Short-range Order Research Articles

Alginate-millet starch composite matrices as novel carriers for controlled delivery of grape seed polyphenols: Preparation, characterization, and in vitro release behaviour

Grape seed polyphenols (GSP) were encapsulated in alginate-modified millet starch composite matrix using internal gelation. Millet starch was modified using ultrasound (US) for 10, 20, 30, and 40 min. The application of US reduced the long-range order and increased the short-range order of starch, consequently increasing its solubility. FESEM analysis revealed that US-treatment induced fissures and grooves on the surface of starch granules and disintegrated the starch particles. Particle size distribution analysis confirmed a significant reduction in mean particle size. US-treatment facilitated enhanced alginate-starch interactions owing to an increased surface area and improved hydrogen bonding, as corroborated by FTIR, XRD, and DSC results. The composite microencapsulates prepared from 40 min US-treated starch demonstrated the highest encapsulation efficiency (89.20 ± 1.10 %), heat and UV-light stability, and delayed GSP release in simulated gastrointestinal fluids. The best fit for the release behaviour of GSP from the composite microencapsulates was observed with Peppas-Sahlin model.

Influences of Weizmannia coagulans PR06 Fermentation on Texture, Cooking Quality and Starch Digestibility of Oolong Tea-Fortified Rice Noodles.

Weizmannia coagulans is increasingly employed in food processing owing to its health benefits. Our previous research developed Oolong tea-fortified rice noodles with unique flavor and potent antioxidant activity; however, their texture still requires improvement. In this study, Oolong tea-fortified rice noodles were fermented using W. coagulans PR06 at inoculation amounts of 1%, 3%, and 5% (v/v), and assessed for cooking quality, texture, and starch digestibility. The results indicated that fermentation with 3% and 5% W. coagulans PR06 altered the amylopectin length distribution in the rice noodles and increased the degree of starch short-range order. Furthermore, the fermentation process increased the storage modulus (G') and loss modulus (G″) values, decreased the tan δ value, and strengthened the interactions among tea polyphenols, proteins, and starch in the rice flour gel. Consequently, this process increased the hardness and chewiness of the rice noodles, decreased their broken strip rate and cooking loss, and significantly reduced their in vitro starch digestibility. Overall, fermentation with W. coagulans PR06 markedly improved the texture and cooking quality of Oolong tea-fortified rice noodles while effectively delaying starch digestion. This study highlights the potential application of W. coagulans PR06 in developing diverse and functional rice noodle products.

Unveiling the thermodynamic landscape of liquid Ti–Al–Ni alloys through first-principles simulations

We conducted ab initio molecular dynamics simulations to systematically examine the composition-dependent thermodynamic properties and atomic-scale interactions in liquid Ti–Al–Ni alloys throughout the entire ternary phase space at 2033 K. The calculated enthalpies of mixing demonstrated exothermic tendencies, with a distinct minimum in the composition of Ti0.0Al0.50Ni0.50, indicating significant Al–Ni attractive interactions. Incorporating ternary interaction parameters into the Redlich-Kister-Muggianu equation enabled accurate modeling of the complex variations in mixing enthalpy. Analysis of partial pair correlation functions and structure factors revealed chemical and topological short-range ordering (SRO), as well as medium-range ordering, within the liquid alloy. Quantifying deviations from ideal configurational entropy clarifies the coupling between chemical SRO and topological SRO, significantly impacting the overall Gibbs energy of mixing. This comprehensive atomistic study provides insights into the thermodynamics of Ti–Al–Ni alloys, paving the way for tailoring their properties for high-performance applications.

Diffusion enhancement by spontaneous formation of Frenkel defects in NaCl-type high-entropy materials

High-entropy materials (HEMs) are attracting attention due to their exceptional properties, such as enhanced mechanical toughness, irradiation resistance, ionic conductivity, and thermoelectric performance. Although diffusion is an important phenomenon as it is closely related to these physical properties of materials, there is a lack of understanding of the mechanisms of diffusion due to the complexity of the atomic interactions in HEMs. Here, we investigates diffusion mechanisms in PbTe-based HEMs AgInSnPbBiTe5, focusing on the role of indium (In). Molecular dynamics simulations reveal that In+ spontaneously forms Frenkel defect and enhancing diffusion not only of In+ but also other cations. Furthermore, as a result of enhanced diffusion, short-range order is formed by structural relaxation. This insight not only enhances comprehension of HEMs diffusion mechanisms but also develops HEMs with properties such as self-healing from damage and high ion permeability, advancing the field of material science.

Strong and ductile Resinvar alloys with temperature- and time-independent resistivity

Materials with well-defined electrical resistivity that does not change with temperature or time are important in robotics, communication and automation. However, the challenge of designing such materials has remained elusive due to the temperature-dependent electron-phonon scattering. Moreover, resistive electrical conductors used in flexible and mobile systems under high mechanical loads must possess both high strength and ductility. Achieving such multi-properties presents a fundamental challenge. Here, we solve this problem by combining multicomponent alloy design with atomic-scale chemistry tuning. We term the resultant material ‘Resinvar’ alloy, due to its invariable resistivity (148 μΩ·cm) over wide temperature ranges from room temperature to 723 K. The alloy also has high tensile strength (948 MPa) at large tensile elongation (53%). The distorted lattice, chemical short-range order and ordered coherent nanoprecipitates in the material enable the invariant resistivity via promoting temperature-independent inelastic electron scattering, and contribute to the excellent strength-ductility synergy by manipulating dislocation slip.

Unlocking fast Li-ion transport in micrometer-sized Mn-based cation-disordered rocksalt cathodes

The development of cation-disordered rocksalt (DRX) cathodes has garnered worldwide attention due to their high capacity, broad chemical space and excellent structural flexibility. However, their low intrinsic Li-ion conductivity necessitates extensive particle pulverization, typically achieved through ball-milling process, which impedes large-scale production. In this work, we present a proton-exchange assisted strategy to activate the Li-ion transport in Mn-based DRX cathodes. Short-range spinel-like ordering is observed to form within the DRX matrix after the post treatment, which significantly enhances the intrinsic Li ion mobility. Notably, more than 280 mAh g−1 discharge capacity can be delivered at a slow rate from micrometer-sized particles with an overall disordered cation arrangement, which retains more than 150 mAh g−1 when cycled at a very high rate of 2000 mA g−1. Furthermore, we also demonstrate that the electrochemical performance of the post-treated cathodes can be further optimized by fine-tuning the reaction parameters.

Structural diversity in condensed matter: A general characterization of crystals, amorphous solids, and the structures between.

A definition of structural diversity, adapted from the biodiversity literature, is introduced to provide a general characterization of structures of condensed matter. Using the favored local structure lattice model as a testbed, the diversity measure is found to effectively filter extrinsic noise and provide a useful differentiation between crystal and amorphous structures. We identify an interesting class of structures intermediate between crystals and glasses that are characterized by a complex combination of short-range ordering and long-range disorder. We demonstrate how the diversity can be used as an order parameter to organize various scenarios by structure change in response to increasing diversity.

High Entropy Protected Sharp Magnetic Transitions in Highly Disordered Spinel Ferrites.

How disorder affects magnetic ordering is always an intriguing question, and it becomes even more interesting in the recently rising high entropy oxides due to the extremely high disorder density. However, due to the lack of high-quality single crystal samples, the strong compositional disorder effect on magnetic transition has not been deeply investigated. In this work, we have successfully synthesized high-quality single crystalline high entropy spinel ferrites (Mg0.2Mn0.2Fe0.2Co0.2Ni0.2)xFe3-xO4. Our findings from high-temperature magnetization and neutron diffraction experiments showed ferrimagnetic transitions at 748, 694, and 674 K for x values of 1, 1.5, and 1.8, respectively. Notably, the magnetic transition almost showed no broadening for x values of 1 and 1.5, compared to Fe3O4. Extended X-ray absorption fine structure measurements provided insights into the elemental distribution among the octahedral and tetrahedral sites. The random distribution of elements across these sites reduced the formation of local clusters and short-range orders, enhancing sample homogeneity and preserving the sharpness of the magnetic transition, despite bond length variation. Our study not only marks the first successful synthesis of an HEO bulk single crystal exhibiting long-range magnetic order but also sheds light on the interaction between high configurational entropy and magnetic orderings. This opens new avenues for future research and applications of magnetic high entropy oxides.

High-Performance Low-Iridium Catalyst for Water Oxidation: Breaking Long-Ranged Order of IrO2 by Neodymium Doping.

Exploring efficacious low-Irelectrocatalysts for oxygen evolution reaction (OER) is crucial for large-scale application of proton exchange membrane water electrolysis (PEMWE). Herein, an efficient non-precious lanthanide-metal-doped IrO2 electrocatalyst is presented for OER catalysis by doping large-ionic-radius Nd into IrO2 crystal. The doped Nd breaks the long-ranged order structure by triggering the strain effect and thus inducing an atomic rearrangement of Nd─IrO2 involving the forming of Nd─O─Ir bonds along with an increased amount of oxygen vacancies (Ov), giving rise of a long-ranged disorder but a short-ranged order structure. The formed Nd─O─Ir bonds tailor the electronic structure of Ir, leading to a lowered d-band center that weakens intermediates absorption on Ir sites. Moreover, doping Nd triggers Nd─IrO2 to catalyze OER mainly through lattice oxygen mechanism (LOM) by activating lattice oxygen owing to abundant Ov. The optimal catalyst only requires a relatively low overpotential of 263 mV@10mA cm-2 with a high mass activity of 216.98 A gIr -1 (at 1.53V) (eightfold of commercial IrO2), and also shows a superior durability at 50mA cm-2 (20h) than commercial IrO2 (3h) due to the oxidation-suppressing effect induced by Nd doping. This work offers insights into designing high-performance low-Ir electrocatalysts for PEMWE application.

Effect of ultrasound combined with exogenous protein treatment on the flushing characteristics of puffed corn flour

To address issues such as clumping, spoon adherence, and the formation of powdery packets in puffed corn flour (PCF), this study incorporated three exogenous proteins—egg white powder (EWP), soybean protein isolate (SPI), and whey protein isolate (WPI)—and applied ultrasonication. This treatment improved PCF's physicochemical properties and microstructure. Ultrasonication increased the starch resistance and reduced the short-range ordering of the samples, as evidenced by in vitro digestion results, X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FT-IR) data. Unexpectedly, the sonicated samples exhibited an A + V crystal structure with diffraction peaks near 13°,17°, and 19.9°. Furthermore, by using ultrasonication, the addition of EWP, SPI, and WPI raised the samples' water solubility index by 2.97%, 1.05%, and 9.87%, respectively; however, light transmittance decreased by 34.91%, 42.60%, and 25.33%. The agglomerate rate was reduced to zero; ultrasonic treatment also resulted in microparticles that were smaller and exhibited more holes and gaps on their surfaces. Additionally, the samples' breakdown and setback values increased, while their stability and anti-aging qualities decreased. These findings suggest that ultrasound combined with protein treatment significantly enhances the flushing properties of puffed cereal flours and supports their expanded use in the food industry.

Impact of freeze-thaw cycles on the physicochemical properties and structure-function relationship of potato starch with varying granule sizes in frozen dough

Starch, as a critical component of dough, significantly influences quality preservation during the freezing process. In particular, the fine structure of potato (B-type) starch in frozen processing is a subject of considerable interest. This study aims to investigate the intrinsic differences of B-type starch and the impact of freeze-thaw (F/T) treatment on its molecular structure and physicochemical properties. Chain length distribution and X-ray photoelectron spectroscopy were utilized to examine the structural characteristics of natural potato starch with different granule sizes. Furthermore, the fine structure, thermal properties, and rheological properties of the isolated starches after F/T treatment were analyzed. The results indicate that potato starch with smaller particle sizes exhibits higher surface CC and PO content along with a higher proportion of very short chains (DP < 6, 8.17 %) and long B chains (DP > 25, 20.68 %). The study found that after F/T treatment, the surface of small-sized starch granules was initially damaged, exhibiting threads on the surface centered on the umbilical point. Following F/T treatment, both the crystallinity (very large (VL): 24.52–18.36 %; small (S): 17.03–16.69 %) and short-range order (VL: 2.97–2.61; S: 2.71–2.35) of starch particle size decreased. Both the amylose content (20.88–14.57 %) and ΔH (10.15–8.62 J/g) of isolated starch after freeze-thaw-treated dough exhibited a decrease to varying degrees. With the exception of the fifth cycle, small-size starch particles exhibited relatively higher G' and G" values and showed significant changes as a result of F/T treatment, demonstrating high hardness and complex viscosity. Clarifying the physicochemical properties of potato starches with different granule sizes is expected to expand their applications in frozen dough.

Combined physicochemical and transcriptomic analyses reveal the effect of the OsGA20ox1 gene on the starch properties of germinated brown rice

Genes play a pivotal role in regulating the germination of cereal grains; however, there is limited research on the impact of germination genes on the physicochemical properties of germinated cereal starch. We investigated the effects of the OsGA20ox1 gene on the multiscale structural features and adhesion behavior of germinated brown rice starch. Compared to the knockout lines group, the wild type exhibited a decrease in double-helix content (62.74 %), relative crystallinity (47.39 %), and short-range molecular ordering (2.47 %), accompanied by enhanced erosion on the surface of starch granules. The damage to glycosidic bonds at the double-helix level and the heightened structural amorphization (90.95 %) led to reduced entanglement and interaction among starch molecules, ultimately resulting in reduced characteristic viscosity. Further transcriptomic analysis revealed that OsGA20ox1 could regulate the expression of starch-related enzyme genes in the starch metabolism pathway during germination of brown rice. This study contributes to understanding the role of germination genes in promoting the physicochemical properties of starch in germinated grains, thereby opening up new avenues for the improvement of plant-based starch, and paving the way for further research in this field.

Short-range order structural response of CdSe nanocrystals under 120 MeV swift heavy ions irradiation: A pair distribution function analysis

Swift heavy ion (SHI) irradiation deposits large amount of energy in the target material which thereby influences the structural features of the sample. In this work, the structural response of CdSe material has been studied under high energetic 120 MeV SHI irradiation. The long-range structural modifications of CdSe under SHI have been analyzed using Rietveld study. On the other hand, the short-range behavior of SHI irradiated CdSe has been studied using Pair distribution function (PDF), which can be interpreted as a distance map between two atoms in terms of a PDF peak. The small-box structural refinement of the samples has been performed using the PDFgui package for the study of modifications in the atomic arrangement after the SHI irradiation. In addition to this, structural characteristics such as unit cell parameters as determined from long-range (Rietveld) refinement are compared to that obtained from short-range (small-box) refinement. Moreover, atomic displacement factor for CdSe also has been determined to study the atomic disorder in the nanocrystal under the influence SHI irradiation. Finally, impact of SHI induced stress generated on the CdSe sample and its influence also has been studied based on the width of the PDF peak.

Bactericidal effect of ultrasound on glutinous rice during soaking and its influence on physicochemical properties of starch and quality characteristics of sweet dumplings

The soaking process of glutinous rice allows the growth and reproduction of microorganisms, which can easily cause food safety problems. In this work, the effects of different ultrasonic powers (150 W, 300 W, 450 W, and 600 W) on the bactericidal effect of glutinous rice, the physicochemical properties of starch and the quality characteristics of sweet dumplings were studied. Compared with soaking for 0 and 2 h, sonication of glutinous rice after soaking for 4 h was more effective at reducing the number of microorganisms in soaked glutinous rice, and the bactericidal effect increased with increasing ultrasound intensity. After 30 min, the total number of bacteria decreased by 2.04 log CFU/g. Moreover, ultrasonic treatment destroys the grain structure of glutinous rice starch, resulting in the formation of dents and cracks on the starch surface, increasing the amylose content, improving its expansion, reducing its short-range order and relative crystallinity, and altering its gelatinization characteristics. In addition, ultrasonic treatment increased the soup transparency of sweet dumplings from 51.8 % to 63.95 %, reducing their hardness, chewiness and adhesiveness. In summary, ultrasonic treatment can not only effectively kill microorganisms in soaked glutinous rice but also improve the quality of glutinous rice dumplings by changing the physicochemical properties of glutinous rice starch. The results of this study provide theoretical support for the application of ultrasonic technology in glutinous rice food production.

The Effect of Maltose on Structural, Physicochemical, and Digestive Properties of Lentil Starch under Electron Beam Irradiation.

This study investigated the effects of electron beam irradiation (EBI) on the structural, physicochemical, and functional properties of lentil starch with varying maltose content. EBI did not significantly disrupt the starch's surface structure or cause amorphization of starch and maltose crystals, but it significantly reduced the intensity of starch's XRD peaks. The presence of maltose intensified internal growth ring damage, leading to more cross-link and rearrangement between short chains, improving short-range ordering of lentil starch and enhancing starch's solubility and thermal stability. Additionally, adding maltose that EBI then treats can lead to an increased content of slowly digestible starch in samples.

Experimental and theoretical investigation of the treatment of Cu-rich Acid Mine Drainage using iron oxide magnetic nanoparticles

Acid Mine Drainage (AMD) is a significant environmental problem in the mining industry due to its high concentration of hazardous metals and metalloids, sulfate compounds, and low pH levels. Despite the attention that iron oxide magnetic nanoparticles (MNP) have received for AMD remediation, there is still a lack of understanding of the physicochemical mechanisms behind their non-specific adsorption, particularly in distinct variations of AMD, such as Cu-rich AMD. In this study, we synthesized, characterized, and applied MNP to the two-step treatment of Cu-rich AMD. The chemical and physical properties of the MNP and magnetically separated sludges after AMD treatment are characterized. Additionally, the chemical species adsorbed onto the MNP, the oxidation state of the resultant sludge after Cu-rich AMD treatment, and the short-range ordering of metal contaminant species on the surface of the MNP are identified. Finally, first-principles calculations using Density Functional Theory were conducted to understand how different Cu ion species adsorb to the MNP surface depending on the pH of the Cu-rich AMD. The bonding between MNP and Cu species occurs primarily through metal cation-oxygen bonds on the surface of MNP, and this bonding is influenced by the pH of the solution. A combination of experimental and theoretical approaches was the key to arrive at this conclusion. This information can aid in the comprehension of how metal contaminants adhere to the surfaces of MNP and in the precise engineering of these nanoparticles.

Influence of egg yolk-curdlan thermal-driven edible coating on the quality and retrogradation behavior of fried rice

To delay the retrogradation and improve the quality of fried rice during freeze-thaw cycles (FTCs), the curdlan (CD) was added to the egg yolk liquid (EYL) to fabricate composite edible coating, leveraging their thermal drive effect. The egg yolk liquid-curdlan (EC) edible coating solutions were investigated using Fourier transform infrared spectroscopy (FTIR) and colorimeter. Results indicated that the blue shift of the egg yolk liquid and the red shift of curdlan confirms the formation of an intermolecular interaction force. Moreover, with the increase of the curdlan concentration, the chroma (C*) of the coating liquid shows a trend of initially increased and then decreased. However, the taste decreased with the increase of the gum concentration in the formula, fortunately, the difference is small at low mass concentrations (≤1%). Additionally, the application of the coating significantly improved the quality of fresh fried rice, especially the moisture content increased by nearly 3.47% and the hardness decreased by nearly 33.19% compared with the pure egg yolk group. During the freeze-thaw cycles, the coating prominently reduced the moisture loss, and delayed the increases of hardness, fluctuation of water migration, and color parameter of fried rice, especially the 1% group. Finally, it also performs well in delayed starch retrogradation after seven freeze-thaw cycles, as reflected by low values for short-range order degree (0.42, 1%), relative crystallinity (8.09%, 1.5%), and retrogradation enthalpy (2.32 J/g, 1%). This further confirms that the egg yolk liquid-curdlan thermal-driven coatings have broad prospects in starch-based food applications.

Self-Stacked 1T-1H Layers in 6R-NbSeTe and the Emergence of Charge and Magnetic Correlations Due to Ligand Disorder.

The emergence of correlated phenomena arising from the combination of 1T and 1H van der Waals layers is the focus of intense research. Here, we synthesize a self-stacked 6R phase in NbSeTe, showing perfect alternating 1T and 1H layers that grow coherently along the c-direction, as revealed by scanning transmission electron microscopy. Angle-resolved photoemission spectroscopy shows a mixed contribution of the trigonal and octahedral Nb bands to the Fermi level. Diffuse scattering reveals temperature-independent short-range charge fluctuations with propagation vector qCO = (0.25 0), derived from the condensation of a longitudinal mode in the 1T layer, while the long-range charge density wave is quenched by ligand disorder. Magnetization measurements suggest the presence of an inhomogeneous, short-range magnetic order, further supported by the absence of a clear phase transition in the specific heat. These experimental analyses in combination with ab initio calculations indicate that the ground state of 6R-NbSeTe is described by a statistical distribution of short-range charge-modulated and spin-correlated regions driven by ligand disorder. Our results demonstrate how natural 1T-1H self-stacked bulk heterostructures can be used to engineer emergent phases of matter.

Machine Learning-Enabled Tomographic Imaging of Chemical Short-Range Atomic Ordering.

In solids, chemical short-range order (CSRO) refers to the self-organization of atoms of certain species occupying specific crystal sites. CSRO is increasingly being envisaged as a lever to tailor the mechanical and functional properties of materials. Yet quantitative relationships between properties and the morphology, number density, and atomic configurations of CSRO domains remain elusive. Herein, it is showcased how machine learning-enhanced atom probe tomography (APT) can mine the near-atomically resolved APT data and jointly exploit the technique's high elemental sensitivity to provide a 3D quantitative analysis of CSRO in a CoCrNi medium-entropy alloy. Multiple CSRO configurations are revealed, with their formation supported by state-of-the-art Monte-Carlo simulations. Quantitative analysis of these CSROs allows establishing relationships between processing parameters and physical properties. The unambiguous characterization of CSRO will help refine strategies for designing advanced materials by manipulating atomic-scale architectures.

Investigating the Synthesis Pathway of a Disordered Rocksalt Phase Via in Situ X-Ray Characterization

Recently, Li-rich disordered rocksalt (DRX) materials have gathered a lot of attention as prospective Li-ion battery cathode materials owing to their high electrochemical storage capacity and high specific energy. In contrast to the current commercialized layered Li-ion battery cathode materials (e.g. LiCoO2, LiNixMnyCo1-x-yO2), which contain toxic and expensive metals, DRX can accommodate a large variety of transition metals, such as Mn and Ti, which are cheap and earth abundant. These characteristics make them a cheaper and a more sustainable alternative to the current commonly used layered cathodes.Unlike the commercial Li-ion battery cathodes, where the transition metals and the Li are arranged in an ordered manner, DRX exhibits a highly disordered cation framework. Fluorine incorporation into DRX was extensively studied, where the fluorine anions are distributed disorderly at the anion sites. Previous studies have shown that the electrochemical performance of DRX cathodes can be enhanced via fluorination, as fluorine can effectively suppress the oxygen redox activity observed in many Li-rich cathodes. However, a large degree of fluorine incorporation into DRX was found to be difficult. As a result, it is important to study the mechanism in which fluorine is incorporated into the structure, and the role of LiF during synthesis of DRX.In addition to fluorination, the degree and type of short-range cation ordering (SRO) presenting in the materials were also found to have a significant impact on the electrochemical performance of DRX materials. The SRO present can be modified with synthesis techniques, where samples annealed at the synthesis temperature for a longer period exhibit a higher degree of SRO. This observation has demonstrated that the synthesis conditions and SRO are highly correlated. It is hence possible to control the SRO in DRX materials via varying synthesis conditions, thereby enhancing their electrochemical performance. Keeping this in mind, it is hence important to understand the mechanism by which DRX is formed.In this work, we have performed in situ synchrotron X-ray diffraction monitoring the phase progression during the solid-state synthesis of Li1.1Mn0.8Ti0.1O1.9F0.1 DRX oxyfluoride. We have observed several crystalline intermediate phases emerged before the formation of the DRX phase. Coupled with X-ray absorption spectroscopy, we are able to gain additional insights into the intermediate phases formed during the synthesis. This poster will describe the investigation of the synthesis pathway of Li1.1Mn0.8Ti0.1O1.9F0.1 DRX oxyfluoride using X-ray characterization techniques. The formation mechanism of this DRX phase will also be discussed.