Fabrication and characterization of dual-functional porous starch with both emulsification and antioxidant properties.

Starchy materials with good antioxidant, emulsification and adsorption properties have potential applications in industry. To improve these properties, a Dual-functional porous starch was prepared through one-pot synthesis. In this case, octenyl succinic anhydride (OSA) and syringic acid (SA) were selected to modify the porous starch (PS) by esterification, with subsequent signals recorded by 1H NMR at 1.2 ppm and FT-IR at 1743 cm-1, indicating the formation of Dual-functional porous starch grafted by OSA and SA. N2 adsorption analysis further proved that the porous structure (2.9 m2g-1) was still maintained after modification. This was followed by measurements of droplet size distribution (34.18 ± 3.80 µm), zeta potential (-39.62 ± 1.89 mV) and emulsion index (85.10 ± 1.76 %), all of which indicated good emulsifying capacity. Meanwhile, results of radical scavenging assay proved that the Dual-functional porous starch had considerable antioxidant properties due to the introduction of SA groups. Besides, the Dual-functional porous starch also showed good resistance to digestion. These findings not only provide a novel strategy for constructing multi-functionalized starchy materials, but also open up potential applications of starch in the food and pharmaceutical industries.

Probing covalent and non-covalent interactions between vanillic acid and starch and their effects on digestibility by solid-state NMR.

Intermolecular interactions play a significant role on the physicochemical properties and digestibility of starchy foods. This study investigated the covalent and non-covalent interactions between vanillic acid (VA) and porous starch (PS) as well as their effects on digestibility using solid-state NMR. VA-PS conjugates and mixtures were synthesized and characterized using 1H NMR, FT-IR, SEM and XRD. 13C NMR peaks at 163 ppm and FT-IR signals at 1737 cm-1 indicated the formation of ester bond in VA-PS conjugates. While differences between covalent and non-covalent interactions were also probed by solid-state NMR. The specific binding sites between VA and PS were subsequently identified by 1H13C HETCOR spectra before assessing the impact of covalent and non-covalent interactions on digestibility through an in vitro digestion test. The results revealed 13C chemical shifts of about 2.0 ppm, indicating stronger intermolecular interactions, and reduced mobility of the VA-PS conjugate due to its covalent bonding. Overall, the results showed that the VA-PS conjugate, characterized by stronger covalent interactions, exhibited superior effects in inhibiting starch digestibility compared with non-covalent interactions.

Insight into structure-activity relationships of hydroxycinnamic acids modified porous starch: The effect of phenolic hydroxy groups.

Antioxidant capacity of hydroxycinnamic acids-modified starch mainly depends on their chemical structure. Herein, cinnamic acid as well as meta-substituted and para-substituted cinnamic acid were selected for esterification with porous starch (labelled as CA@PS, m-CA@PS and p-CA@PS), with the successful formation of porous starch (labelled as PS) esters then confirmed by 1H NMR, 13C solid-state NMR and FT-IR spectroscopy. Three PS esters with almost same degrees of substitution (DS) were obtained, and antioxidant assays, including DPPH radical scavenging, reducing power and hydroxyl radical scavenging tests, were subsequently used to evaluate the antioxidant activity of the esterified PS. Overall, CA@PS showed weak antioxidant activity because of the absence of phenolic hydroxy, while p-CA@PS displayed better antioxidant capacity. Because its conjugated structure offered the stronger electron-donating effect, that could enhance antioxidant capacity. Therefore, antioxidant capacity depended significantly on overall chemical structure, including numbers and substitution positions of phenolic hydroxy groups.

Electrospun Nanofiber Membrane: An Efficient and Environmentally Friendly Material for the Removal of Metals and Dyes.

With the rapid development of nanotechnology, electrospun nanofiber membranes (ENM) application and preparation methods have attracted attention. With many advantages such as high specific surface area, obvious interconnected structure, and high porosity, ENM has been widely used in many fields, especially in water treatment, with more advantages. ENM solves the shortcomings of traditional means, such as low efficiency, high energy consumption, and difficulty in recycling, and it is suitable for recycling and treatment of industrial wastewater. This review begins with a description of electrospinning technology, describing the structure, preparation methods, and factors of common ENMs. At the same time, the removal of heavy metal ions and dyes by ENMs is introduced. The mechanism of ENM adsorption on heavy metal ions and dyes is chelation or electrostatic attraction, which has excellent adsorption and filtration ability for heavy metal ions and dyes, and the adsorption capacity of ENMs for heavy metal ions and dyes can be improved by increasing the metal chelation sites. Therefore, this technology and mechanism can be exploited to develop new, better, and more effective separation methods for the removal of harmful pollutants to cope with the gradually increasing water scarcity and pollution. Finally, it is hoped that this review will provide some guidance and direction for research on wastewater treatment and industrial production.

Molecular interactions between apigenin and starch with different amylose/amylopectin ratios revealed by X-ray diffraction, FT-IR and solid-state NMR.

Starch can readily form complexes with polyphenols. However, its two components, namely amylose and amylopectin, differ significantly in their ability to complex with phenolic compounds. Given that the mechanism of their interaction is still poorly studied, this work investigated intermolecular interactions between apigenin and starch with different amylose/amylopectin ratios using 1H NMR, FT-IR, XRD, DSC and solid-state NMR. Results showed that corn starch with high amylose/amylopectin ratios had a better complexing ability and higher complexing index with apigenin than amylopectin. Besides, solid-state NMR suggested that the molecular mechanism behind the strong intermolecular interactions between corn starch and apigenin involved hydrogen bonds. Furthermore, the detailed binding sites of hydrogen bonds, that linked by hydroxyl-starch and phenyl-apigenin were also confirmed by 1H13C heteronuclear correlation (HETCOR) spectra. This study revealed the molecular mechanism on amylose/amylopectin complexing with apigenin and provides a theoretical basis for further developing polyphenols in starchy food.

Probing molecular interactions of amylose-morin complex and their effect on antioxidant capacity by 2D solid-state NMR spectroscopy.

Interaction of polyphenols and starch significantly governed the further applications on polyphenol-starchy foods. Elucidation of inter-molecular interaction is, however, a challenge because conventional characterizations could not detect the change of micro-environment caused by weak interactions. Herein, a facile strategy for molecular detection of amylose-polyphenol interactions was reported using two-dimensional solid-state NMR spectroscopy. Amylose-morin complex was prepared and characterized using 1H NMR, FT-IR, DSC, XRD and SEM. Significantly, variation of chemical shifts, splitted peaks and peak width, monitored by 13C CP/MAS and 1H NMR spectra, identified the strong inter-molecular interaction and binding sites. Furthermore, correlated signals from 1H-13C HETCOR confirmed the binding sites of interactions. These findings confirmed the interaction was inter-molecular hydrogen bonds, which generated between hydroxy-3,5,7 of morin and hydroxy groups of amylose. Besides, DPPH radical scavenging and reducing power assay indicated inter-molecular hydrogen bonds are not strong enough to interfere antioxidant capacity of morin.

pH-responsive in situ gelling properties of thiolated citrus high-methoxyl pectin and its potential gel mechanism.

pH-responsive in situ gelling properties of thiolated citrus high-methoxyl pectin (TCHMP) were investigated in this study. The gelation capacity results revealed that the in situ gelation behavior of TCHMP only occurred when the pH value was higher than 6.25. The gel strength increased from 26.63 g to 42.77 g as the pH value increased from 7.4 to 8.9. Rheological measurements confirmed that the apparent viscosity and viscoelasticity of TCHMP were highly dependent on pH value and dialysis time. Compared with the control group, the apparent viscosity of TCHMP dialyzed in phosphate-buffered saline (PBS) of pH 8.9 for 180 min increased 695-fold. During the dialysis process of TCHMP at different pH values (7.4-8.9), the final thiol groups content decreased and the final disulfide bonds content increased with the increase in pH value. This illustrates that the mechanism of in situ gelation is mainly the oxidation of thiol-thiol groups to form disulfide bonds. These results can put forward new insights into the pH-responsive in situ gelling properties of TCHMP and provide a theoretical basis for the application of TCHMP in neutral and alkaline gel systems.

Construction of caffeic acid modified porous starch as the dual-functional microcapsule for encapsulation and antioxidant property.

A dual-functional food-grade microcapsule, which was constructed by caffeic acid and porous starch was obtained. Caffeic acid modified porous starch (CA-PS) was accordingly synthesized successfully by esterification. Carbonyl signal observed by 13C solid state NMR (170 ppm) and FT-IR (1745 cm-1), indicating the formation of ester bond. BET of CA-PS was determined as 44.8 m2/g by N2 adsorption analysis. The results proved CA-PS has both excellent adsorption and antioxidant activity. Furthermore, it has been applied for encapsulation of linoleic acid (LA) to prevent its degradation effectively, because LA adsorbed in porous adsorbents without antioxidant activity may still suffer serious oxidation. Besides, 1H NMR Integral of LA did not show a significant decay. This observation demonstrated CA-PS indeed has the better performance on protection of LA than PS. We expect this work will boost research on designing and employing multi-functional starchy materials for further applications.

Compound treatment of thiolated citrus high-methoxyl pectin and sodium phosphate dibasic anhydrous improved gluten network structure.

The effects of pectin or thiolated pectin alone and combined with sodium phosphate dibasic anhydrous (Na2HPO4) on the performances of gluten were studied. Results showed that compared with pectin treated gluten, the thiols of thiolated pectin treated gluten increased by 8.7 times. Analysis of the extensibility and rheological properties revealed that pectin reduced gluten strength, whereas thiolated pectin improved the strength and viscoelasticity of gluten, especially with the assistance of Na2HPO4. Furthermore, thiolated pectin and Na2HPO4 compound increased enthalpy (ΔH, from 150.42 to 168.60 J/g) and decreased Imax (from 5255.33 to 2775.33) markedly, indicating gluten aggregation. The highest ß-sheet (76.47%) and the lowest α-helix/ß-sheet ratio (0.11) were found in gluten treated with thiolated pectin and Na2HPO4 and suggested gluten stability was enhanced. SEM observation confirmed that thiolated pectin and Na2HPO4 compound strengthened the gluten structure. These results are of great significance for the supplementation of pectin in wheat products.

Insights into the gelatinization of potato starch by in situ 1H NMR.

The gelatinization of potato starch and the effect of NaCl on starch gelatinization were monitored successfully in situ by 1H NMR spectroscopy. Variable temperature (VT) 1H NMR measurement, from 316 K to 340 K, was conducted on a suspension of potato starch and deuterium water as well as a mixture of potato starch, NaCl and deuterium water. The hydration level of starch was determined with the increase of temperature. In the presence of NaCl, the initial gelatinization temperature of potato starch was decreased from 331 to 328 K. Meanwhile, in situ 1H NMR spectroscopy as a function of time was also carried out to monitor the gelatinization with a time resolution of 90 s per spectrum. Furthermore, the effect of using different processing methods during gelatinization, including varying the temperature or time duration, was investigated in detail. It was confirmed that protons from different groups of starch showed different accessibility for water during hydration of starch granules. In comparison with temperature, gelatinization time as the major factor for reaching complete gelatinization was confirmed. We expect that this research, as a continuing effort to apply NMR spectroscopy for characterizing starch, will pave a new way in the structural elucidation of starch.

Construction of ferulic acid modified porous starch esters for improving the antioxidant capacity.

For exploration of a type of synthetic antioxidant dietary fiber (ADF), porous starch (PS), modified by esterification with ferulic acid (FA) moieties, was synthesized successfully, with different degree of substitution (DS). The ester linkage of FA modified PS was confirmed by 13C solid-state NMR and FT-IR. XRD analysis showed that starch ferulates had a different crystal structure from the V-type pattern of native starch, suggesting that the starch gelled during the esterification reaction, then re-crystallized into a different structure. Morphological studies revealed that FA modified PS esters had a different morphology of irregular beehive-like and dense fibrous-like structures compared with that of native starch. In vitro antioxidant assays showed that starch ferulates had excellent antioxidant capacity. In particular, FA modified PS esters had a much higher antioxidant capacity than free FA in the ß-carotene-linoleic acid assay. This study has advanced the technology of using porous starches for modifying the biological activity of an antioxidant polyphenol. We expect this work would inspire further studies on the interactions of phenolics with other food ingredients in the food industry.

A Novel COVID-19-Related Drug Discovery Approach Based on Non-Equidimensional Data Clustering.

The novel coronavirus disease (COVID-19) caused by severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) has spread all over the world. Since currently no effective antiviral treatment is available and those original inhibitors have no significant effect, the demand for the discovery of potential novel SARS-CoV-2 inhibitors has become more and more urgent. In view of the availability of the inhibitor-bound SARS-CoV-2 Mpro and PLpro crystal structure and a large amount of proteomics knowledge, we attempted using the existing coronavirus inhibitors to synthesize new ones, which combined the advantages of similar effective substructures for COVID-19 treatment. To achieve this, we first formulated this issue as a non-equidimensional inhibitor clustering and a following cluster center generating problem, where three essential challenges were carefully addressed, which are 1) how to define the distance between pairwise inhibitors with non-equidimensional molecular structure; 2) how to group inhibitors into clusters when the dimension is different; 3) how to generate the cluster center under this non-equidimensional condition. To be more specific, a novel matrix Kronecker product (p, m)-norm ⋅ p m ⊗ was first defined to induce the distance D p (A, B) between two inhibitors. Then, the hierarchical clustering approach was conducted to find similar inhibitors, and a novel iterative algorithm-based Kronecker product (p, m)-norm was designed to generate individual cluster centers as the drug candidates. Numerical experiments showed that the proposed methods can find novel drug candidates efficiently for COVID-19, which has provided valuable predictions for further biological evaluations.

Molecular insight into the interactions between starch and cuminaldehyde using relaxation and 2D solid-state NMR spectroscopy.

The interaction between cuminaldehyde and starch mainly governed the effect of further handling on food applications of cuminaldehyde. However, little information is available about the interactions of these components. We utilized relaxation and heteronuclear correlation (HETCOR) solid-state NMR spectroscopy to investigate the interaction between cuminaldehyde and porous starch at molecular level. We found that the interactions occurred mainly through hydrogen bonds. Cuminaldehyde molecules were restricted by starch, which resulted in the limitation of their movements and the longer 1H T1 relaxation time. Furthermore, the well resolved correlated peaks in 2D 1H-13C HETCOR spectrum confirmed the formation of hydrogen bonds. The oxygen atoms at hydroxyl-2,3 of starch were the binding sites, which combined with hydrogens of cuminaldehyde. This present work not only afford a new approach to obtain a molecular understanding of interactions, but also expanded the application of solid-state NMR to investigation of the interaction on functional components.

The gelation behavior of thiolated citrus high-methoxyl pectin induced by sodium phosphate dibasic dodecahydrate.

The present study found that sodium phosphate dibasic dodecahydrate (Na2HPO4) was capable of inducing the gelation of thiolated citrus high-methoxyl pectin (TCHMP). TCHMP was synthesized by amidation of citrus high-methoxyl pectin. The gel formation exhibited an obvious concentration-dependence, including TCHMP and Na2HPO4 concentration. For Na2HPO4-induced TCHMP gels (TCHMPGs), gel strength and water holding capacity (WHC) increased, while the microcellular network structure was more compact with the increase of TCHMP and Na2HPO4 concentration. Dynamic viscoelastic experiment showed when Na2HPO4 concentration was more than or equal to 0.5 mol/L, TCHMP sols could be transferred into gels within 30 min. Crystal property was not changed while thermal stability was improved after phase transition. Gelling forces analysis indicated that disulfide bonds were the main interaction forces in TCHMPGs. Consequently, TCHMPGs were covalently crosslinked and exhibited satisfactory gel performance. The results provide a theoretical basis for the formation of gels by Na2HPO4 induced TCHMP.

Identifying Disease Related Genes by Network Representation and Convolutional Neural Network.

The identification of disease related genes plays essential roles in bioinformatics. To achieve this, many powerful machine learning methods have been proposed from various computational aspects, such as biological network analysis, classification, regression, deep learning, etc. Among them, deep learning based methods have gained big success in identifying disease related genes in terms of higher accuracy and efficiency. However, these methods rarely handle the following two issues very well, which are (1) the multifunctions of many genes; and (2) the scale-free property of biological networks. To overcome these, we propose a novel network representation method to transfer individual vertices together with their surrounding topological structures into image-like datasets. It takes each node-induced sub-network as a represented candidate, and adds its environmental characteristics to generate a low-dimensional space as its representation. This image-like datasets can be applied directly in a Convolutional Neural Network-based method for identifying cancer-related genes. The numerical experiments show that the proposed method can achieve the AUC value at 0.9256 in a single network and at 0.9452 in multiple networks, which outperforms many existing methods.

Insights into the microstructure and interconnectivity of porosity in porous starch by hyperpolarized 129Xe NMR.

For the first time, hyperpolarized (HP) 129Xe NMR measurements are utilized to explore porous structures of porous starch (PS) successfully. Some micropores resided inside the mesopore walls of PS were detected by variable temperature (VT) HP 129Xe NMR, and the pore sizes of micropores were also estimated using the empirical relationship. Furthermore, the interconnectivity of pores was investigated in detail by two-dimensional (2D) exchange spectroscopy (EXSY). The exchange process of xenon from microporosity within pore walls to the free gas space was occurred at the mixing time of ≥12 ms at 173 K, which indicated the well interconnectivity between micropores and mesopores. This study not only exhibits a new approach for investigation of pores and hollows of PS, but also provides a better understanding of porous structures for rational design in adsorbing functional compounds.

129Xe NMR: A powerful tool for studying the adsorption mechanism between mesoporous corn starch and palladium.

For the first time, 129Xe NMR measurements are utilized to explore adsorption mechanism between porous structures of mesoporous corn starch and Palladium. Dithiocarbamate modified mesoporous corn starch (donated as DTC MS) was synthesized and applied for adsorption of Pd (II) ion successfully. The structural characterization of DTC MS was carried out by FT-IR, 13C solid-state NMR and XRD, respectively. To study the adsorption mechanism, variable temperature 129Xe NMR was measured on samples of DTC MS and Pd adsorbed in DTC mesoporous starch (donated as Pd-DTC MS), respectively. It was found that Pd ions were mainly located inside pores and channels instead of the surface of mesoporous starch. The results not only demonstrate that 129Xe NMR spectroscopy is a powerful tool to assess the porous structure of MS, but also pave the way for investigating the interaction between functional molecules and porous starch.

Construction of octenyl succinic anhydride modified porous starch for improving bioaccessibility of ß-carotene in emulsions.

Modified porous starch (PS), by introducing octenyl succinic anhydride (OSA) moieties, was synthesized successfully, which was applied as an emulsion of ß-carotene for the first time. The pores and channels within porous starch provided more possibilities for OSA to modify starch. The ester linkage of OSA modified PS with different degrees of substitution (DS) were confirmed by both 13C solid-state NMR and Fourier transform-infrared spectroscopy (FT-IR). The hydrophobic octenyl succinic and hydrophilic hydroxyl groups of OSA modified PS showed the good emulsifying capability, which could be utilized to prepare ß-carotene emulsions. And the bioaccessibility of ß-carotene was also enhanced with increasing DS of OSA modified starch. This study not only paves a new way using porous starches for modification of starch, but also offers an attractive alternative for obtaining emulsion-based delivery systems for bioactive components.

Damage to Trichothecium roseum caused by sodium silicate is independent from pH.

Trichothecium roseum is one of the most important postharvest pathogens in arid and semiarid regions. Sodium silicate (NaSi) and environmental pH have significant inhibitory effects on fungal growth. However, no study has addressed the relationship of NaSi and pH in combination and the effects on T. roseum. In this work, we showed that spore germination, germ tube elongation, and mycelial growth of T. roseum were significantly inhibited by various NaSi concentrations, which had corresponding increasing pHs. Furthermore, these NaSi solutions showed a much greater impact than did pH treatments alone. The pathogenicity of NaSi-treated conidia on a model assay (conidia-inoculated apple fruit) was dramatically reduced, whereas no changes of pathogenicity were evident for the corresponding pH (various sodium hydroxide (NaOH) solutions) treatments. Fluorescent microscopy, using propidium iodide staining, showed damage of the plasma membranes of T. roseum conidia treated with both NaSi and NaOH, although the damage was more severe with NaSi. Leakage of proteins and sugars was significantly higher in NaSi-treated and NaOH-treated conidia than in untreated controls. In addition, serious damage was observed in the conidia exposed to NaSi for longer periods of time. Ultrastructural observations showed that treatment with either NaSi or NaOH caused a plasmolysis state and disorganized organelles. Taken together the results show that NaSi has inhibitory effects on T. roseum and that the inherent higher pH of NaSi solutions of higher concentrations simply acts as an enhancer of the inhibitory effects of NaSi.

Identifying protein complexes in protein-protein interaction networks by using clique seeds and graph entropy.

The identification of protein complexes plays a key role in understanding major cellular processes and biological functions. Various computational algorithms have been proposed to identify protein complexes from protein-protein interaction (PPI) networks. In this paper, we first introduce a new seed-selection strategy for seed-growth style algorithms. Cliques rather than individual vertices are employed as initial seeds. After that, a result-modification approach is proposed based on this seed-selection strategy. Predictions generated by higher order clique seeds are employed to modify results that are generated by lower order ones. The performance of this seed-selection strategy and the result-modification approach are tested by using the entropy-based algorithm, which is currently the best seed-growth style algorithm to detect protein complexes from PPI networks. In addition, we investigate four pairs of strategies for this algorithm in order to improve its accuracy. The numerical experiments are conducted on a Saccharomyces cerevisiae PPI network. The group of best predictions consists of 1711 clusters, with the average f-score at 0.68 after removing all similar and redundant clusters. We conclude that higher order clique seeds can generate predictions with higher accuracy and that our improved entropy-based algorithm outputs more reasonable predictions than the original one.