications in real time using a real-time analyzer. Initial validation on DNA extracts from fecal cultures and synthetic DNA sequences (gBlocks) showed that the MAST ISOPLEX® VTEC kit provides a method for sensitive simultaneous triplex detection in a single assay with a limit of detection (LOD) of less than 100 target copies/assay and 96% and 100% sensitivity and specificity, respectively.

A Lithium‐Oxygen Battery Exploiting Carbon Nanotubes, Graphene and Gold Catalyst

AbstractLithium‐oxygen (Li‐O2) battery is considered a high‐energy alternative to Li‐ion one due its characteristic electrochemical conversion process, with the additional advantage of lower cost and environmental impact. However, this emerging battery still requires an enhancement of stability and lifespan to allow its use as a practical energy storage system. In this work we investigate an electrode material benefitting of multiwalled carbon nanotubes (MWCNTs), few layer graphene (FLG), and gold nano‐powder catalyst to improve the Li‐O2 battery performances in terms of energy efficiency, cycle life and stability. Morphological, structural, and electrochemical tests indicate that the composite electrode can actually boost the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and enhance the Li‐O2 process reversibility, with a capacity of 1000 mAh g−1 over 70 cycles. On the other hand, the tests reveal the role of the gold in decreasing the polarization and increasing the cell life. Therefore, the results suggest the combination of carbons with various morphologies as a suitable architecture for hosting the Li‐O2 reaction products and allowing their reversible reaction. On the other hand, the results highlight the necessity for a better tuning the noble metal characteristics to further enhance the cell performances.

Design Optimization of a Novel Catalytic Approach for Transglucosylated Isomaltooligosaccharides into Dietary Polyols Structures by Leuconostoc mesenteroides Dextransucrase.

Polyols, or sugar alcohols, are widely used in the industry as sweeteners and food formulation ingredients, aiming to combat the incidence of diet-related Non-Communicable Diseases. Given the attractive use of Generally Regarded As Safe (GRAS) enzymes in both academia and industry, this study reports on an optimized process to achieve polyols transglucosylation using a dextransucrase enzyme derived from Leuconostoc mesenteroides. These enzyme modifications could lead to the creation of a new generation of glucosylated polyols with isomalto-oligosaccharides (IMOS) structures, potentially offering added functionalities such as prebiotic effects. These reactions were guided by a design of experiment framework, aimed at maximizing the yields of potential new sweeteners. Under the optimized conditions, dextransucrase first cleared the glycosidic bond of sucrose, releasing fructose with the formation of an enzyme-glucosyl covalent intermediate complex. Then, the acceptor substrate (i.e., polyols) is bound to the enzyme-glucosyl intermediate, resulting in the transfer of glucosyl unit to the tested polyols. Structural insights into the reaction products were obtained through nuclear maneic resonance (NMR) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) analyses, which revealed the presence of linear α(1 → 6) glycosidic linkages attached to the polyols, yielding oligosaccharide structures containing from 4 to 10 glucose residues. These new polyols-based oligosaccharides hold promise as innovative prebiotic sweeteners, potentially offering valuable health benefits.

OH radical initiated oxidative degradation of imidacloprid in the environment: An assessment of breakdown kinetics and environmental hazards

Imidacloprid (IMI) is a common neonicotinoid pesticide that acts via a similar mechanism of action to nicotine, a naturally occurring insecticide. It is therefore important to understand its chemical fate in the environment. Hydroxyl radicals (HO) are significant oxidizing species in natural aquifers due to their strong reactivity towards organic substrates. Therefore, principal photo-oxidation products are expected to form with the involvement of HO in the self-cleaning process of water in nature. Here quantum chemical calculations are used to examine the reaction of IMI with HO in the atmosphere and aqueous environments. It was found that the principal mechanism of the HO + IMI reaction is the hydrogen transfer that, in a two-step process, produces stable cations in the gas phase. Within the atmospheric temperature range of 253–323 K, the overall rate constants for the HO + IMI reaction decreased from 4.35 × 1010 to 2.13 × 1010 M−1 s−1. Consequently, IMI can undergo rapid gaseous degradation within a comparatively brief period of 2.81 × 10−4 – 5.75 × 10−4 years. However, differences in environmental temperature and pH in aqueous environments influence the processes, rate constants, and products of IMI breakdown by the HO radical. The data indicate that IMI breakdown by OH radicals is strongly temperature and pH-dependent, resulting in the generation of different reaction products. The results imply that at all pH levels, the interaction between IMI and the ambient HO radical in water produces toxic chemical species. According to the computed data, it appears that IMI and the vast majority of degradation products present potentially carcinogenic and/or mutagenic hazards, and they also lack downstream biodegradability.

Optical and Catalytic Properties of Nanozymes for Colorimetric Biosensors: Advantages, Limitations, and Perspectives

AbstractDetection of colorimetric signals is commonly used in various analytical methods and for testing in non‐laboratory and resource‐limited settings. The performance of colorimetric assays is largely based on nanoparticles and their unique optical properties. Multifunctional nanoparticles combining optical and enzyme‐like catalytic properties—known as nanozymes—hold great promise for analytical applications as signal‐generating labels. However, the extensive focus on the catalytic properties leaves their unique optical properties overlooked. In this article, the use of the optical and catalytic properties of nanozymes is reviewed for analytical applications relying on the inherent optical properties of nanozymes, the colorimetric detection of a catalytically‐formed product, and colorimetric changes of nanoparticles caused by the catalytically‐formed product. The impact of the extinction coefficient of nanozymes and reaction products, as well as the kinetic parameters of nanozymes on the sensitivity and limit of detection of assays, are quantitatively evaluated. Finally, the existing limitations and prospects of nanozymes for colorimetric biosensors are summarized.

Kinetic Study of OH Radical Reactions with Cyclopentenone Derivatives.

We investigated the reactions of the hydroxyl radical (OH) with cyclopentenone derivatives and cyclopentanone in a quasi-static reaction cell at 4 Torr across a 300-500 K temperature range. The OH radicals were generated using pulsed laser photolysis of hydrogen peroxide vapors, and the ketone reactants were introduced in excess. The relative concentrations of the radicals were monitored as a function of reaction time using laser-induced fluorescence. At room temperature, the reaction rate coefficients were measured to be 1.2(±0.1) × 10-11 cm3 s-1 for reaction with 2-cyclopenten-1-one (R1); 1.7(±0.2) × 10-11 cm3 s-1 for reaction with 2-methyl-2-cyclopenten-1-one (R2); and 4.4(±0. 7) × 10-12 cm3 s-1 for reaction with 3-methyl-2-cyclopenten-1-one (R3). Over the experimental temperature range, the rate coefficients can be fitted with the modified Arrhenius expressions k1(T) = 1.2 × 10-11 (T/300)0.26 exp (6.7 kJ mol-1/R {1/T - 1/300}) cm3 s-1, k2(T) = 1.7 × 10-11 (T/300)6.4 exp (27.6 kJ mol-1/R {1/T - 1/300}) cm3 s-1, k3(T) = 4.4 × 10-12 (T/300)17.8 exp (57.8 kJ mol-1/R {1/T - 1/300}) cm3 s-1. In the cases of 2-cyclopenten-1-one and 2-methyl-2-cyclopenten-1-one, the temperature dependence of the rate coefficients is similar to that calculated or measured for noncyclic conjugated ketones. We also found that the reaction with 3-methyl-2-cyclopenten-1-one was slower, with rate coefficients similar to those measured for the reaction with the saturated cyclic ketone cyclopentanone. To discuss the experimental data, we use potential energy surfaces (PES) calculated at the CCSD(T)/cc-pVTZ//M06-2X/6-311+G** level of theory. RRKM-based Master equation calculations were also performed to infer the most likely reaction products over a wide range of temperatures and pressures. We suggest that both abstraction and addition mechanisms contribute to the overall OH removal, forming radical products stabilized by resonance. We also discuss the relevance for combustion and atmospheric chemistry.

The Effects of Ceric Ammonium Nitrate in the Oxidation of 2-Benzyl-1,4-dimethoxybenzene Derivatives

The one- or two-electron reduction in quinone compounds gives rise to semiquinones and hydroquinones, respectively, which, in turn, can be oxidized back to quinones, generating a cyclic redox system with the production of reactive oxygen species (ROS). For these reasons, quinone derivatives participate in various biological processes in metabolic pathways, such as oxidative reactions and electron transport. In addition, natural quinone compounds as well as their semisynthetic and/or synthetically produced derivatives are of great pharmacological interest for the discovery and design of new drugs. As a result, their chemical reactivity as well as new methods for their synthesis are being investigated on an ongoing basis. Herein, a mild and efficient synthesis to obtain 2-(4-benzyl substituted)-1,4-dimethoxybenzene derivatives is reported. In addition, an evaluation of the effects on the quinone/diquinone ratio in the reaction product in relation to different ways of adding the oxidant CAN to the arene solution is discussed.

Electro-activation for efficient lactulose production: The impact of operational parameters, electrolyte types, and environmental conditions

The electro-activation (EA) process has been employed to convert lactose into lactulose, a potent prebiotic with numerous health benefits. The study identified optimal conditions for lactulose production, including a specific current density, the use of calcium chloride as an efficient electrolyte, and the superiority of a steel cathode over a graphite cathode. The formation of intermediates other than lactulose increased as the temperature increased. The changes in pH and oxidation-reduction potential during the isomerization process were observed, highlighting their vital role in the formation of an ideal alkaline environment for lactulose production. The resultant solution produced by the EA process has significant antioxidant characteristics, likely due to the formation of Maillard Reaction Products during lactulose production. In conclusion, the EA system, with optimal operating conditions, is an energy-efficient, reagent-free, and environmentally friendly alternative for lactulose production.

Elucidating the Hydrolysis and Polymerization Reactions of Al3+‐Solvated Molecules by Reactive Molecular Dynamics Simulation

ABSTRACTUtilizing the reactive molecular dynamics (ReaxFF MD) simulation, we conducted a comprehensive study on the impact of basicity (OH−/Al3+ ratio), concentration, and temperature on the hydrolysis and polymerization reactions of Al3+‐solvated molecules. Through simulations, we analyzed the structural changes, energy fluctuations of the system, and the evolution patterns of reaction products under different parameters, which were subsequently validated by experimental data. The research results indicate that hydroxide ions in the solution directly influence the breakage of OH bonds in the coordinating water molecules of solvated aluminum ions. This, in turn, affects the number of H2O and OH− ions coordinated with Al3+, leading to changes in hydrolysis products. Additionally, the number of OH− ions surrounding Al3+ affects the electrostatic repulsion, making it easier for polymerization reactions to occur as the system approaches the point of zero charge. On the other hand, an increase in concentration and temperature enhances the frequency of cluster collisions, thus contributing to an increase in polymerization degree. The experimental results align closely with our simulated predictions. As the pH value increases, the particle size exhibits a trend of first increasing and then decreasing, reaching a maximum at the point of zero charge. Simultaneously, an increase in concentration also prompts an increase in particle size. The combination of these empirical results with simulations enhances the credibility and reliability of our model's predictive capabilities. This study not only expands our understanding of the relevant chemical reaction processes but also provides important theoretical support for practical applications in related fields.

Glucose Oxidase-Based Glucose Biosensing with a Simple Dual Ag/AgCl Probe Conductivity Readout.

We describe a conductometric assay of the enzymatic conversion of glucose to gluconic acid by dissolved glucose oxidase (GOx), using the generation of proton and gluconate from the reaction product dissociation for glucose detection. Simple basics of ionic conductivity, a silver/silver chloride wire pair, and a small applied potential translate glucose-dependent GOx activity into a scalable cell current. Enzyme immobilization and complex sensor design, involving extra nanomaterials or microfabrication of electrode structures, are entirely avoided, in contrast to all modern electrochemical glucose biosensors. Assay calibration showed a response linearity up to 500 μM, with a sensitivity of about 1.3 nA/μM. Selectivity tests excluded signals from sugars other than glucose, and glucose quantifications with recovery rates close to 100% were reached with a model sample and a beverage. Easy use of elementary physicochemical phenomena and a satisfactory performance are assets of the proposed non-amperometric glucose biosensing strategy. Assay integration into a planar dual electrode platform, with or without microfluidic application option, is feasible because of the simplicity of the sensor readout and suggests a route to affordable glucose analysis in beverage, food, and body fluid samples.

Spatial distribution of antioxidant activity in baguette and its modulation of proinflammatory cytokines in RAW264.7 macrophages

Baguette is a globally acclaimed bakery staple, composed by a crispy crust and soft crumb, both containing Maillard reaction products (MRPs) with potential bioactivities. However, MRPs’ impacts on the nutritional and health attributes of baguette, particularly in terms of cellular and biological functions, are yet to be clearly elucidated. This study chemically characterizes the crust and crumb of baguettes and investigates the influence of the Maillard reaction on baguette’s nutritional profile, especially in the antioxidant and anti-inflammatory effects. The findings indicate an increase in browning intensity and advanced glycation end products (AGEs) from the baguette’s interior to its exterior, alongside a significant rise in the antioxidant capacity of the crust, suggesting the Maillard reaction’s role in boosting antioxidative properties. Both the crust and crumb demonstrated strong cytocompatibility with immune cells, capable of reducing cellular oxidative stress and regulating intracellular free radical levels. The crust effectively countered peroxyl radical-induced cell membrane hyperpolarization by 91% and completely neutralized the suppression of oxygen respiration in mitochondria, displaying higher efficacy than the crumb. In contrast, crumb extracts were more potent in inhibiting lipopolysaccharide-induced expression of proinflammatory cytokines, such as interleukins-1β (IL-1β) and IL-6, in macrophages. It could provide the fundamental data and cell-based approach for investigating the biological impacts of bread on immune responses, contributing to the refinement and supplementation of nutritional recommendations.

Influence of vacuum and high-temperature on the evolution of mechanical strength and microstructure of alkali-activated lunar regolith simulant

Alkali-activated lunar regolith (AALR) has become one of the most promising lunar building materials, offering the potential to support the construction of large-scale lunar structures. This paper presents a comprehensive experimental investigation on the fresh properties, physical properties, mechanical performance and microstructural characteristics of alkali-activated lunar regolith simulant (AALRS) considering the effects of lunar environments (high-temperature, vacuum and coupled high-temperature and vacuum), alkaline activators (sodium hydroxide and sodium silicate) and curing age. The results show that AALRS under high-temperature environment exhibits higher strength while the strength development is limited. However, AALRS under vacuum environment exhibits lower strength but the strength increases as the curing time increases. In terms of pore structure, the volume fractions of macro voids for SH-V and SS-V account for up to 50.94 % and 63.64 %, respectively, which are 12.22 % and 7.95 % higher than those of SH-H and SS-H. Regarding the impact of coupled high-temperature and vacuum environment, the compressive strength of SH-HV-7 is reduced by 47.8 % compared to that of SH-H-7, while the compressive strength of SS-HV-7 exhibits a 57.2 % increase over that of SS-H-7. The sodium hydroxide-activated (SH-activated) system and sodium silicate-activated (SS-activated) system demonstrate fundamentally intrinsic differences in terms of reaction products, structure build-up and pore structure. The positive optimization mechanism and reverse degradation effect of vacuum environment on the performance of AALRS paste were revealed. Finally, the evolution of structural characteristics of AALRS paste under different environments was elucidated.

12-Nor-rotenoids and other cytotoxic constituents of Pachyrhizus erosus seeds

Five previously undescribed compounds, including three 12-nor-rotenoids, were isolated from Pachyrhizus erosus seeds. A brief survey on the dealkylation of selected rotenoids with BBr3 was undertaken. Spectroscopic data of these previously undescribed compounds and reaction products are reported. The proposal of absolute configurations at stereocenters in the isolates and reaction products was based on NMR and ECD data. Most of the isolates and reaction products were evaluated for their growth inhibitory activities against four cancer cell lines and a Vero cell line. Many compounds exhibited strong to moderate activities with IC50 values ranging from 0.06 to 20.9 μM, and their structure-activity relationships were evaluated.

Molecular Basis of the Substrate Specificity of Phosphotriesterase from Pseudomonas diminuta: A Combined QM/MM MD and Electron Density Study.

The occurrence of organophosphorus compounds, pesticides, and flame-retardants in wastes is an emerging ecological problem. Bacterial phosphotriesterases are capable of hydrolyzing some of them. We utilize modern molecular modeling tools to study the hydrolysis mechanism of organophosphorus compounds with good and poor leaving groups by phosphotriesterase from Pseudomonas diminuta (Pd-PTE). We compute Gibbs energy profiles for enzymes with different cations in the active site: native Zn2+cations and Co2+cations, which increase the steady-state rate constant. Hydrolysis occurs in two elementary steps via an associative mechanism and formation of the pentacoordinated intermediate. The first step, a nucleophilic attack, occurs with a low energy barrier independently of the substrate. The second step has a low energy barrier and considerable stabilization of products for substrates with good leaving groups. For substrates with poor leaving groups, the reaction products are destabilized relative to the ES complex that suppresses the reaction. The reaction proceeds with low energy barriers for substrates with good leaving groups with both Zn2+and Co2+cations in the active site; thus, the product release is likely to be a limiting step. Electron density and geometry analysis of the QM/MM MD trajectories of the intermediate states with all considered compounds allow us to discriminate substrates by their ability to be hydrolyzed by the Pd-PTE. For hydrolyzable substrates, the cleaving bond between a phosphorus atom and a leaving group is elongated, and electron density depletion is observed on the Laplacian of electron density maps.

Design-driven approach for engineered geopolymer composite with recorded low fiber content

How to design an engineered cementitious composite (ECC) achieving both economic viability and ultra-sustainability has been the longstanding goal of ECC community. This study presents a design-driven approach to tackle this challenge through yielding a low matrix fracture toughness and a sufficiently strong interfacial bonding between fiber and matrix concurrently. As a result, only 0.2 % fiber content was sufficient for achieving robust strain-hardening in Engineered Geopolymer Composite (EGC), which, to the authors’ knowledge, is the lowest recorded thus far. The tensile strain-to-fiber content ratio reached 25, a remarkable 233 % higher than the existing strain-hardening composites. Besides, the compressive strength was around 40 MPa, marking the highest specific strength among the ECCs with a density below 1450 kg/m3. Leveraging the high porosity of 38 % and the presence of shrinkage micro-cracks in the matrix, a low fracture toughness, combined with a robust friction between fiber and matrix, facilitated the noticeable strain-hardening. The reaction product was identified as a dense alkaline aluminosilicate hydrate (N-A-S-H) gel, benefiting the interfacial bonding and compressive strength. The embodied energy and carbon of the EGC diminished by 27 % and 63 % compared to ordinary concrete, respectively, and the corresponding cost was 79 % lower than the classic M45-ECC, contributing significantly to ultra-sustainability.

Three-dimensional phase field modeling, orientation prediction and stress field analyses of twin-twin, twin-grain boundary reactions mediated by disclinations in hexagonal close-packed metals

Crystalline defects, such as dislocations, disclinations, twins and grain boundaries, play critical roles in determining the mechanical properties of metals and alloys. In particular, with multiple competitive deformation modes activated, the mechanical behaviors of hexagonal close-packed metals are strongly influenced by the interactions and reactions of various types of defects. Despite extensive studies on the elastic interactions of defects, a theoretical framework capturing crystallographic reactions, especially reaction products and associated local stress concentration, is still unavailable. Here we suggest a disclination-based method to quantify defect reactions. By using a combination of crystallographic calculations and phase field modeling/simulations, twin-twin and twin-grain boundary reactions in hexagonal close-packed metals have been quantitatively analyzed. It has been found that partial disclinations, accompanied with other defects (e.g., {112¯6} and {112¯2} high-index twins), can be generated by defect reactions as typical byproducts. The orientation change and stress fields caused by disclination formation have been systematically calculated, which offers a rigorous mathematical foundation to explore twin-twin, twin-grain boundary reactions. By quantitatively determining defect reactions and local stress fields, our work provides new insights into the deformation mechanism and microstructure-property relationship in metallic materials.