Structure-stability Relationship Research Articles

Supramolecular Handshakes: Characterization of Urea-Carboxylate Interactions Within Calixarene Frameworks.

The research of molecular capsules offers high application potential and numerous benefits in various fields. With the aim of forming supramolecular capsules which can be reversibly assembled and dissociated by simple external stimuli, we studied interactions between calixarenes containing urea and carboxylate moieties. To this end two ureido-derivatives of p-tert-butylcalix[4]arene comprising phenylureido-moieties and diacetate-calix[4]arenes were prepared. The binding of acetate by ureido-derivatives of calixarene in acetonitrile was characterized, revealing high affinity of ureido-calixarenes for carboxylates. This suggested high potential for uniting the complementary calix[4]arenes via H-bonds between carboxylic groups and urea moieties. The assembly of calixarenes was examined in detail by means of UV, 1H NMR, ITC, DOSY, MS, and conductometry providing insight in the structure-stability relationship. The tetraureido-calixarene derivative formed the most stable heterodimers with diacetate-calix[4]arenes featuring practically quantitative association upon mixing the two calixarene counterparts. The possibility of controlling the formation of the heterodimer by protonating the carboxylates, thereby hindering the interactions critical for capsule assembly, was investigated. Indeed, the reversibility of breaking and re-forming the heterodimer by addition of an acid and base to the solution containing urea- and carboxylate-derivative calix[4]arene was demonstrated using NMR spectroscopy.

Deactivation of porphyrin metal-organic framework in advanced oxidation process: Photobleaching and underlying mechanism

Porphyrin metal-organic frameworks (MOFs) are widely used in photocatalytic advanced oxidation processes (AOP). However, the stability and deactivation of MOFs, crucial for reusability, have been understudied compared to their catalytic activity. We investigated photobleaching in porphyrin MOFs PCN-224-M (M= H2, Fe, Co, Cu, Zn) under visible light and H2O2. The MOFs exhibited crystallinity loss, ring-opening cleavage, and linker degradation. Photobleaching resulted from direct redox reactions between porphyrin sites and H2O2. Metal-oxo-porphyrin intermediates played a key role in the "group effect," with different functional groups affecting the photobleaching rate: PCN-224-Fe ≈ PCN-224-Co > PCN-224-H2 > PCN-224-Cu ≈ PCN-224-Zn. This trend related to chelated metal ions' electronic structures and their propensity for metal-oxo intermediate formation, establishing a structure-stability relationship. Our study enhances understanding of deactivation mechanisms in porphyrin MOFs during AOP, aiding the design of resilient and efficient MOF catalysts for environmental applications.

Elucidating the structure-stability relationship of Cu single-atom catalysts using operando surface-enhanced infrared absorption spectroscopy

Understanding the structure-stability relationship of catalysts is imperative for the development of high-performance electrocatalytic devices. Herein, we utilize operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) to quantitatively monitor the evolution of Cu single-atom catalysts (SACs) during the electrochemical reduction of CO2 (CO2RR). Cu SACs are converted into 2-nm Cu nanoparticles through a reconstruction process during CO2RR. The evolution rate of Cu SACs is highly dependent on the substrates of the catalysts due to the coordination difference. Density functional theory calculations demonstrate that the stability of Cu SACs is highly dependent on their formation energy, which can be manipulated by controlling the affinity between Cu sites and substrates. This work highlights the use of operando ATR-SEIRAS to achieve mechanistic understanding of structure-stability relationship for long-term applications.

Dissecting the structure-stability relationship of Y-series electron acceptors for real-world solar cell applications

Dissecting the structure-stability relationship of Y-series electron acceptors for real-world solar cell applications

A positive complexity-stability relationship emerges in pollinator-plant-consumer tripartite networks disturbed by plant invasion

The relationship between network structure and system stability has been debated for decades. Recent studies have found that species invasions are able to change the structure-stability relationship in mutualistic or antagonistic bipartite networks. However, whether and how species invasion can alter the structure-stability in tripartite networks with both mutualistic and antagonistic interactions remain largely unexplored. Here, we establish a patch-occupancy dynamic (including species colonization-extinction processes) model to explore the effect of plant invasion (e.g., fragrant eupatorium herb invades native plant community in southern Yunnan, China) on the relationship between network structure (i.e., connectance, network size, modularity and nestedness) and community stability (robustness to invasion) in a pollinator-plant-consumer tripartite network (e.g., Lepidoptera insect-herbaceous vegetation-phytophagous insect tripartite network). Theoretical results show that nestedness and modularity have opposite effects on community stability. Specifically, our work reveals that, in both mutualistic and antagonistic bipartite networks, the effect of modularity on community stability is positive, whereas the effect of nestedness is negative. Moreover, increasing network size increases system stability. Finally, we find a positive connectance-stability relationship in both mutualistic and antagonistic bipartite networks. Overall, our patch-dynamic framework provides new insights into how species invasion affects the stability of tripartite networks with multiple interaction types.

Accelerating the Discovery of Transition Metal Borides by Machine Learning on Small Data Sets.

Accurate and efficient prediction of the stability and structure-stability relationship is important to discover materials; however, it requires tremendous efforts via traditional trial-and-error schemes. Here, we presented a small-data set machine learning (ML) method to accelerate the discovery of promising ternary transition metal boride (MAB) candidates. Based on data sets obtained by ab initio calculations, we developed three robust neural networks to predict the decomposition energy (ΔHd) and assess the thermodynamic stability of 212-typed MABs (M2AB2). The quantitative relation between ΔHd and stability was unraveled by several composition-and-structure descriptors. Three hexagonal M2AB2, i.e., Nb2PB2, Nb2AsB2, and Zr2SB2, were discovered to be stable with negative ΔHd, and 75 metastable MABs were identified with ΔHd less than 70 meV/atom. Finally, the dynamical stability and mechanical properties of MABs were investigated by ab initio calculations, whose results further verified the reliability of our ML models. This work provided a ML approach on small data sets to accelerate the discovery of compounds and expanded the MAB phase family to VA and VIA groups.

Research Progress of Grassland Ecosystem Structure and Stability and Inspiration for Improving Its Service Capacity in the Karst Desertification Control

The structure and stability of grassland ecosystems have a significant impact on biodiversity, material cycling and productivity for ecosystem services. However, the issue of the structure and stability of grassland ecosystems has not been systematically reviewed. Based on the Web of Science (WOS) and China National Knowledge Infrastructure (CNKI) databases, we used the systematic-review method and screened 133 papers to describe and analyze the frontiers of research into the structure and stability of grassland ecosystems. The research results showed that: (1) The number of articles about the structure and stability of grassland ecosystems is gradually increasing, and the research themes are becoming increasingly diverse. (2) There is a high degree of consistency between the study area and the spatial distribution of grassland. (3) Based on the changes in ecosystem patterns and their interrelationships with ecosystem processes, we reviewed the research progress and landmark results on the structure, stability, structure-stability relationship and their influencing factors of grassland ecosystems; among them, the study of structure is the main research focus (51.12%), followed by the study of the influencing factors of structure and stability (37.57%). (4) Key scientific questions on structural optimization, stability enhancement and harmonizing the relationship between structure and stability are explored. (5) Based on the background of karst desertification control (KDC) and its geographical characteristics, three insights are proposed to optimize the spatial allocation, enhance the stability of grassland for rocky desertification control and coordinate the regulation mechanism of grassland structure and stability. This study provided some references for grassland managers and relevant policy makers to optimize the structure and enhance the stability of grassland ecosystems. It also provided important insights to enhance the service capacity of grassland ecosystems in KDC.

Structure-Stability Relationship in Aqueous Colloids of Latex Particles and Gemini Surfactants.

The influence of gemini surfactants (GSs) on the charging and aggregation features of anionic sulfate modified latex (SL) particles was investigated by light scattering techniques in aqueous dispersions. The GSs of short alkyl chains (2-4-2 and 4-4-4) resembled simple inert salts and aggregated the particles by charge screening. The adsorption of GSs of longer alkyl chains (8-4-8, 12-4-12, and 12-6-12) on SL led to charge neutralization and overcharging of the particles, giving rise to destabilization and restabilization of the dispersions, respectively. The comparison of the interfacial behavior of dimeric and the corresponding monomeric surfactants revealed that the former shows a more profound influence on the colloidal stability due to the presence of double positively charged head groups and hydrophobic tails, which is favorable to enhancing both electrostatic and hydrophobic particle-GS and GS-GS interactions at the interface. The different extent of the particle-GS interactions was responsible for the variation of the GS destabilization power, following the 2-4-2 < 4-4-4 < 8-4-8 < 12-4-12 order, while the length of the GS spacer did not affect the adsorption and aggregation processes. The valence of the background salts strongly influenced the stability of the SL-GS dispersions through altering the electrostatic interactions, which was more pronounced for multivalent counterions. These findings indicate that both electrostatic and hydrophobic effects play crucial roles in the adsorption of GSs on oppositely charged particles and in the corresponding aggregation mechanism. The major interparticle forces can be adjusted by changing the structure and concentration of the GSs and inorganic electrolytes present in the systems.

Minimising chemical crosslinking for stabilising collagen in acellular bovine pericardium: Mechanistic insights via structural characterisations

Chemically crosslinked acellular bovine pericardium (ABP) has been widely used in clinical practice as bioprostheses. To ensure its consistency and durability, crosslinkers are used in excess, with stability guided by indicators including the hydrothermal denaturation temperature, the enzymatic resistance and the degree of crosslinking. Yet, understanding of the intermolecular structure in collagen fibrils which imparts the intrinsic stability of the ABPs is lacking, and the discrepancies in the stability criteria in varied conditions are poorly explained. In this study, synchrotron small-angle X-ray scattering (SAXS) in combination with thermal and colorimetric methods are employed to investigate the changes in the structure and the stability of ABPs during crosslinking using glutaraldehyde (GA) or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) at different concentrations. Based on the findings, a mechanism is proposed to explicate the crosslinking effects on collagen structure and the relationship between the structure and each stability indicator. At low crosslinker concentrations, the telopeptidyl-helical linkages are preferred, which cause rearrangements in the intermolecular structure of collagen, and efficiently contribute to its stabilities. Excess crosslinking is revealed by a revert trend in structural changes and the plateauing of the stabilities, assigning to the helical-helical linkages and monovalent bindings. The former would improve thermal stability but not collagenase resistance, whereas the latter have negligible effects. Overall, this study provides a mechanistic understanding of the chemical crosslinking of ABPs, which will contribute to the future development of more efficient and economically viable strategies to produce bioprostheses. Statement of significanceChemical crosslinking imparts suitable properties to acellular bovine pericardium (ABP) for clinical applications, yet the understanding is lacking on the structure-stability relationship especially under different crosslinking conditions. Structural evidence in this study differentiates the binding sites during crosslinking in collagen fibrils at different crosslinker concentrations, highlighting the excess usage in the conventional crosslinking treatments. The mechanism based on the structure of collagen also successfully explains the dissimilarity in hydrothermal and enzymatic stabilities with varied crosslinking conditions. Future researches focusing on developing biomaterials via chemical crosslinking of ABPs would benefit from this study, for its contribution to the better understanding of the relationship of collagen structure and functions.

Recent advances on the stability of dietary polyphenols

Recent advances on the stability of dietary polyphenols

Mapping metastability of Lennard-Jones clusters by maximum vibrational frequency

We study the structure-stability relationship of the Lennard-Jones (LJ) clusters from a point of view of vibrations. By assuming the size up to $N=1610$, we demonstrate that the $N$-dependence of the maximum vibrational frequency reflects the geometry of the core (the interior of cluster) that will determine the overall geometry of the cluster. This allows us to identify the formation of non-icosahedral structures for $N\le 150$, the vacancy formation at the core for $N\ge 752$, and the transition from icosahedral to decahedral structures at $N = 1034$. We apply the maximum frequency analysis to classify metastable clusters for $19\le N \le 39$, where transformation pathways between different structures are visualized, and the energy barrier height is estimated simultaneously.

Structure-Stability Relationship of NLRP3 Inflammasome-Inhibiting Sulfonylureas.

In recent drug development efforts, particular emphasis has been devoted to the chemical interference with the NLRP3 inflammasome. A series of 12 tailored sulfonylureas was designed, prepared through convergent syntheses with a final sodium hydride-promoted reaction of isocyanates and sulfonamides, and subjected to a systematic, high-performance liquid chromatography-based survey of the chemical stability, a critical issue of sulfonylureas in terms of preparation, storage, and application. NLRP3 binding was determined by surface plasmon resonance spectroscopy. Sulfonylurea 2 was identified to be equipotent and similarly stable compared to the prototypical NLRP3 inhibitor MCC950.

Structure–Stability Relationship of Amorphous IrO2–Ta2O5 Electrocatalysts on Ti Felt for Oxygen Evolution in Sulfuric Acid

Structure–Stability Relationship of Amorphous IrO₂–Ta₂O₅ Electrocatalysts on Ti Felt for Oxygen Evolution in Sulfuric Acid

Quantum Mechanical Methods for Thermal Hazard Risk Assessment in Early Phase Pharmaceutical Development

Quantum mechanical (QM) applications to predict heat of reaction (ΔHr) and thermal stability of strained aminocarbocylic salts, diazo compounds, and nitroalkanes for early phase thermal hazard risk assessment is presented. We provide examples on the use of explicit solvation to predict accurate ΔHr. Based on the QM calculations, the criticality class of a copper-catalyzed C–N coupling reaction is determined according to Stoessel’s reaction criticality class and the predictions are consistent with RC1 calorimetric experiment. We emphasize that to predict accurate ΔHr, it is important to consider the roles of reagents and solvents in QM calculations rather than simply considering the bond formation and bond breaking steps involved with reactants and products. Further, the use of predicted ΔHr for salt formation is applied to predict the thermal stability of bromoacetylene azetidine compounds to establish structure–stability relationship which would be useful to identify stable salt intermediates for safe reaction design. A strong correlation between ΔHr and the left limit of the DSC onset temperature (Tinit, °C) of the of exothermic peak is identified (Tinit = −2.85 ΔHr − 99.5). We propose that this model can be used as a prediction tool for novel azetidine salts to provide an estimate of thermal stability before synthesis. In this paper, for the first time we report molecular electrostatic potential (MESP) descriptor for the prediction of Tinit of diazo compounds. The deepest MESP minimum (Vmin) on the diazo group is considered as a probe to quantify the variation in structural effects. A strong correlation between Vmin and Tinit is found which would provide a new way of interpreting the thermal stability of novel diazo molecules just based on chemical structure. Further, the applicability of Vmin is verified on another set of compounds (nitroalkanes) and a good correlation is obtained. The structure–stability relationships that involves Vmin can be a useful QM descriptor for thermal stability prediction of a variety of molecules.

Structural alterations on the TEMPO scaffold and their impact on the performance as active materials for redox flow batteries

A comparative study was performed with five new and one known TMA-TEMPO derivatives, to elucidate the structure–stability relationship of the TEMPO scaffold and to investigate the influence on the battery performance.

A DFT investigation of lithium adsorption on graphenes as a potential anode material in lithium-ion batteries

We present a detailed study of the Li+ ion adsorption on two different hydrogenated carbon nanostructures, namely as pristine graphene (PG) and topologic Stone-Wales defective graphene (SWG) using the density functional theory (DFT). The studies are focused to analyze the structure-stability relationship with the estimated electronic and electrical properties for lithium-ion batteries (LIB) formed with an anode based on the Li/Li+#PG and Li/Li+#SWG systems. In addition, the electronic effects induced due to Li+ adsorption and the presence of SW defect on the graphene models were analyzed by the frontier molecular orbitals, ChelpG charges, Raman and UV–Vis spectra. It was verified that Li+ is more stably adsorbed on the edges on both graphene structures through an electrostatic interaction between cation and more negatively charged edges of nanostructures. TD-DFT calculations showed that the metallic nature of isolated graphene is disturbed after the adsorption of Li+, and this was demonstrated from the calculated HOMO-LUMO gap. The same Li+-Graphene geometries were optimized by introducing neutral charge in order to enable the calculation of ionization potentials. I was also found that such systems potentially contributed to the modeling of graphene-based anodes with reasonable electrical voltage responses estimated for a LIB. The simulation of Raman and UV–Vis spectra revealed significant variations in intensity and shifts the typical bands of graphene due to the presence of the Li+ ion that can contribute to point out new experiments to the spectroscopic characterization of these systems. Our results suggest that these carbon nanostructures are potential candidates for efficient applications in electrochemical systems, mainly dealing with LIB.

Prodrug-type antisense oligonucleotides with enhanced nuclease stability and anti-tumour effects

The potential therapeutic and diagnostic applications of oligonucleotides have attracted great attention. However, natural antisense oligonucleotides (ASONs) are susceptible to degradation by intracellular and extracellular nucleases. In this study, we developed a new class of prodrug-type ASONs, which typically bear the hairpin-end conformation with a responsive disulphide switch. The hairpin-end conformation provides protection against nuclease degradation, and, upon stimulation, the molecule converts into the native antisense structure upon entering a tumour microenvironment due to the high concentration of glutathione. The structure-stability relationship analysis indicated that the location, size and composition of the hairpin structure affect the anti-degradation capability. One optimal prodrug-type ASON, O2, exhibited a higher stability against nucleases in serum-containing medium as well as an increased anti-tumour activity both in vitro and in vivo, compared to the linear control. This work presents a new strategy for the design of ASON drugs with novel structures and offers insight on the stability and biological efficacy of general nucleic acid-based therapeutics.

Theory of dynamical stability for two- and three-dimensional Lennard-Jones crystals

The dynamical stability of three-dimensional (3D) Lennard-Jones (LJ) crystals has been studied for many years. The fcc and hcp structures are dynamically stable, while the bcc structure is stable only for long-range LJ potentials that are characterized by relatively small integer pairs $(m,n)$. Here, we study the dynamical stability of two-dimensional (2D) LJ crystals, where the planar hexagonal, the buckled honeycomb, and the buckled square structures are assumed. We demonstrate that the stability property of 2D and 3D LJ crystals can be classified into four groups depending on $(m,n)$. The instabilities of the planar hexagonal, the buckled square, and the bcc structures are investigated within analytical expressions. The structure-stability relationship between the LJ crystals and the elemental metals in the periodic table is also discussed.

Computational Analysis of Thermal Adaptation in Extremophilic Chitinases: The Achilles' Heel in Protein Structure and Industrial Utilization.

Understanding protein stability is critical for the application of enzymes in biotechnological processes. The structural basis for the stability of thermally adapted chitinases has not yet been examined. In this study, the amino acid sequences and X-ray structures of psychrophilic, mesophilic, and hyperthermophilic chitinases were analyzed using computational and molecular dynamics (MD) simulation methods. From the findings, the key features associated with higher stability in mesophilic and thermophilic chitinases were fewer and/or shorter loops, oligomerization, and less flexible surface regions. No consistent trends were observed between stability and amino acid composition, structural features, or electrostatic interactions. Instead, unique elements affecting stability were identified in different chitinases. Notably, hyperthermostable chitinase had a much shorter surface loop compared to psychrophilic and mesophilic homologs, implying that the extended floppy surface region in cold-adapted and mesophilic chitinases may have acted as a “weak link” from where unfolding was initiated. MD simulations confirmed that the prevalence and flexibility of the loops adjacent to the active site were greater in low-temperature-adapted chitinases and may have led to the occlusion of the active site at higher temperatures compared to their thermostable homologs. Following this, loop “hot spots” for stabilizing and destabilizing mutations were also identified. This information is not only useful for the elucidation of the structure–stability relationship, but will be crucial for designing and engineering chitinases to have enhanced thermoactivity and to withstand harsh industrial processing conditions

Stabilization mechanism of arsenic-sulfide slag by density functional theory calculation of arsenic-sulfide clusters

Stabilization of arsenic sulfur slag (As‒S slag) is of high importance to prevent the release of deadly As pollutants into environment. However, the molecular understanding on the stability of As‒S slag is missing, which in turn restricts the development of robust approach to solve the challenge. In this work, we investigated the structure-stability relationship of As‒S slag with adopting various As‒S clusters as prototypes by density functional theory (DFT). Results showed that the configuration of S multimers-covering-(As2S3)n is the most stable structure amongst the candidates by the analysis of energies and bonding characteristics. The high stability is explained by orbital composition that the 4p-orbital (As) binding with 3p-orbital (S) decreases energy level of highest occupied molecular orbital (HOMO). Inspired from the calculations, an excess-S-based hydrothermal method was successfully proposed and achieved to promote the stabilization of As‒S slag. Typically, the As concentration from the leaching test of stabilized As‒S slag is only 0.8 mg/L, which is much lower than the value from other stabilized slag.