Identification of Key Hypolipidemic Components and Exploration of the Potential Mechanism of Total Flavonoids from Rosa sterilis Based on Network Pharmacology, Molecular Docking, and Zebrafish Experiment.

Hyperlipidemia is a prevalent chronic metabolic disease that severely affects human health. Currently, commonly used clinical therapeutic drugs are prone to drug dependence and toxic side effects. Dietary intervention for treating chronic metabolic diseases has received widespread attention. Rosa sterilis is a characteristic fruit tree in China whose fruits are rich in flavonoids, which have been shown to have a therapeutic effect on hyperlipidemia; however, their exact molecular mechanism of action remains unclear. Therefore, this study aimed to investigate the therapeutic effects of R. sterilis total flavonoid extract (RS) on hyperlipidemia and its possible mechanisms. A hyperlipidemic zebrafish model was established using egg yolk powder and then treated with RS to observe changes in the integral optical density in the tail vessels. Network pharmacology and molecular docking were used to investigate the potential mechanism of action of RS for the treatment of hyperlipidemia. The results showed that RS exhibited favorable hypolipidemic effects on zebrafish in the concentration range of 3.0-30.0 µg/mL in a dose-dependent manner. Topological and molecular docking analyses identified HSP90AA1, PPARA, and MMP9 as key targets for hypolipidemic effects, which were exerted mainly through lipolytic regulation of adipocytes and lipids; pathway analysis revealed enrichment in atherosclerosis, chemical carcinogenic-receptor activation pathways in cancers, and proteoglycans in prostate cancer and other cancers. Mover, chinensinaphthol possessed higher content and better target binding ability, which suggested that chinensinaphthol might be an important component of RS with hypolipidemic active function. These findings provide a direction for further research on RS interventions for the treatment of hyperlipidemia.

Hypolipidemic and Antithrombotic Effect of 6'-O-Caffeoylarbutin from Vaccinium dunalianum Based on Zebrafish Model, Network Pharmacology, and Molecular Docking.

Vaccinium dunalianum leaf buds make one of the most commonly used herbal teas of the Yi people in China, which is used to treat articular rheumatism, relax tendons, and stimulates blood circulation in the body. In addition, 6'-O-caffeoylarbutin (CA) is a standardized extract of V. dunalianum, which has been found in dried leaf buds, reaching levels of up to 31.76%. Because of the uncommon phenomenon, it is suggested that CA may have a potential therapeutic role in hyperlipidemia and thrombosis. This study was designed to study the efficacy of CA on treating hyperlipidemia and thrombosis and the possible mechanisms behind these effects. Hyperlipidemia and thrombosis zebrafish models were treated with CA to observe variations of the integrated optical density within the vessels and the intensity of erythrocyte staining within the hearts. The possible mechanisms were explored using network pharmacology and molecular docking. The results demonstrate that CA exhibits an excellent hypolipidemic effect on zebrafish at concentrations ranging from 3.0 to 30.0 µg/mL and shows thrombosis inhibitory activity in zebrafish at a concentration of 30.0 µg/mL, with an inhibition rate of 44%. Moreover, network pharmacological research shows that MMP9, RELA, MMP2, PRKCA, HSP90AA1, and APP are major targets of CA for therapy of hyperlipidemia and thrombosis, and may relate to pathways in cancer, chemical carcinogenesis-receptor activation, estrogen signaling pathway, and the AGE-RAGE signaling pathway in diabetic complications.

Bio-Based Ca2+-Selective Supramolecular Metallohydrogels with Ultra-mechanical Responsiveness, Selective Dye Adsorption, and Recycling.

Water pollution is one of the major problems that need to be solved in modern society, and there is a need to develop an effective adsorbent to purify the polluted water. In this article, three supramolecular metallohydrogels containing a three-dimensional network structure have been prepared from rosin derivatives. The supramolecular metallohydrogels have good thermal stability and maintain mechanical strength at high temperatures. Interestingly, the sodium N-(dehydroabiety1)maleamate/Ca2+ supramolecular metallohydrogels exhibit rare multi-stimulus responsiveness (mechanical vibration, temperature, pH, EDTA, etc.), especially to mechanical vibration with over 10 cycles, indicating ultra-mechanical response properties. More importantly, the unique three-dimensional network structure of the metallohydrogels can effectively adsorb cationic dyes in the wastewater. The adsorption amount and adsorption rate of this supramolecular metallohydrogels for rhodamine 6G after 48 h were at least 160.6 mg/g and 97%, respectively. The adsorption kinetic process of this metallohydrogel follows a quasi-secondary kinetic model, where the adsorption process is mainly electrostatic and weak π-π interactions. And the metallohydrogels can also be recovered by 0.5 mol/L hydrochloric acid solution desorption after adsorption of the dye. This is the first supramolecular metallohydrogel system prepared from the natural product rosin and applied to dye adsorption. This broadens the application of rosin in the field of supramolecular gel and dye adsorption and recycling.

Pickering Emulsions and Viscoelastic Solutions Constructed by a Rosin-Based CO2-Responsive Surfactant.

Designing stimulus-switch viscoelastic solutions and Pickering emulsions with reversible CO2-responsive behavior remains a challenge. A rosin-based CO2-responsive surfactant, N-cetyl-maleimidepimaric acid N,N-dimethylenediamide (C16MPAN), was synthesized and used to prepare CO2-triggered viscoelastic solutions and Pickering emulsions. This surfactant exhibited excellent CO2-responsive performance in water and formed a viscoelastic solution. This viscoelastic system was investigated by dynamic light scattering (DLS), rheology, and cryogenic transmission electron microscopy (Cory-TEM). The shear viscosity of the system increased by 3-4 orders of magnitude after bubbling with CO2 and a large number of elongated, flexible, tubular wormlike micelles were observed. Further, Pickering emulsions were prepared by C16MPAN+ synergistically with cellulose nanocrystals (CNCs), whose stability and switchability were investigated via adsorption isotherm, droplet size, contact angle, and macroscopic photographs. C16MPAN+ was adsorbed with CNCs to form mechanical barriers at the oil-water interface, making the emulsion stable for at least three months, and desorption from CNCs enabled emulsion breaking. The cycle could be switched reversibly multiple times and the particle size distribution of emulsion was basically the same. This work enriches the application of biomass resources in intelligent responsive materials.

Alkynylation of Isatin Derivatives Catalyzed by a Silver-Chiral Quaternary Ammonium Salt Derived from Quinine.

Asymmetric addition of terminal alkynes catalyzed by a transition metal to isatins obviously is an efficient and economic method for the synthesis of 3-alkynyl-3-hydroxy-2-oxindoles. The new dimeric chiral quaternary ammoniums derived from a natural chiral alkaloid, quinine, can be used as cationic inducers of the enantioselectivity for the Ag(I)-catalyzed alkynylation of isatin derivatives under mild conditions. The desired chiral 3-alkynyl-3-hydroxy-2-oxindoles can be obtained in good to high yields with high to excellent enantioselectivites (≤99% ee). A variety of aryl-substituted terminal alkynes and substituted isatins are tolerated in this reaction.

Facile Construction of Bio-Based Supramolecular Hydrogels from Dehydroabietic Acid with a Tricyclic Hydrophenanthrene Skeleton and Stabilized Gel Emulsions.

Supramolecular hydrogels have attracted great attention due to their special properties. In this research, bio-based supramolecular hydrogels were conveniently constructed by heating and ultrasounding two components of dehydroabietic acid with a rigid tricyclic hydrophenanthrene skeleton and morpholine. The microstructures and properties of hydrogels were investigated by DSC, rheology, SAXS, CD spectroscopy, and cryo-TEM, respectively. The critical gel concentration (CGC) of the hydrogel was 0.3 mol·L-1 and the gel temperature was 115 °C. In addition, the hydrogel showed good stability and mechanical properties according to rheology results. Cryo-TEM images reveal that the microstructure of hydrogel is fibrous meshes; its corresponding mechanism has been studied using FT-IR spectra. Additionally, oil-in-water gel emulsions were prepared by the hydrogel at a concentration above its CGC, and the oil mass fraction of the oil-in-water gel emulsions could be freely adjusted between 5% and 70%. This work provides a convenient way to prepare bio-based supramolecular hydrogels and provides a new method for the application of rosin.

Phase Behavior and Aggregation in a Catanionic System Dominated by an Anionic Surfactant Containing a Large Rigid Group.

The phase behavior and aggregates of a catanionic system have been investigated. The anionic surfactants in the mixed systems were sodium N-alkylmaleimidepimaric carboxylate (Cn -MPA-Na, n=12, 14, 16), which were prepared from rosin and contain a large rigid skeleton and a flexible alkane chain, and the cationic surfactant was cetyltrimethylammonium bromide (CTAB). The phase behavior of the C14 -MPA-Na/CTAB system transformed sequentially from a viscoelastic solution to an aqueous surfactant two-phase system (ASTP), an aqueous surfactant three-phase system (AS3P), and an anisotropic homogeneous phase as the concentration of C14 -MPA-Na was continuously increased from 10 to 35 mm. The C16 -MPA-Na/CTAB system showed similar phase behavior, whereas the C12 -MPA-Na/CTAB system did not form the AS3P system. The corresponding microstructures in the different phases were investigated by using rheology and cryogenic transmission electron microscopy (Cryo-TEM). The aggregates in the viscoelastic solutions are thread-like, annular, and worm-like micelles. The microstructures in the upper phase of the ASTP are worm-like micelles, and in the lower phase are spherical and rod-like micelles. The aggregates in the upper and lower phases of the AS3P are worm-like micelles and spherical and rod-like micelles, respectively. The aggregates in the middle phase of the AS3P and the anisotropic homogeneous phase are sponge-like micelles. The clear Cryo-TEM images of the sponge-like micelles are presented.

Annular and threadlike wormlike micelles formed by a bio-based surfactant containing an extremely large hydrophobic group.

A novel bio-based anionic surfactant containing a large rigid group and a flexible alkyl chain, namely, sodium N-dodecyl-maleimidepimaric carboxylate (C12-MPA-Na), was synthesized from rosin. The molecular structure of C12-MPA-Na was identified using 1H NMR, FT-IR spectroscopy and MS. Despite containing 36 carbon atoms, C12-MPA-Na showed good water solubility at room temperature. Large spherical aggregates with diameters of 100-200 nm were formed by C12-MPA-Na when its concentration was above 0.1 mM, which was slightly higher than the critical micelle concentration (0.078 mM). Annular wormlike micelles were discovered with increasing C12-MPA-Na concentration, and began to change into extremely long threadlike wormlike micelles when the C12-MPA-Na concentration reached approximately 58 mM. The viscoelastic properties of the wormlike micelle solutions were investigated using steady state and oscillatory shear sweep rheological measurements. The zero-shear viscosity (η0) strongly depended on the concentration of C12-MPA-Na, and the scaling exponent was 34.1. Cryo-TEM confirmed the formation of large spherical aggregates and wormlike micelles. 1H-1H 2D nuclear Overhauser effect spectroscopy (NOESY) was used to detect the molecular interactions of C12-MPA-Na. The results indicated that the alkyl chain of C12-MPA-Na was partially overlapped with its non-planar rigid structure in aqueous solution, and the possible aggregation process for C12-MPA-Na was proposed.

High Add Valued Application of Turpentine in Crop Production through Structural Modification and QSAR Analysis.

Turpentine is a volatile component of resin, which is an abundant forest resource in Southern China. As one of the most important components, the integrated application of ß-pinene has been studied. The broad-spectrum evaluation of ß-pinene and its analogues has, therefore, been necessary. In an attempt to expand the scope of agro-activity trials, the preparation and the evaluation of the herbicidal activity of a series of ß-pinene analogues against three agricultural herbs were carried out. In accordance with the overall herbicidal activity, it is noteworthy that compounds 6k, 6l, and 6m demonstrated extreme activity with IC50 values of 0.065, 0.065, and 0.052 mol active ingredients/hectare against E. crus-galli. The preliminary structure-activity relationship (SAR) was analyzed and the compounds with the appropriate volatility and substituent type that had beneficial herbicidal activity were analyzed. Simultaneously, the quantitative structure-activity relationship (QSAR) model was built and the most important structural features were indicated, which was, to a certain extent, in line with the SAR study. The study aimed to study the application of the forest resource turpentine in agriculture as a potential and alternative approach for comprehensive utilization.

One-pot synthesis and antimicrobial evaluation of novel 3-cyanopyridine derivatives of (-)-ß-pinene.

A series of novel 3-cyanopyridine derivatives of (-)-ß-pinene were designed and synthesized by one-pot four-component domino reactions. The targeted compounds were evaluated for their antimicrobial activity against four bacteria (Klebsiella pneumoniae, Enterobacter aerogenes, Staphylococcus aureus, Staphylococcus epidermidis) and a fungus (Candida albicans). The results showed that most of the minimal inhibitory concentrations (MICs) of these 3-cyanopyridine derivatives against the tested strains was in the range of 15.6-125 mg/L. Among these 3-cyanopyridine derivatives, the MICs of compound 5h against S. epidermidis and C. albicans were 15.6 mg/L, which revealed that compound 5h featured double fluoro substituents at meta- and para-position was the most active compound. In addition, the preliminary structure-activity relationship analysis indicated that the change of substituents on the pyridine ring and benzene ring of 3-cyanopyridine derivatives was an important factor for inducing antimicrobial activity. This research would promote the development of heterocyclic derivatives of ß-pinene with antimicrobial activity.

Crystal structure of (E)-1-(4-chloro-phen-yl)ethanone O-de-hydro-abietyloxime.

The title compound, C28H34ClNO2 {systematic name: (E)-1-(4-chloro-phen-yl)ethanone O-[(1R,4aS,10aR)-7-isopropyl-1,4a-di-methyl-1,2,3,4,4a,9,10,10a-octa-hydro-phenanthrene-1-carbonyl]oxime}, was synthesized from de-hydro-abietic acid. In the de-hydro-abietyl moiety, the central and terminal cyclo-hexane rings display chair and half-chair conformations, respectively, and a trans-ring junction. The C=N bond is in an E conformation and the C-O-N=C torsion angle is 148.1 (5)°. No directional inter-actions except van der Waals contacts occur in the crystal structure.

Crystal structure of (E)-1-(4-meth-oxy-phen-yl)ethanone O-de-hydro-abietyloxime.

In the title compound, C29H37NO3 {systematic name: (E)-1-(4-meth-oxy-phen-yl)ethanone O-[(1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octa-hydro-phenanthrene-1-carbon-yl]oxime}, a new derivative of de-hydro-abietic acid, the two cyclo-hexane rings exhibit a trans-ring junction and are in chair and half-chair conformations. The C=N double bond exhibits an E conformation.

Effect of rosin based quaternary ammonium salt on mechanical, hydrophily, antibacterial of cornstarch/polydopamine film for food packaging.

Food packaging made of biobased materials is environmentally friendly, among which starch film is a type of biobased packaging with great development value. Some existing studies have attempted to add polydopamine (PDA) to enhance cross-linking, but there are still problems such as weakness and hydrophilicity, which greatly limit its application. Therefore, this study synthesized rosin based quaternary ammonium salt-modified cornstarch (ST-B), which was used to replace part of unmodified cornstarch (ST). In the prepared ST/PDA0.5/ST-B5 film, the introduction of a rigid rosin structure increased the stress and water contact angle of the ST/PDA0.5 film by 62 % and 26 %, respectively, while reducing its wettability and WVP; thus, further enhancing its antioxidant activity. Due to the antibacterial ability of rosin quaternary ammonium cations, the packaging film containing 7 wt% ST-B can kill >94.6 % of S. aureus and 99.9 % of E. coli, and can also extend the shelf life of strawberries. In addition, it is proven that the packaging film has good biocompatibility and high safety within cytotoxicity tests and 30-day gavage tests in mice. Therefore, the prepared ST/PDA/ST-B film has more potential for application in food preservation.

Gut microbiome and metabolic profiles of mouse model for MeCP2 duplication syndrome.

The extra copy of the methyl-CpG-binding protein 2 (MeCp2) gene causes MeCP2 duplication syndrome (MDS), a neurodevelopmental disorder characterized by intellectual disability and autistic phenotypes. However, the disturbed microbiome and metabolic profiling underlying the autistic-like behavioral deficits of MDS are rarely investigated. Here we aimed to understand the contributions of microbiome disruption and associated metabolic alterations, especially the disturbed neurotransmitters in MDS employing a transgenic mouse model with MeCP2 overexpression. We analyzed metabolic profiles of plasma, urine, and cecum content and microbiome profiles by both 16 s RNA and shotgun metagenomics sequence technology. We found the decreased levels of Firmicutes and increased levels of Bacteroides in the single MeCP2 gene mutation autism-like mouse model, demonstrating the importance of the host genome in a selection of microbiome, leading to the heterogeneity characteristics of microbiome in MDS. Furthermore, the changed levels of several neurotransmitters (such as dopamine, taurine, and glutamate) implied the excitatory-inhibitory imbalance caused by the single gene mutation. Concurrently, a range of microbial metabolisms of aromatic amino acids (such as tryptophan and phenylalanine) were identified in different biological matrices obtained from MeCP2 transgenic mice. Our investigation revealed the importance of genetic variation in accounting for the differences in microbiomes and confirmed the bidirectional regulatory axis of microbiota-gut-brain in studying the role of microbiome on MDS, which could be useful in deeply understanding the microbiome-based treatment in this autistic-like disease.

Detection of a temporal salient object benefits from visual stimulus-specific adaptation in avian midbrain inhibitory nucleus.

Food and predators are the most noteworthy objects for the basic survival of wild animals, and both are often deviant in both spatial and temporal domains and quickly attract an animal's attention. Although stimulus-specific adaptation (SSA) is considered a potential neural basis of salient sound detection in the temporal domain, related research on visual SSA is limited and its relationship with temporal saliency is uncertain. The avian nucleus isthmi pars magnocellularis (Imc), which is central to midbrain selective attention network, is an ideal site to investigate the neural correlate of visual SSA and detection of a salient object in the time domain. Here, the constant order paradigm was applied to explore the visual SSA in the Imc of pigeons. The results showed that the firing rates of Imc neurons gradually decrease with repetitions of motion in the same direction, but recover when a motion in a deviant direction is presented, implying visual SSA to the direction of a moving object. Furthermore, enhanced response for an object moving in other directions that were not presented ever in the paradigm is also observed. To verify the neural mechanism underlying these phenomena, we introduced a neural computation model involving a recoverable synaptic change with a "center-surround" pattern to reproduce the visual SSA and temporal saliency for the moving object. These results suggest that the Imc produces visual SSA to motion direction, allowing temporal salient object detection, which may facilitate the detection of the sudden appearance of a predator.

Synthesis, characterization and antifungal properties of maleopimaric anhydride modified chitosan.

Fruit spoilage can cause huge economic losses, in which fungal infection is one of the main influencing factors, how to effectively control mould and spoilage of fruits and prolong their shelf-life has become a primary issue in the development of fruit and vegetable industry. In this study, rosin derivative maleopimaric anhydride (MPA) was combined with biodegradable and antifungal chitosan (CS) to enhance its antifungal and preservative properties. The modified compounds were characterized by FTIR, 1H NMR spectra and XRD, and the in vitro antifungal properties of the modified compounds were evaluated by the radial growth assay and the minimal inhibitory concentration assay. The preservation effect on small mandarin oranges and longan was studied. The analysis revealed that the modification product (CSMA) of MPA access to C6-OH of CS had a better antifungal effect. In addition, CSMA was more environmentally friendly and healthier than the commercially available chemical preservative (Imazalil), and had the same antifungal preservative effect in preserving small mandarin orange, and was able to extend the shelf life to >24 d. In the preservation of longan, CSMA was more effective against tissue water loss and was able to maintain the moisture in the longan pulp and extend the shelf life. Therefore, CSMA has good application potentials in longan keeping-fresh.

Phenanthroimidazole-based fluorescence probe for discriminative detecting of hydrazine and bisulfite and its applications in environmental samples.

Hydrazine (N2H4) and bisulfite (HSO3-) detection methods are urgently needed due to its harmful to the human health and environment safety. Herein, we reported a dual-response fluorescence probe EPC, which is capable of sequential detection of N2H4 and HSO3- by two different fluorescence signals. The probe EPC itself showed yellow florescence. In presence of N2H4, probe EPC exhibited an obviously fluorescence change (from yellow to green). However, a new addition product came into being after probe EPC mixed with HSO3-, followed with weak yellow emission. More important, probe EPC exhibited excellent fluorescence response properties for N2H4 and HSO3-, such as high sensitivity (0.182 µM for N2H4, 0.093 µM for HSO3-), rapid response (55 s for N2H4, 45 s for HSO3-), excellent selectivity and anti-interference performance. The sensing mechanisms for N2H4 and HSO3- were proved by 1H NMR and MS spectra. Practical applications were studied. EPC based test paper can be utilized for quantitative detecting N2H4 in actual water samples. And, probe EPC has been successfully applied to recognize N2H4 contaminant in soil samples. Moreover, EPC has great potential to be used to detect HSO3- in real food samples.

Construction of Ni/In2O3 Integrated Nanocatalysts Based on MIL-68(In) Precursors for Efficient CO2 Hydrogenation to Methanol.

The efficient and economic conversion of CO2 and renewable H2 into methanol has received intensive attention due to growing concern for anthropogenic CO2 emissions, particularly from fossil fuel combustion. Herein, we have developed a novel method for preparing Ni/In2O3 nanocatalysts by using porous MIL-68(In) and nickel(II) acetylacetonate (Ni(acac)2) as the dual precursors of In2O3 and Ni components, respectively. Combined with in-depth characterization analysis, it was revealed that the utilization of MIL-68(In) as precursors favored the good distribution of Ni nanoparticles (∼6.2 nm) on the porous In2O3 support and inhibited the metal sintering at high temperatures. The varied catalyst fabrication parameters were explored, indicating that the designed Ni/In2O3 catalyst (Ni content of 5 wt %) exhibited better catalytic performance than the compared catalyst prepared using In(OH)3 as a precursor of In2O3. The obtained Ni/In2O3 catalyst also showed excellent durability in long-term tests (120 h). However, a high Ni loading (31 wt %) would result in the formation of the Ni-In alloy phase during the CO2 hydrogenation which favored CO formation with selectivity as high as 69%. This phenomenon is more obvious if Ni and In2O3 had a strong interaction, depending on the catalyst fabrication methods. In addition, with the aid of in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory (DFT) calculations, the Ni/In2O3 catalyst predominantly follows the formate pathway in the CO2 hydrogenation to methanol, with HCOO* and *H3CO as the major intermediates, while the small size of Ni particles is beneficial to the formation of formate species based on DFT calculation. This study suggests that the Ni/In2O3 nanocatalyst fabricated using metal-organic frameworks as precursors can effectively promote CO2 thermal hydrogenation to methanol.

A new dehydroabietic acid-based arylamine fluorescent probe: Synthesis, structure analysis and in vitro biodiagnose function.

A new fluorescent probe (methyl 13-(α-naphthalene)aminodeisopropyldehydroabietate) has been synthesized, and its structure was optimized by theoretical DFT calculation and determinated by single-crystal X-ray diffraction analysis. The optimized data are in agreement with the experimental values. The fluorescence properties, photostability, cell toxicity and in vitro fluorescence imaging of the compound have been investigated. The results indicated that it can be effectively taken up by HeLa, 7721, 7901 and A549 cells and strong blue fluorescence signals were detected in these cells.

N,N-Di-methyl-dehydro-abietyl-ammonium chloride ethanol monosolvate.

The title compound {systematic name: 1-[(1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octa-hydro-phenan-thren-1-yl]-N,N-di-methyl-methanaminium chloride ethanol monosolvate}, C22H36N(+)·Cl(-)·C2H6O, was synthesized from dehydroabietylamine by N-methyl-ation with formaldehyde/formic acid and transformation into the hydro-chloride. The de-hydro-abietyl moiety exhibits the usual conformation with the two cyclo-hexane rings in chair and half-chair conformations and a trans-ring junction. The crystal structure is built up from columns of the de-hydro-abietyl moieties stacked along the a axis. These columns are held together by the chloride ions via N-H⋯Cl and C-H⋯Cl inter-actions, which establish a two-dimensional network parallel to (010). The ethanol solvent mol-ecules are located between the columns and anchored via O-H⋯Cl hydrogen bonds.