Structural Modifications Research Articles

Metallo-Supramolecular Helicates as Surface-Enhanced Raman Scattering (SERS) Substrates with High Tailorability.

The exploration of novel functionalized supramolecular coordination complexes (SCCs) can enable new applications in domains that include purification and sensing. In this study, employing a coordination-driven self-assembly strategy, we designed and prepared a series of benzochalcogenodiazole-based metallohelicates as high-efficiency charge transfer surface-enhanced Raman scattering (SERS) substrates, expanding the range of applications for these metallohelicates. Through structural modifications, including the substitution of single heteroatoms on ligands, replacement of coordinating metals, and alteration of ligand framework linkages, the Raman performance of these metallohelicates as substrates were systematically optimized. Notably, the SERS enhancement factors (EFs) of the metallohelicate-based SERS substrates were significantly enhanced to levels as high as 1.03 × 107, which rivals the EFs of noble metals devoid of "hot spots". Additionally, the underlying Raman enhancement mechanisms of these metallohelicates have been investigated through a combination of control experiments and theoretical calculations. This study not only demonstrates the utility of metallohelicates as SERS substrates but also offers insights and materials for the development of high-efficiency new charge transfer SERS substrates.

Theoretical exploration of novel alkannin derived D-π-A conjugated organic dyes as efficient sensitizer in dye-sensitized solar cells

The advancement of cost-effective, highly efficient sensitizers plays a crucial role in the progress of dye-sensitized solar cells (DSSCs). Employing density functional theory (DFT) and time-dependent density functional theory (TD-DFT), a range of metal-free organic dyes with D - π - A configuration, featuring different donor and acceptor groups, have been investigated to enhance the effectiveness of sensitizer dyes. We developed metal-free organic dyes (Ak1-Ak6) with a D - π - A structure through structural modifications of alkannin reference dye. Calculations were conducted to assess the electronic and optical properties, along with key parameters such as short-circuit current density (Jsc) and open-circuit voltage (Voc), including light-harvesting efficiency (LHE), electronic injection-free energy (ΔG inject), and regeneration driving forces (ΔG reg) of the designed dyes. The outcomes of this study offer valuable insights for the design of highefficiency DSSCs.

Glycoxidation of mammalian whole histone generates highly immunogenic aggregates: Sera of SLE patients contain autoantibodies against aggregates.

Non-enzymatic glycation and oxidation of self-proteins, causing formation and accumulation of advanced glycation end products (AGEs), have been reported in an array of pathologies, including systemic lupus erythematosus (SLE). Such modifications may generate neo-epitopes, break immunological tolerance, and induce antibody response. In this study, we have first analysed the structural modifications of whole histone in the presence of deoxyribose followed by oxidation with hydroxyl radicals. Changes in the secondary and tertiary structure of the whole histone were determined by spectroscopic techniques and biochemical assays. Fluorescence spectroscopy and UPLC-MS showed the generation of AGEs such as carboxymethyl lysine and pentosidine, while DLS and TEM indicated the presence of amorphous AGE-aggregates. Moreover, rabbits immunized with these histone-AGEs exhibited enhanced immunogenicity and ELISA and western immunoblot of IgG antibodies from SLE patients' sera showed a significantly higher specificity towards modified histone-AGEs than the native histone.

Hydrothermal synthesis of La0.5Sr0.5MnO3 nanostructures for enhanced CO oxidation

This study focuses on the synthesis and characterization of La0.5Sr0.5MnO3 (LSMO) perovskite nanostructures via the hydrothermal method and their catalytic performance evaluation in CO oxidation. Structural analysis using techniques like XRD, FE-SEM, FTIR, and Raman spectroscopy analysis verified the development of LSMO nanostructures exhibiting a rhombohedral phase configuration. The catalytic activity of the annealed LSMO nanostructures was assessed, demonstrating significant CO conversion efficiency attributed to structural modifications enhancing catalytic performance. These findings highlight the potential of LSMO perovskite nanostructures as efficient catalysts for CO oxidation.

Noise Reduction in an Interior Permanent Magnet Synchronous Motor through Structural Modifications

Noise Reduction in an Interior Permanent Magnet Synchronous Motor through Structural Modifications

Electrochemical CO2 Reduction in Acidic Electrolytes: Spectroscopic Evidence for Local pH Gradients.

Inspired by recent advances in electrochemical CO2 reduction (CO2R) under acidic conditions, herein we leverage in situ spectroscopy to inform the optimization of CO2R at low pH. Using attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and fluorescent confocal laser scanning microscopy, we investigate the role that alkali cations (M+) play on electrochemical CO2R. This study hence provides important information related to the local electrode surface pH under bulk acidic conditions for CO2R, both in the presence and absence of an organic film layer, at variable [M+]. We show that in an acidic electrolyte, an appropriate current density can enable CO2R in the absence of metal cations. In situ local pH measurements suggest the local [H+] must be sufficiently depleted to promote H2O reduction as the competing reaction with CO2R. Incrementally incorporating [K+] leads to increases in the local pH that promotes CO2R but only at proton consumption rates sufficient to drive the pH up dramatically. Stark tuning measurements and analysis of surface water structure reveal no change in the electric field with [M+] and a desorption of interfacial water, indicating that improved CO2R performance is driven by suppression of H+ mass transport and modification of the interfacial solvation structure. In situ pH measurements confirm increasing local pH, and therefore decreased local [CO2], with [M+], motivating alternate means of modulating proton transport. We show that an organic film formed via in situ electrodeposition of an organic additive provides a means to achieve selective CO2R (FECO2R ∼ 65%) over hydrogen evolution reaction in the presence of strong acid (pH 1) and low cation concentrations (≤0.1 M) at both low and high current densities.

Use of molecular simulation to design modification of a chromium‐based MOF for adsorptive removal of inhalation anaesthetic agents

AbstractMIL‐101‐Cr‐X (X = OH−, F−) has been reported to be the most suitable material so far for adsorptive removal of inhalation anaesthetic agents (IAA) sevoflurane and desflurane at the working conditions in hospital operation rooms. To further enhance its affinity and uptake capacity towards IAA, several structural modifications were proposed, and their isotherms were predicted using our molecular simulation approach adopted in our previous publication for the case of the pristine MIL‐101‐Cr (X = F−, OH−) structure. The proposed modifications include (1) grafting the metal‐cluster site with coordinated NH3 ligands to produce MIL‐101‐Cr@NH3 (X = F−, OH−), (2) anion exchange of the fluorine atom bonded to chromium with chlorine to synthesize MIL‐101‐Cr (X = Cl−), and (3) functionalization of the benzene rings of the ligand linkers in the MOFs with amino‐ and nitro‐ groups in order to form NH2‐MIL‐101‐Cr (X = Cl−) and NO2‐MIL‐101‐Cr (X = Cl), respectively. Simulated adsorption isotherms of IAA on these modifications were verified by the experimental results using the standard volumetric technique and they clearly demonstrated that MIL‐101‐Cr@NH3 (X = F−, OH−) possesses the highest equilibrium capacity for IAA. This observation can be attributed to the electron‐transfer contribution of the coordinated ammonium molecules to the unsaturated coordinated sites of the MOF while doing away with steric hindrance inside the pore cages. The new compound can significantly enhance the economy of adsorptive removal of IAA from vented gas mixtures.

Recycling arsenic-containing bio-leaching residue after thermal treatment in cemented paste backfill: Structure modification, binder properties and environmental assessment

Recycling arsenic-containing bio-leaching residue after thermal treatment in cemented paste backfill: Structure modification, binder properties and environmental assessment

Triboelectrically Empowered Biomimetic Heterogeneous Wettability Surface for Efficient Fog Collection.

Biomimetic engineering surfaces featuring heterogeneous wettability are vital for atmospheric water harvesting applications. Existing research predominantly focuses on the coordinated regulation of surface wettability through structural and chemical modifications, often overlooking the prevalent triboelectric charge effect at the liquid-solid interface. In this work, we designed a heterogeneous wettability surface by strategic masking and activated its latent triboelectric charge using triboelectric brushes, thereby enhancing the removal and renewal of surface droplets. By examining the dynamic evolution of droplets, the mechanism of triboelectric enhancement in the water collection efficiency is elucidated. Leveraging this inherent triboelectric charge interaction, fog collection capacity can be augmented by 29% by activating the system for 5 s every 60 s. Consequently, the advancement of triboelectric charge-enhanced fog collection technology holds both theoretical and practical significance for overcoming the limitations of traditional surface wettability regulation.

A comparative study on the slow pyrolysis of Miscanthus (Miscanthus×giganteus Greef et Deu.) cultivated on agricultural and contaminated soils: Assessment of distribution of final products

This study aims to investigate the slow pyrolysis behavior of uncontaminated (MSC-I - reference) and heavy metals contaminated (MSC-R) samples with heavy metals from the tailings of a Pb-Zn-Cu flotation mine, consisting of whole stems of Miscanthus. Physicochemical properties of raw materials were investigated through instrumental characterization techniques (Atomic Absorption Spectrometry (AAS), Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, and X-ray diffraction (XRD)), while the pyrolysis process was monitored by simultaneous thermal analysis techniques (thermogravimetry (TG) – derivative thermogravimetry (DTG)), coupled with Mass spectrometry (MS), for evolved gas analysis. After determination of the lignocellulose content (cellulose, hemicellulose, and lignin) and extractive of the MSC-I and MSC-R samples, it was found that Pb, Zn, Fe, and Mn in MSC-R lead to very fast decomposition of extractive fraction, which facilitates their distribution in formed bio-char, together with lignin char-participation, acting catalytically. It was established that a much greater fraction of extractives decomposition products and non-volatile heavy metals are incorporated in MSC-R bio-char increasing its yield (23 %), compared to MSC-I bio-char yield (21.5 %). It was identified that MSC-R has increased production of H2, CO, and CO2, while decreased production of CH4, influenced by Fe (Fe has a significant positive effect on CO2 evaluation during MSC-R pyrolysis, enhancing decarboxylation process). It was established that CH4 reforming reactions catalyzed by iron additionally affect methane reduction, and increase production of H2, compared to the reference sample. Isoconversional kinetic analysis showed that pyrolysis reactions profile was strongly conditioned by the presence of heavy metals, such as Cd, Pb, and Zn, because they affect the modification of biomass lignocellulosic structure. Also, it was found that small amounts of Cd present in MSC-R can increase pyrolysis activation energy of three pseudo-components, and inhibit their deoxygenation, thus increasing yield of bio-char.

Aerodynamic Optimization Design of a Supergravity Centrifuge: A Low-Resistance Strategy

Wind resistance optimization is crucial for enhancing the rotational speed of supergravity centrifuges. We conducted a study using computational fluid dynamics on the Centrifugal Hypergravity and Interdisciplinary Experiment Facility (CHIEF) under construction at Zhejiang University and validated it experimentally using a ZJU400gt centrifuge. Our findings indicate significant reductions in wind resistance through structural modifications of the CHIEF. Reducing the outer radius from 4650 to 4150 mm decreased wind resistance by 16%, primarily due to reduced effective viscosity in the wake region’s gases. More substantial reductions were achieved by lowering the height of the outer wall from 2200 to 1400 mm, which cut wind resistance by 25%. This height reduction suppressed vortex shedding and Kármán vortex street development via the Venturi effect. Adjustments to the roughness height of wall surfaces further decreased wind resistance, with minimal impact from arm roughness. A critical roughness height was identified, below which no further reductions in wind resistance could be attained. Notably, using disc-shaped arms reduced wind resistance by approximately 73% because of their minimal pressure–resistance components and predominant frictional resistance, highlighting their potential in future high-speed centrifuge designs.

Direct N[sbnd]H heteroarylation of NH-sulfoximines under electrochemical conditions

Given the pivotal importance of sulfoximines in the field of medicine, they have garnered considerable attention in synthetic chemistry, and the development of novel catalytic methods to achieve their functionalization is highly valuable. Herein, a direct and practical electrochemical strategy for the synthesis of heteroaromatic-substituted products was developed using NH-sulfoximines and quinoxalin-2(1H)-ones as starting materials. The direct construction of the NC(sp2) bonds of NH-sulfoximines is achieved through the cleavage of the C3H bonds of quinoxalin-2(1H)-ones. This protocol features good functional group tolerance, simplicity in operation, and easy to scalability. By utilizing this electrochemical strategy, the structural modification of biomolecular derivatives has been successfully carried out, which is unattainable with other traditional oxidants. The mechanistic investigation demonstrates that quinoxalin-2(1H)-ones serve dual roles as both substrates and redox mediators, thereby avoiding the addition of extra hydrogen atom transfer (HAT) reagents.

Investigation of mechanical properties and high temperature wear resistance of CoFeNi1.5VZr0.4Six high entropy alloys optimized by Si alloying

The current work studies the mechanical properties and high-temperature wear resistance of CoFeNi1.5VZr0.4Six high entropy alloys by Si alloying. The Si alloying transforms Ni7Zr2 into a more wear-resistant silicide phase, and the microstructure changes from lamellar eutectic structure to dendritic structure. The high temperature microhardness, compressive strength and fracture toughness of the HEAs increase first and then decrease with the increasing Si content. The Si alloying in HEAs brings about significant improvements in wear resistance at elevated temperature through the combined effects of phase structure modifications and compositional changes in the tribo-layer. The augmented mechanical properties of the worn subsurface layer contribute to improved wear resistance at elevated temperatures.

Carboxymethylation of paramylon derived from Euglena gracilis and its hypoglycemic mechanism in diabetic mice.

Paramylon is a polysaccharide primarily composed of β-1,3-glucan, characterized by its high crystallinity and insolubility in water. Enhancing its water solubility through structural modifications presents an effective strategy to unlock its biological activity. In this study, carboxymethylation was employed to produce carboxymethylated paramylon (CEP) with varying carboxyl concentrations. The successful introduction of carboxyl groups led to a notable improvement in water solubility. In vivo experiments demonstrated that CEP reduced fasting blood glucose levels by 24.42%, improved oral glucose tolerance, and enhanced insulin sensitivity in diabetic mice. Additionally, CEP regulated lipid homeostasis and ameliorated liver damage. Through modulation of the adenosine monophosphate-activated protein kinase/phosphoinositide 3-kinase/protein kinase B pathway and the glucose-6-phosphatase/phosphoenolpyruvate carboxykinase pathway, CEP effectively regulated hepatic glucose absorption and production. Furthermore, CEP mitigated diabetes-induced lipid metabolism disorders. These findings suggest that CEP holds significant promise in ameliorating glucose metabolism disorder, indicating its potential as a novel hypoglycemic functional food.

Engineering Central Substitutions in Heptamethine Dyes for Improved Fluorophore Performance.

As a major family of red-shifted fluorophores that operate beyond visible light, polymethine dyes are pivotal in light-based biological techniques. However, methods for tuning this kind of fluorophores by structural modification remain restricted to bottom-up synthesis and modification using coupling or nucleophilic substitutions. In this study, we introduce a two-step, late-stage functionalization process for heptamethine dyes. This process enables the substitution of the central chlorine atom in the commonly used 4'-chloro heptamethine scaffold with various aryl groups using aryllithium reagents. This method borrows the building block and designs from the xanthene dye community and offers a mild and convenient way for the diversification of heptamethine fluorophores. Notably, this efficient conversion allows for the synthesis of heptamethine-X, the heptamethine scaffold with two ortho-substituents on the 4'-aryl modification, which brings enhanced stability and reduced aggregation to the fluorophore. We showcase the utility of this method by a facile synthesis of a fluorogenic, membrane-localizing fluorophore that outperforms its commercial counterparts with a significantly higher brightness and contrast. Overall, this method establishes the synthetic similarities between polymethine and xanthene fluorophores and provides a versatile and feasible toolbox for future optimizing heptamethine fluorophores for their biological applications.

Exploring metastable phase formation: Swift heavy ion effects on partially stabilized zirconia

Zirconium dioxide shows great potential for use in the nuclear power industry. It exhibits high radiation stability (neutron and heavy ions) and can withstand harsh environments. The paper presents a study on the effects of 710 MeV Bi ion irradiation on polycrystalline partially yttria-stabilized zirconia using the combination of experimental techniques - X-ray diffraction, transmission electron microscopy and Raman spectroscopy. It was revealed that bismuth ion induced tracks retain their crystalline structure and their density tends to saturate at ∼1 × 1012 cm−2. As a result of dense ionization stimulated structural modification a t → t'' phase transformation was observed. The radiation stability of t'' phase against swift heavy ion impact was found to be higher compared to the t phase. No amorphization was detected up to Bi ion fluence of 2 × 1013 cm−2.

Antifungal activity of carvacrol-based solids and their effects on Whatman and Kraft paper

The degradation of cellulose-based materials by fungi represents a menace to the cultural heritage conservation. Carvacrol-based β-cyclodextrins and cocrystals proved effective antifungal remedies in vitro but their effects on paper structure and properties were not studied. The aim of this study was to investigate possible structural modifications and alterations of the mechanical, optical and chemical properties of artificially aged and unaged Whatman and Kraft paper subjected to the treatment with carvacrol-based β-ciclodextrins and cocrystals. The pH of the samples did not significantly change after the treatment, as well as no colour-related alterations were detected (1.00<ΔE<2.00). The tensile strength of both Whatman and Kraft paper was not affected by the vapours of carvacrol and spectroscopic analysis (FTIR and XRD) revealed no carvacrol-related damages of paper structure. The antifungal efficacy of the carvacrol-cocrystal was also proved on a book prototype made of Whatman and Kraft paper, kept under 98% of humidity for 28 days, and purposely inoculated with a mix of fungal species (A. alternata, Aspergillus sp. section Nigri, C. cladosporioides, and T. orientale). These results show the applicability of a carvacrol-releasing system, effective as antifungal remedy, and at the same time not harmful to Whatman and Kraft paper, as these materials did not show treatment-induced degradation.

Zinc blende ZnS (001) surface structure investigated by XPS, LEED, and DFT

The formation and stability of the zinc blende ZnS (001) single crystal surface have been examined by x-ray photoemission spectroscopy (XPS), low-energy electron diffraction (LEED), and density-functional theory (DFT) calculations. LEED patterns obtained from the ZnS (001) surface prepared in ultrahigh vacuum conditions at 1420 K reveal the formation of a (1 × 2) reconstructed structure. Surface chemical characterization performed by XPS indicates that the surface region consists of a Zn-deficient (sulfur-rich) phase. Our DFT theoretical calculations confirm that the ZnS (001) (1x2) surface structure is energetically favorable and consists of a Zn-terminated topmost surface layer stabilized by Zn-vacancies. The calculations also suggest that the remaining Zn-cations on the surface are displaced inward, driven by surface energy minimization related to zinc-blend ZnS (001) polar nature. Notably, the observed surface structural modifications have potential implications for the ZnS physical and chemical properties.

Effect of ultrasound on the characterization and peptidomics of foxtail millet bran protein hydrolysates

Protein hydrolysates have attracted much attention for their high biological activity and are a crucial product form for the utilization of foxtail millet bran by-products. In this study, changes in the structure, functionality, activity and peptide profile of foxtail millet bran protein hydrolysates (FMBPHs) at different ultrasound powers (0 – 600 W) were investigated. The results showed that ultrasound promoted the transformation of α-helix and β-sheet to random coils and β-turn, and the exposure of hydrophobic groups and sulfhydryl groups in FMBPHs. The average particle size of the samples decreased, and the absolute value of the ζ-potential increased significantly. Simultaneously, smaller porous particles and loose fragments appeared on the surface of FMBPHs when the ultrasonic power was increased to 450 W. Additionally, 450 W ultrasound treatment improved solubility, foaming properties, emulsifying properties, thermal stability of FMBPHs. The DPPH, ABTS and hydroxyl radical scavenging ability (IC50, 2.65, 1.06 and 3.02 mg/mL), Fe2+ chelating activity (IC50, 2.62 mg/mL), and reducing power of the samples were also enhanced. The peptidomics results demonstrated that ultrasonication increased the number of active peptides in the hydrolysate, and the relative abundance of 17 active peptides was obviously elevated at 450 W. Peptide map analysis showed that ultrasound-induced structural modifications affected the peptide profiles of Ubiquitin-like domain-containing protein, Cupin type-1 domain-containing protein, 40S ribosomal protein S19, and Oleosin 1, showing changes in the abundance of certain peptides, which may be related to changes in the characterization of FMBPHs.

Topological Anderson phases in heat transport

Topological Anderson phases (TAPs) offer intriguing transitions from ordered to disordered systems in photonics and acoustics. However, achieving these transitions often involves cumbersome structural modifications to introduce disorders in parameters, leading to limitations in flexible tuning of topological properties and real-space control of TAPs. Here, we exploit disordered convective perturbations in a fixed heat transport system. Continuously tunable disorder-topology interactions are enabled in thermal dissipation through irregular convective lattices. In the presence of a weak convective disorder, the trivial diffusive system undergos TAP transition, characterized by the emergence of topologically protected corner modes. Further increasing the strength of convective perturbations, a second phase transition occurs converting from TAP to Anderson phase. Our work elucidates the pivotal role of disorders in topological heat transport and provides a novel recipe for manipulating thermal behaviors in diverse topological platforms.