Interfacial interactions between spider silk protein and cellulose studied by molecular dynamics simulation.

CONTEXT: Due to their excellent biocompatibility and degradability, cellulose/spider silk protein composites hold a significant value in biomedical applications such as tissue engineering, drug delivery, and medical dressings. The interfacial interactions between cellulose and spider silk protein affect the properties of the composite. Therefore, it is important to understand the interfacial interactions between spider silk protein and cellulose to guide the design and optimization of composites. The study of the adsorption of protein on specific surfaces of cellulose crystal can be very complex using experimental methods. Molecular dynamics simulations allow the exploration of various physical and chemical changes at the atomic level of the material and enable an atomic description of the interactions between cellulose crystal planes and spider silk protein. In this study, molecular dynamics simulations were employed to investigate the interfacial interactions between spider silk protein (NTD) and cellulose surfaces. Findings of RMSD, RMSF, and secondary structure showed that the structure of NTD proteins remained unchanged during the adsorption process. Cellulose contact numbers and hydrogen bonding trends on different crystalline surfaces suggest that van der Waals forces and hydrogen bonding interactions drive the binding of proteins to cellulose. These findings reveal the interaction between cellulose and protein at the molecular level and provide theoretical guidance for the design and synthesis of cellulose/spider silk protein composites. METHODS: MD simulations were all performed using the GROMACS-5.1 software package and run with CHARMM36 carbohydrate force field. Molecular dynamics simulations were performed for 500 ns for the simulated system.

Fabrication of a MXene-based shape-memory hydrogel and its application in the wound repair of skin.

Wound dressings can generally complete hemostasis and provide temporary protection after skin damage. Herein, a MXene-based hydrogel was prepared from MXene, gelatin, poly(ethylene glycol)diacrylate (PEGDA) and N,N'-methylenebis(acrylamide) (HEAA) to prepare wound-dressing hydrogels for skin repair. HEAA and PEGDA crosslink polymerization formed the first layer of the network. Hydrogen bonds between MXene, PHEAA, and gelatin formed the second layer of the network. To make the hydrogel more suitable for skin repair, the mechanical properties of the hybrid hydrogel were adjusted. The MXene-based hydrogel could recover its original shape in 16 s upon immersion in water or for a few minutes under light irradiation. The obtained hydrogel showed good photothermal properties upon light irradiation (808 nm, 1 W cm-2) for 20 s, and its temperature on the surface could reach 86.4 °C. Due to its good photothermal properties, this MXene-based hydrogel was suitable for skin repair.

Molecular insights into inhibiting effects of lignin on cellulase investigated by molecular dynamics simulation.

The hydrolysis of lignocellulose into fermentable monosaccharides using cellulases represents a critical stage in lignocellulosic bioconversion. However, the inactivation of cellulase in the presence of lignin is attributed to the high cost of biofinery. To address this challenge, a comprehensive investigation into the structure-function relationship underlying lignin-driven cellulase inactivation is essential. In this study, molecular docking and molecular dynamics (MD) simulations were employed to explore the impacts of lignin fragments on the catalytic efficiency of cellulase at the atomic level. The findings revealed that soluble lignin fragments and cellulose could spontaneously form stable complexes with cellulase, indicating a competitive binding scenario. The enzyme's structure remained unchanged upon binding to lignin. Furthermore, specific amino acid residues have been identified as involved in interactions with lignin and cellulose. Hydrophobic interactions were found to dominate the binding of lignin to cellulase. Based on the mechanisms underlying the interactions between lignin fragments and cellulase, decreased hydrophobicity and change in the charge of lignin may mitigate the inhibition of cellulase. Furthermore, site mutations and chemical modification are also feasible to improve the efficiency of cellulase. This study may contribute valuable insights into the design of more lignin-resistant enzymes and the optimization of lignocellulosic pretreatment technologies.Communicated by Ramaswamy H. Sarma.

Interstitial Hydrogen Atom to Boost Intrinsic Catalytic Activity of Tungsten Oxide for Hydrogen Evolution Reaction.

Tungsten oxide (WO3 ) is an appealing electrocatalyst for the hydrogen evolution reaction (HER) owing to its cost-effectiveness and structural adjustability. However, the WO3 electrocatalyst displays undesirable intrinsic activity for the HER, which originates from the strong hydrogen adsorption energy. Herein, for effective defect engineering, a hydrogen atom inserted into the interstitial lattice site of tungsten oxide (H0.23 WO3 ) is proposed to enhance the catalytic activity by adjusting the surface electronic structure and weakening the hydrogen adsorption energy. Experimentally, the H0.23 WO3 electrocatalyst is successfully prepared on reduced graphene oxide. It exhibits significantly improved electrocatalytic activity for HER, with a low overpotential of 33 mV to drive a current density of 10 mA cm-2 and ultra-long catalytic stability at high-throughput hydrogen output (200 000 s, 90 mA cm-2 ) in acidic media. Theoretically, density functional theory calculations indicate that strong interactions between interstitial hydrogen and lattice oxygen lower the electron density distributions of the d-orbitals of the active tungsten (W) centers to weaken the adsorption of hydrogen intermediates on W-sites, thereby sufficiently promoting fast desorption from the catalyst surface. This work enriches defect engineering to modulate the electron structure and provides a new pathway for the rational design of efficient catalysts for HER.

Construction of Wash-Resistant Photonic Crystal-Coated Fabrics based on Hydrogen Bonds and a Dynamically Cross-Linking Double-Network Structure.

Structural coloration as the most possible way to realize the ecofriendly dying process for textiles or fabrics has attracted significant attention in the past decades. However, photonic crystals (PCs) are a typical example of materials with structural color usually located on the surface of the fabrics or textiles, which make them not stable when rubbed, bent, or washed due to the weak interaction between the PC coatings and fabrics. Here, double networks were constructed between the PC coatings and the fabrics for the first time via a hydrogen bond by introducing tannic acid (TA) and dynamic cross-linking with 2-formylphenylboronic acid to increase the wash resistance of the structural colored fabrics. On modifying the monodispersed SiO2 nanoparticles, poly(dimethylsiloxane), and the fabrics, the interaction between the PC coatings and the fabrics increased by the formation of double networks. The structural color, wash, and rub resistance of the PC-coated fabrics were systematically studied. The obtained fabrics with the TA content at 0.030% (SiDT30) showed the best wash and rub resistance. The construction of double networks not only improved the wash and rub resistance of PCs but also retained the bright structural color of the PC coatings, facilitating the practical application of structural coloration in the textile industry.

Structurally colored aramid fabric construction and its application as a recyclable photonic catalyst.

Structural colors can be used in fabric coloring due to their bright color and non-fading properties. However, it is still a challenge to construct structural color on high crystallinity, smooth surfaced and yellow colored aramid fabrics. Herein, for the first time, photonic crystals (PCs) with structural color were constructed on aramid fabrics by introducing dopamine to modify aramid fabrics and synthesizing monodisperse high refractive index zinc sulfide nanoparticles (ZnS). The influence of the PC coatings on the structural color, mechanical properties, and thermal stability of the structurally colored aramid fabrics or fibers was further investigated. Moreover, due to the excellent catalytic properties of ZnS and the slow photon effects of PCs, the structurally colored fabrics showed good photocatalytic properties, which will be beneficial in reusing the catalysts, which is crucial to their application in the coloring of fabrics but also facilitates the recycling of waste PC coated aramid fabrics.

Molecular and thermodynamic insights into interfacial interactions between collagen and cellulose investigated by molecular dynamics simulation and umbrella sampling.

Cellulose/collagen composites have been widely used in biomedicine and tissue engineering. Interfacial interactions are crucial in determining the final properties of cellulose/collagen composite. Molecular dynamics simulations were carried out to gain insights into the interactions between cellulose and collagen. It has been found that the structure of collagen remained intact during adsorption. The results derived from umbrella sampling showed that (110) and ([Formula: see text]) faces exhibited the strongest affinity with collagen (100) face came the second and (010) the last, which could be attributed to the surface roughness and hydrogen-bonding linkers involved water molecules. Cellulose planes with flat surfaces and the capability to form hydrogen-bonding linkers produce stronger affinity with collagen. The occupancy of hydrogen bonds formed between cellulose and collagen was low and not significantly contributive to the binding affinity. These findings provided insights into the interactions between cellulose and collagen at the molecular level, which may guide the design and fabrication of cellulose/collagen composites.

Exogenous Ca2+ priming can improve peanut photosynthetic carbon fixation and pod yield under early sowing scenarios in the field.

Harnessing cold-resilient and calcium-enriched peanut production technology are crucial for high-yielding peanut cultivation in high-latitude areas. However, there is limited field data about how exogenous calcium (Ca2+) application would improve peanut growth resilience during exposure to chilling stress at early sowing (ES). To help address this problem, a two-year field study was conducted to assess the effects of exogenous foliar Ca2+ application on photosynthetic carbon fixation and pod yield in peanuts under different sowing scenarios. We measured plant growth indexes, leaf photosynthetic gas exchange, photosystems activities, and yield in peanuts. It was indicated that ES chilling stress at the peanut seedling stage led to the reduction of Pn, gs, Tr, Ls, WUE, respectively, and the excessive accumulation of non-structural carbohydrates in leaves, which eventually induced a chilling-dependent feedback inhibition of photosynthesis due mainly to weaken growth/sink demand. While exogenous Ca2+ foliar application improved the export of nonstructural carbohydrates, and photosynthetic capacity, meanwhile activated cyclic electron flow, thereby enhancing growth and biomass accumulation in peanut seedlings undergoing ES chilling stress. Furthermore, ES combined with exogenous Ca2+ application can significantly enhance plant chilling resistance and peanut yield ultimately in the field. In summary, the above results demonstrated that exogenous foliar Ca2+ application restored the ES-linked feedback inhibition of photosynthesis, enhancing the growth/sink demand and the yield of peanuts.

Overfertilization reduces tomato yield under long-term continuous cropping system via regulation of soil microbial community composition.

Long-term monoculture cropping and overfertilization degrade soil fertility, which reduces crop growth and promotes the development of soil-borne diseases. However, it remains unclear what the temporal effects of the above factors are on the tomato yield and microbial community structure. Thus, a greenhouse experiment with different amounts of fertilization [2,196 kg ha-1 (control) and 6,588 kg ha-1 (overfertilization) of inorganic fertilizers (NPK)] was carried out with the soils used previously for 1, 2, and 12 years under monoculture of tomato. A 12-year overfertilization decreased soil pH by 1.37 units. Soil electrical conductivity (EC) and concentrations of soil nutrients are enhanced with the increase in tomato cropping duration. Higher content of soil nutrients was found under overfertilization compared to the control in the 12-year soil. Overfertilization decreased the activity of ß-1,4-glucosidase (BG) and oxidase compared to the control in the 12-year soil. Bacterial diversity and richness decreased by 6 and 31%, respectively, under overfertilization in 12-year soil compared to the control. The relative abundance of Gemmatimonas and Gp6 in 12-year soil under overfertilization was 17 and 78%, respectively, lower than in control soil. Soil pH and total carbon (TC) were the major factors explaining changes in microbial composition. A 38% decrease in yield was caused by overfertilization in 12-year soil compared to the control. Microbial community composition was the main factor that moderated tomato yield. In addition, fertilization rather than cropping duration had a greater impact on tomato yield. Therefore, our results suggest that long-term overfertilization influenced soil pH, soil TC, and soil microbial community composition to regulate tomato yield.

Sesquiterpene lactone dimers from the fruit of Carpesium abrotanoides L.

Seven undescribed sesquiterpene lactone dimers (SLDs) (carpeabrodilactones A-G), one known SLD, and six known sesquiterpenes were isolated from the fruit of Carpesium abrotanoides L. Carpeabrodilactone A was a dimeric carabrane featuring a rare C-13-C-13' linkage. Carpeabrodilactones B and C are the first two SLDs to be described possessing a carabranolide unit and a guaianolide unit connected by an O-ether linkage. The structures of the SLDs were assigned based on HRESIMS, NMR analysis, 13C NMR calculation, ECD calculation, and modified Mosher's method. Four SLDs showed potent cytotoxicity against K562 and/or A549 cells, with IC50 values below 10 µM, but none inhibited protein tyrosine phosphatases at 40 µM, including PTP1B, SHP1, CD45, and TCPTP.

A Review of Characteristics of Bio-Oils and Their Utilization as Additives of Asphalts.

Transforming waste biomass materials into bio-oils in order to partially substitute petroleum asphalt can reduce environmental pollution and fossil energy consumption and has economic benefits. The characteristics of bio-oils and their utilization as additives of asphalts are the focus of this review. First, physicochemical properties of various bio-oils are characterized. Then, conventional, rheological, and chemical properties of bio-oil modified asphalt binders are synthetically reviewed, as well as road performance of bio-oil modified asphalt mixtures. Finally, performance optimization is discussed for bio-asphalt binders and mixtures. This review indicates that bio-oils are highly complex materials that contain various compounds. Moreover, bio-oils are source-depending materials for which its properties vary with different sources. Most bio-oils have a favorable stimulus upon the low temperature performance of asphalt binders and mixtures but exhibit a negative impact on their high-temperature performance. Moreover, a large amount of oxygen element, oxygen-comprising functional groups, and light components in plant-based bio-oils result in higher sensitivity to ageing of bio-oil modified asphalts. In order to increase the performance of bio-asphalts, most research has been limited to adding additive agents to bio-asphalts; therefore, more reasonable optimization methods need to be proposed. Furthermore, upcoming exploration is also needed to identify reasonable evaluation indicators of bio-oils, modification mechanisms of bio-asphalts, and long-term performance tracking in field applications of bio-asphalts during pavement service life.

New protein tyrosine phosphatase inhibitors from fungus Aspergillus gorakhpurensis F07ZB1707.

Twelve new compounds, aspergorakhins A-L (1-12) coupled with one known xanthone leptosphaerin D (13), were isolated from the extract of soil-derived fungus Aspergillus gorakhpurensis F07ZB1707. Their structures were elucidated by spectroscopic data analysis including UV, IR, NMR, and HRESIMS. The absolute configurations of 5 and 8-11 were identified using ECD and OR calculations. All compounds were tested by enzyme inhibitory activity assay in vitro. Aspergorakhin A (1) showed selective activities against PTP1B and SHP1 over TCPTP with IC50 values 0.57, 1.19, and 22.97 µM, respectively. Compounds 1 and 2 exhibited modest cytotoxicity against tumor cell lines A549, HeLa, Bel-7402, and SMMC-7721 with IC50 values in the range of 6.75-83.4 µM.

Tumor supernatant derived from hepatocellular carcinoma cells treated with vincristine sulfate have therapeutic activity.

Vincristine sulfate (VCR), a commonly used chemotherapeutic agent, kills cancer cells as well as the normal cells for its cytotoxicity. But it is still unclear whether it can exert therapeutic effect on untreated cancer cells by changing the supernatant of cancer cells. Here, we explored the subsequent cascade effects of the supernatant of cancer cells that were transiently treated with VCR on untreated tumor cells and its responsible mechanisms. VCR and three different hepatocellular carcinoma (HCC) cell lines were used for an experiment. The experiment was conducted in vitro to eliminate the body's internal factors and the effects of the immune system. The results suggested that drug-free tumor supernatant (TSN) could promote the differentiation, repress the transcription of liver cancer stem cell's markers and the proliferation in SMMC-7721, Bel-7402 and Huh7 cells. Furthermore, we found that the TSN could abolish YAP1 transcriptional activity to inhibit the proliferation and increase the transcriptional activity of HNF4α to promote the differentiation in SMMC-7721 and Bel-7402 cells. In conclusion, the TSN could inhibit the proliferation and induce differentiation in different HCC cells.

Supplementary Calcium Restores Peanut (Arachis hypogaea) Growth and Photosynthetic Capacity Under Low Nocturnal Temperature.

Peanut (Arachis hypogaea L.) is a globally important oil crop, which often experiences poor growth and seedling necrosis under low nocturnal temperatures (LNT). This study assessed the effects of supplementary calcium (Ca2+) and a calmodulin inhibitor on peanut growth and photosynthetic characteristics of plants exposed to LNT, followed by recovery at a higher temperature. We monitored key growth and photosynthetic parameters in a climate-controlled chamber in pots containing soil. LNT reduced peanut growth and dry matter accumulation, enhanced leaf nonstructural carbohydrates concentrations and non-photochemical quenching, decreased the electron transport rate, increased the transmembrane proton gradient, and decreased gas exchange rates. In peanuts subjected to LNT, foliar application of Ca2+ restored growth, dry matter production and leaf photosynthetic capacity. In particular, the foliar Ca2+ application restored temperature-dependent photosynthesis feedback inhibition due to improved growth/sink demand. Foliar sprays of a calmodulin inhibitor further deteriorated the effects of LNT which validated the protective role of Ca2+ in facilitating LNT tolerance of peanuts.

Antitumor activity of the Ailanthus altissima bark phytochemical ailanthone against breast cancer MCF-7 cells.

Ailanthone is isolated from the bark of Ailanthus altissima (Mill.) Swingle (Simaroubaceae). The mechanism that underlies the activity of ailanthone on MCF-7 cells was investigated by MTT assay. Breast cancer MCF-7 cells were treated with 0.5, 1.0, 2.0, 4.0 and 8.0 µg/ml ailanthone for 24, 48 and 72 h. The inhibition of proliferation induced by treatment with ailanthone was assessed by MTT assay. Apoptosis and cell cycle distribution in MCF-7 cells with the same doses of ailanthone for 48 h were determined by flow cytometry. Expression of apoptosis-associated genes and proteins were analyzed by reverse transcription-polymerase chain reaction (RT-PCR) and western blot analysis, respectively. The results revealed that ailanthone inhibited MCF-7 cell proliferation. Flow cytometry assay demonstrated that ailanthone induced apoptosis and G0/G1 cell cycle arrest in MCF-7 cells. Western blotting and RT-PCR assays demonstrated that upregulation of pro-apoptotic caspase-3 and Bcl-associated X, and downregulation of anti-apoptotic apoptosis regulator B-cell lymphoma-2 in MCF-7 cells may be associated with the induction of apoptosis and inhibition of proliferation. To the best of our knowledge, the present study is the first to investigate the antitumor activity of ailanthone from A. altissima on MCF-7 cells and to attempt to elucidate the underlying mechanism. The present study revealed the presence of ailanthone-mediated antitumor effects, indicating that ailanthone may be a novel phytomedicine with potential use in breast cancer therapy.

Sophoraflavenone G Restricts Dengue and Zika Virus Infection via RNA Polymerase Interference.

Flaviviruses including Zika, Dengue and Hepatitis C virus cause debilitating diseases in humans, and the former are emerging as global health concerns with no antiviral treatments. We investigated Sophora Flavecens, used in Chinese medicine, as a source for antiviral compounds. We isolated Sophoraflavenone G and found that it inhibited Hepatitis C replication, but not Sendai or Vesicular Stomatitis Virus. Pre- and post-infection treatments demonstrated anti-flaviviral activity against Dengue and Zika virus, via viral RNA polymerase inhibition. These data suggest that Sophoraflavenone G represents a promising candidate regarding anti-Flaviviridae research.

Xylomexicanins I and J: Limonoids with Unusual B/C Rings from Xylocarpus granatum.

Two tetranortriterpenoids with new skeletons, xylomexicanins I and J (1 and 2), were isolated during the investigation of chemical constituents from seeds of the Chinese mangrove, Xylocarpus granatum. Xylomexicanin I (1) is an unprecedented limonoid with bridged B- and C-rings. A biosynthesis pathway for 1 from xylomexicanin F is proposed.

A chemometric-assisted LC-MS/MS method for the simultaneous determination of 17 limonoids from different parts of Xylocarpus granatum fruit.

The marine mangrove Xylocarpus granatum is used as a folk medicine and is rich in bioactive limonoids. The quantitative determination of the chemical composition and distribution of limonoids in different parts of X. granatum fruit (fruit peel, seed coat, seed kernels, seed, and fruit) is significant for authentication and quality control purposes. However, the quantitative determination of limonoids in X. granatum has not yet been reported. In this study, a chemometric-assisted liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the simultaneous determination of 17 limonoids to reveal the chemical composition and distribution in different parts of X. granatum fruit. Ultrasonic-assisted extraction, optimized by response surface methodology (RSM), was more accurate than the general one-variable-at-a-time method. The overall distribution of 17 limonoids in different parts of X. granatum fruit had the following order: seed kernels > seed > fruit, and 13 limonoids showed a rank order of seed kernels > seed > fruit > fruit peel > seed coat. Furthermore, principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) were used to analyze the LC-MS/MS data and provide a chemometric model for easy visualization and interpretation to classify the different parts of X. granatum fruit. In addition, the study indicated that the chemometric-assisted strategy, consisting of RSM, PCA, and OPLS-DA for the development, optimization, and data analysis of multicomponent quantitation by LC-MS/MS, is effective and feasible. This study provided the chemical composition and distribution evidence for the authentication and quality control of X. granatum fruit.

Study on the metabolites of isoalantolactone in vivo and in vitro by ultra performance liquid chromatography combined with Triple TOF mass spectrometry.

Isoalantolactone (IAL) is an active sesquiterpene naturally present in many vegetables, condiments and medicinal plants. In this study, an efficient strategy was developed for the identification of metabolites following the in vivo metabolism and in vitro biotransformation of IAL with rat intestinal bacteria utilizing ultra performance liquid chromatography combined with Triple TOF mass spectrometry (UPLC-Triple TOF-MS/MS). As a result, 46 metabolites including 34 novel sulfur-containing products were identified. The results demonstrated that IAL could undergo general metabolic reactions, including oxidation, hydration, hydrogenation, demethylation, cysteine conjugation and N-acetylcysteine conjugation, but the most noticeable characteristic of IAL metabolism was the H2S addition to the double bond between C-11 and C-13 and subsequent reactions to produce a series of novel sulfur-containing dimers. This is the first study of IAL metabolism in vivo, whose results provide novel and useful data for a better understanding of the safety and efficacy of IAL.

Identification of in vitro and in vivo metabolites of alantolactone by UPLC-TOF-MS/MS.

Alantolactone (AL), an active sesquiterpene originating from Inula helenium, is a potential anticancer and anti-inflammatory agent. However so far, studies on AL metabolism have not been reported. In the present study, we have investigated for the first time the in vivo and in vitro metabolites of AL using ultra performance liquid chromatography combined with time of flight mass spectrometry (UPLC-TOF-MS/MS). A unique on-line information-dependent acquisition (IDA) method multiple mass defect filter (MMDF) combined with dynamic background subtraction (DBS) was applied to trace all of the probable metabolites of AL. Five MMDF templates were set according to the core structure of AL and the general metabolite biotransformation patterns, and other five sulfur-containing dimer filter templates were first established on the basis of structural elucidation of AL metabolites obtained from rat intestinal bacteria biotransformation. As a result, 44 metabolites were characterized: 41 metabolites from rat urine, bile and feces after oral administration of AL, and 13 metabolites from AL biotransformation by rat intestinal bacteria. Particularly, 26 metabolites were identified as novel sulfur-containing products. The results indicated that addition of double bond at Δ((11,13)) and oxidization were the main metabolic reactions of AL. A new metabolism pathway to produce addition products of H2S to AL and further generate a series of sulfur-containing dimers of AL was revealed. This study significantly enriched our knowledge about AL metabolism, which will lead to a better understanding of the safety and efficacy of AL. At the same time, the established methodology can be widely applied for the structural determination of the metabolites of other sesquiterpene containing α-methylene-γ-lactone moiety.