Waste Cooking Oil-Modified Epoxy Asphalt Rubber Binders with Improved Compatibility and Extended Allowable Construction Time

The application of crumb rubber from end-of-life tires and waste cooking oil (WCO) in road pavements is of significant importance from an economic and environmental viewpoint. However, the incorporation of crumb rubber greatly shortens the allowable construction time of epoxy asphalt binders due to the high viscosity of the epoxy asphalt rubber (EAR) binder and poor compatibility between crumb rubber and asphalt binder. To lower the viscosity of asphalt rubber, extend the allowable construction time and improve the compatibility of EAR binder, waste cooking oil (WCO) was introduced. The effect of WCO on the viscosity–time behavior, thermal stability, dynamic modulus, glass transitions, crosslink density, damping ability, compatibility, mechanical properties and phase separation of WCO-modified EAR binders was investigated by using the Brookfield viscometer, thermogravimetric analysis, dynamic mechanical analysis, universal testing machine and laser confocal microscopy. The test results demonstrated that the incorporation of WCO declined the viscosity and extended the allowable construction time of the unmodified EAR binder. The inclusion of WCO improved the compatibility between asphalt and crumb rubber and the damping ability and elongation at the break of the unmodified EAR binder. The presence of WCO had a marginal effect on the thermal stability of the unmodified EAR binder. Confocal microscopy observation revealed that asphalt rubber particles aggregated in the epoxy phase of the unmodified EAR binder. With the inclusion of WCO, co-continuous asphalt rubber particles became more spherical.     

Analysis of Components and Properties of Extractives from Alnus cremastogyne Pods from Different Provenances

Chemical components with anti-oxidant, anti-inflammatory, and anti-cancer properties extracted from Alnus bark and leaves have been extensively studied. However, less attention has been paid to extractives from Alnus pods, which are mostly treated as waste. Here, extractives of Alnus cremastogyne pods from 12 provenances in Sichuan Province were studied for high value-added utilization of Alnus waste. The extractives were analyzed by Gas Chromatography-Mass Spectrometer (GC-MS), Ultraviolet-visible spectroscopy (UV-Vis spectra), and 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging activity. A total of 58, 49, and 51 chemical components were found when the organic solvents of ethanol, petroleum ether, and ethyl acetate were used to collect extractives, respectively. These chemical components including Phytol, CIS-5,8,11,14,17-eicosapentaenoic acid, Germacrene D, Lupeol, and β-sitosterol, etc., have wide applications in the fields of pharmacy and cosmetics. Moreover, it was also found that extractives in ethanol and ethyl acetate had impressive UV resistance, especially for UV-C and UV-B blocking. The results showed that the maximum block ratio towards UV-C and UV-B could reach 99%. In addition, the ethanol extract showed good anti-oxidant activity with a maximum free radical scavenging rate of 96.19%. This comprehensive and systematic study on extractives from Alnus cremastogyne pods promotes the development of high-value utilization of Alnus components.     

Lipase-Catalyzed Phospha-Michael Addition Reactions under Mild Conditions

Organophosphorus compounds are the core structure of many active natural products. The synthesis of these compounds is generally achieved by metal catalysis requiring specifically functionalized substrates or harsh conditions. Herein, we disclose the phospha-Michael addition reaction of biphenyphosphine oxide with various substituted β-nitrostyrenes or benzylidene malononitriles. This biocatalytic strategy provides a direct route for the synthesis of C-P bonds with good functional group compatibility and simple and practical operation. Under the optimal conditions (styrene (0.5 mmol), biphenyphosphine oxide (0.5 mmol), Novozym 435 (300 U), and EtOH (1 mL)), lipase leads to the formation of organophosphorus compounds in yields up to 94% at room temperature. Furthermore, we confirm the role of the catalytic triad of lipase in this phospha-Michael addition reaction. This new biocatalytic system will have broad applications in organic synthesis.     

Lanostane Triterpenoids and Ergostane Steroids from Ganoderma luteomarginatum and Their Cytotoxicity

Macrofungus Ganoderma luteomarginatum is one of the main species of Ganoderma fungi distributed in Hainan province of China, the fruiting bodies of which have been widely used in folk as a healthy food to prevent tumors. To explore the potential cytotoxic constituents from G. luteomarginatum, the phytochemical investigation on the ethyl acetate soluble fraction of 95% ethanolic extract from the fruiting bodies of this fungus led to the isolation of twenty-six lanostane triterpenoids (1–26), including three undescribed ones (1–3), together with eight ergostane steroids (27–34). The structures of three new lanostane triterpenoids were elucidated as lanosta-7,9(11)-dien-3β-acetyloxy-24,25-diol (1), lanosta-7,9(11)-dien-3-oxo-24,26-diol-25-methoxy (2), and lanosta-8,20(22)-dien-3,11,23-trioxo-7β,15β-diol-26-oic acid methyl ester (3) by the analysis of 1D, 2D NMR, and HRESIMS spectroscopic data. All isolates were assayed for their cytotoxic activities using three human cancer cell lines (K562, BEL-7402, and SGC-7901) and seven lanostane triterpenoids (1, 2, 7, 13, 18, 22, and 24), and one ergostane steroid (34) showed definite cytotoxicity with IC₅₀ values that ranged from 6.64 to 47.63 μg/mL. Among these cytotoxic lanostane triterpenoids, compounds 2 and 13 showed general cytotoxicity against three human cancer cell lines, while compounds 1 and 18 exhibited significant selective cytotoxicity against K562 cells with IC₅₀ values of 8.59 and 8.82 μg/mL, respectively. Furthermore, the preliminary structure–cytotoxicity relationships was proposed.     

Aerial Oxygen-Driven Selenocyclization of O-Vinylanilides Mediated by Coupled Fe3+/Fe2+ and I2/I− Redox Cycles

In the past decade, selenocyclization has been extensively exploited for the preparation of a wide range of selenylated heterocycles with versatile activities. Previously, selenium electrophile-based and FeCl₃-promoted methods were employed for the synthesis of selenylated benzoxazines. However, these methods are limited by starting material availability and low atomic economy, respectively. Inspired by the recent catalytic selenocyclization approaches based on distinctive pathways, we rationally constructed an efficient and greener double-redox catalytic system for the access to diverse selenylated benzoxazines. The coupling of I₂/I⁻ and Fe³⁺/Fe²⁺ catalytic redox cycles enables aerial O₂ to act as the driving force to promote the selenocyclization. Control and test redox experiments confirmed the roles of each component in the catalytic system, and a PhSeI-based pathway is proposed for the selenocyclization process.     

Maternal Physiological Variations Induced by Chronic Gestational Hypoxia: 1H NMR-Based Metabolomics Study

Metabolomics have been widely used in pregnancy-related diseases. However, physiological variations induced by chronic hypoxia during pregnancy are not well characterized. We aimed to investigate physiological variations induced by chronic hypoxia during pregnancy. A Sprague–Dawley (SD) pregnant rat model of chronic hypoxia was established. Plasma and urine metabolite profiles at different stages of the pregnancy were detected by ¹H NMR (nuclear magnetic resonance). Multivariate statistical analysis was used to analyze changes in plasma and urine metabolic trajectories at different time-points. We identified hypoxia-induced changes in the levels of 30 metabolites in plasma and 29 metabolites in urine during different stages of pregnancy; the prominently affected metabolites included acetic acid, acetone, choline, citric acid, glutamine, isoleucine, lysine, and serine. Most significant hypoxia-induced changes in plasma and urine sample metabolites were observed on the 11th day of gestation. In summary, chronic hypoxia has a significant effect on pregnant rats, and may cause metabolic disorders involving glucose, lipids, amino acids, and tricarboxylic acid cycle. Metabolomics study of the effect of hypoxia during pregnancy may provide insights into the pathogenesis of obstetric disorders.     

Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide

Halogen bonds (XBs) between metal anions and halides have seldom been reported because metal anions are reactive for XB donors. The pyramidal-shaped Mn(CO)₅⁻ anion is a candidate metallic XB acceptor with a ligand-protected metal core that maintains the negative charge and an open site to accept XB donors. Herein, Mn(CO)₅⁻ is prepared by electrospray ionization, and its reaction with CH₃I in gas phase is studied using mass spectrometry and density functional theory (DFT) calculation. The product observed experimentally at m/z = 337 is assigned as [IMn(CO)₄(OCCH₃)]⁻, which is formed by successive nucleophilic substitution and reductive elimination, instead of the halogen-bonded complex (XC) CH₃−I···Mn(CO)₅⁻, because the I···Mn interaction is weak within XC and it could be a transient species. Inspiringly, DFT calculations predict that replacing CH₃I with CF₃I can strengthen the halogen bonding within the XC due to the electro-withdrawing ability of F. More importantly, in so doing, the nucleophilic substitution barrier can be raised significantly, ~30 kcal/mol, thus leaving the system trapping within the XC region. In brief, the combination of a passivating metal core and the introduction of an electro-withdrawing group to the halide can enable strong halogen bonding between metallic anion and iodide.     

Natural Deep Eutectic Solvent-Assisted Extraction,Structural Characterization,and Immunomodulatory Activity of Polysaccharides from Paecilomyces hepiali

Polysaccharides, which can be affected by different preparations, play a crucial role in the biological function of Paecilomyces hepiali (PHPS) as a health food. To explore high-valued polysaccharides and reduce the negative influence of human involvement, a green tailorable deep eutectic solvent (DES) was applied to optimize the extraction of polysaccharides (PHPS-D), followed by the evaluation of the structural properties and immunomodulation by comparison with the hot-water method (PHPS-W). The results indicated that the best system for PHPS-D was a type of carboxylic acid-based DES consisting of choline chloride and succinic acid in the molar ratio of 1:3, with a 30% water content. The optimal condition was as follows: liquid–solid ratio of 50 mL/g, extraction temperature of 85 °C, and extraction time of 1.7 h. The actual PHPS-D yield was 12.78 ± 0.17%, which was obviously higher than that of PHPS-W. The structural characteristics suggested that PHPS-D contained more uronic acid (22.34 ± 1.38%) and glucose (40.3 ± 0.5%), with a higher molecular weight (3.26 × 10⁵ g/mol) and longer radius of gyration (78.2 ± 3.6 nm), as well as extended chain conformation, compared with PHPS-W, and these results were confirmed by AFM and SEM. Immunomodulatory assays suggested that PHPS-D showed better performance than PHPS-W regarding pinocytic activity and the secretion of NO and pro-inflammatory cytokines (IL-6, TNF-α and IL-1β) by activating the corresponding mRNA expression in RAW264.7 cells. This study showed that carboxylic acid-based DES could be a promising tailorable green system for acidic polysaccharide preparation and the valorization of P. hepiali in functional foods.     

A smelting–rolling strategy for ZnIn bulk phase alloy anodes

Reversibility and stability are considered as the key indicators for Zn metal anodes in aqueous Zn-ion batteries, yet they are severely hindered by uncontrolled Zn stripping/plating and side reactions. Herein, we fabricate a bulk phase ZnIn alloy anode containing trace indium by a typical smelting–rolling process. A uniformly dispersed bulk phase of the whole Zn anode is constructed rather than only a protective layer on the surface. The Zn deposition can be regarded as instantaneous nucleation due to the adsorption of the evenly dispersed indium, and formation of the exclusion zone for further nucleation can be prevented at the same time. Owing to the bulk phase structure of ZnIn alloy, the indium not only plays a crucial role in Zn deposition, but also improves the Zn stripping. Consequently, the as-designed ZnIn alloy anode can sustain stable Zn stripping/plating for over 2500 h at 4.4 mA cm⁻² with nearly 6 times smaller voltage hysteresis than that of pure Zn. Moreover, it enables a substantially stable ZnIn//NH₄V₄O₁₀ battery with 96.44% capacity retention after 1000 cycles at 5 A g⁻¹. This method of regulating the Zn nucleation by preparing a Zn-based alloy provides a potential solution to the critical problem of Zn dendrite growth and by-product generation fundamentally.

A ZnIn alloy anode with trace indium is obtained by smelting–rolling method. The Zn deposition could be regarded as instantaneous nucleation that can alleviate the effect of deposition layer for the diffusion zone and suppresses dendrite growth.