Constituents from Dendrobium aphyllum: Bibenzyls, furfurals, phenanthrenes, and phenylpropanoids and their antioxidant and anti-inflammatory potentials.

Chemical investigation on the aqueous extract of Dendrobium aphyllum led to the isolation of thirty-one constituents with structures identified by analysis of the extensive spectroscopic data (1D/2D NMR, MS, UV, and ECD), including previously undescribed two bibenzyls, one furfural, and one phenolic acid, namely trigonopol D (1), trigonopol C (2), dendrofunan A (10), and 6-(4-hydroxy-3-methoxyphenyl)-3,6-dioxohexyl acetate (30), respectively, as well as twenty-seven known ones. Among them, there were one new natural product (11), seven compounds (6-7, 9, 12, 20, 28, 31) described from the genus Dendrobium for the first time, and fifteen compounds (8, 13-17, 19, 21-27, 29) isolated from D. aphyllum for the first time. Further, the antioxidant and anti-inflammatory potentials of fifteen compounds (4-5, 8, 11-12, 14-19, 22, 24, 26, and 29) with significant scavenging capacities against DPPH and hydroxyl radicals, and virtual docking activities inhibiting COX-2 and 5-LOX, respectively. Our study may draw the attention of medicinal plant taxonomists and supply potential quality markers for discrimination of D. aphyllum from other species in Dendrobium genus.

A small-molecule degron with a phenylpropionic acid scaffold.

Targeted protein degradation (TPD), employing proteolysis-targeting chimeras (PROTACs) composed of ligands for both a target protein and ubiquitin ligase (E3) to redirect the ubiquitin-proteasome system (UPS) to the target protein, has emerged as a promising strategy in drug discovery. However, despite the vast number of E3 ligases, the repertoire of E3 ligands utilized in PROTACs remains limited. Here, we report the discovery of a small-molecule degron with a phenylpropionic acid skeleton, derived from a known ligand of S-phase kinase-interacting protein 2 (Skp2), an E3 ligase. We used this degron to design PROTACs inducing proteasomal degradation of HaloTag-fused proteins, and identified key structural relationships. Surprisingly, our mechanistic studies excluded the involvement of Skp2, suggesting that this degron recruits other protein(s) within the UPS.

New Phenylpropanoids and Disulphides Dimers from Ferula Kuhistanica.

Five undescribed compounds, including three phenylpropanoid derivatives, 4'-methoxycinnamyl isobutyrate (1), 4'-methoxycinnamyl-2"-methyl butyrate (2) and (2Z)-3',4'-dimethoxycinnamyl isovalerate (3) and two disulphides dimers, kuhistanicasulphide A (7) and kuhistanicasulphide B (8) together with five known ones, including three phenylpropanoids (4-6) and two disulphides (9-10), were isolated from the roots of Ferula kuhistanica Korovin. Their structures were elucidated on the basis of spectroscopic analysis, including IR, UV, HRESIMS, NMR and quantum 13C NMR DP4+ probability. Anti-inflammatory and cytotoxic (Hela, A549 and HT-29 cell lines) activities of the obtained compounds was tested, which compounds 4 and 5 demonstrated good anti-inflammatory with IC50 values of 25.41±2.30 µM and 31.70±3.82 µM, respectively.

Exploring the role of γ-Oryzanol on stabilization mechanism of Pickering emulsion gels loaded by α-Lactalbumin or ß-Lactoglobulin via multiscale approaches.

The research explored the role of γ-oryzanol (γs) on stabilization behavior of Pickering emulsion gels (PEGs) loaded by α-lactalbumin (α-LA) or ß-lactoglobulin (ß-LG), being analyzed by experimental and computer methods (molecular dynamic simulation, MD). Primarily, the average particle size of ß-LG-γS was expressed 100.07% decrease over that of α-LA-γS. In addition, γs decreased the dynamic interfacial tension of two proteins with the order of ß-LG < α-LA. Meanwhile, quartz crystal microbalance with dissipation proved that ß-LG-γS exhibited higher adsorption mass and denser rigid interface layer than α-LA-γS. Moreover, the hydrophobic group of γS had electrostatic repulsion with polar water molecules in the aqueous phase, which spread to the oil phase. ß-LG-γS had lower RMSD/Rg value and narrower fluctuation compared with α-LA-γS. This work strength the exploration of interfacial stabilization mechanism of whey protein-based PEGs, which enriched its theoretical research for industrial-scale production as the replacement of trans fat and cholesterol.

Bonding of Lignin and Coniferyl Alcohol by a Redox Shuttle of Low-Molecular-Weight Lignols in Enzymatic Oxidative Dehydrogenative Polymerization.

Lignin is an aromatic polymer that constitutes plant cell walls. The polymerization of lignin proceeds by radical coupling, and this process requires radicalization of the phenolic end of lignin by enzymes. However, due to the steric hindrance between enzymes, lignin, and polysaccharides, the direct oxidation of the phenolic end of lignin by the enzyme would be difficult, and the details of the growth of lignin are still unknown. In this study, enzymatic dehydrogenative polymerization experiments were conducted using coniferyl alcohol (CA) and the deuterium-labeled lignin model compound (D-LM) under a noncontact condition in which horseradish peroxidase cannot directly oxidize D-LM due to separation by a dialysis membrane. Analysis of deuterium-labeled degraded compounds obtained by a combination of methylation and thioacidolysis revealed the formation of the bond between the phenolic end of D-LM and CA, suggesting that membrane-permeable, low-molecular-weight lignols functioned as a redox shuttle mediator.

An Insight into the Thermal Degradation Pathway of γ-Oryzanol and the Effect on the Oxidative Stability of Oil.

Thermal stability and antioxidant ability of γ-oryzanol in oil have been widely studied. However, further research is needed to explore its thermal degradation products and degradation pathways. The thermal degradation products of γ-oryzanol in stripped soybean oil were identified and quantified by employing high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) during heating at 180 °C. The results revealed that γ-oryzanol undergoes ester bond cleavage to form trans-ferulic acid and free sterols, and trans-ferulic acid generated intermediate compound 4-vinylguaiacol, which ultimately generated vanillin. Analysis of kinetic and thermodynamic parameters revealed the thermal stability ranking of the four components of γ-oryzanol as follows: CampFA > CAFA > 24MCAFA > SitoFA. Furthermore, γ-oryzanol exhibited superior antioxidant activity at lower temperatures. The results of this study provide a theoretical basis for a better understanding of the thermal stability and antioxidant properties of γ-oryzanol in oil under thermal oxidation conditions.

Active Anchoring Stimuli-Responsive Nano-Craft to Relieve Pulmonary Vasoconstriction by Targeting Smooth Muscle Cell for Hypoxic Pulmonary Hypertension Treatment.

Recently, nanotechnology-based drug delivery platforms in treating pulmonary arterial hypertension (PAH) have gradually emerged. However, large mechanical stress and shear stress in blood vessels greatly affect the retention of nanopreparative materials at lesion sites, severely limiting nanotechnology-based drug delivery. Herein, a stimuli-responsive nanocraft is rationally designed by actively anchoring E-selectin overexpressed on pulmonary arterial endothelial cells (PAECs), under hypoxic conditions, allowing effective accumulation and retention of the drug at the lesion site. Briefly, a nitrobenzene group is incorporated into the framework of a nanocarrier, and then it is simultaneously linked with chitosan. Additionally, the surface of the nanocarrier with sialic acid (SA) and encapsulated the clinically used drug ambrisentan (Am), which enables the anchoring of E-selectin and subsequent drug delivery is modifed. This system facilitates intercellular transport to pulmonary artery smooth muscle cells (PASMCs) when targeting PAECs and specifically responds to a reductive hypoxic microenvironment with elevated nitroreductase in PASMCs. Moreover, compared with free Am, nanoencapsulation and SA-PEG2000-NH2 prolong the blood circulation time, achieving better therapeutic outcomes in preventing vascular remodeling and reversing systolic dysfunction. The originality and contribution of this work reveal the promising value of this pulmonary arterial anchoring stimuli-responsive nanocraft as a novel therapeutic strategy for satisfactory PAH treatment.

Effects of artepillin C on model membranes displaying liquid immiscibility

It has been hypothesized that the therapeutic effects of artepillin C, a natural compound derived from Brazilian green propolis, are likely related to its partition in the lipid bilayer component of biological membranes. To test this hypothesis, we investigated the effects of the major compound of green propolis, artepillin C, on model membranes (small and giant unilamelar vesicles) composed of ternary lipid mixtures containing cholesterol, which display liquid-ordered (lo) and liquid-disordered (ld) phase coexistence. Specifically, we explored potential changes in relevant membrane parameters upon addition of artepillin C presenting both neutral and deprotonated states by means of small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and confocal and multiphoton excitation fluorescence microscopy. Thermotropic analysis obtained from DSC experiments indicated a loss in the lipid cooperativity of lo phase at equilibrium conditions, while at similar conditions spontaneous formation of unilamellar vesicles from SAXS experiments showed that deprotonated artepillin C preferentially located at the surface of the membrane. Time-resolved experiments using fluorescence microscopy showed that at doses above 100 µM, artepillin C in its neutral state interacted with both liquid-ordered and liquid-disordered phases, inducing curvature stress and promoting dehydration at the membrane interface.

Biosynthesis of (R)-2-hydroxy-3-phenylpropionic acid using whole recombinant Escherichia coli cells in an aqueous/n-octane biphasic system / 浙江大学学报（英文版）（B辑：生物医学和生物技术）

(R)-2-hydroxy-3-phenylpropionic acid (PLA) is an ideal antimicrobial compound with broad-spectrum activity against a wide range of Gram-positive bacteria, some Gram-negative bacteria, and fungi. We studied the bioconversion of phenylpyruvate (PPA) to PLA using whole recombinant Escherichia coli cells in a series of buffer/organic solvent systems. Octane was found to be the best organic solvent. The optimum volume ratio of the water phase to the n-octane phase, conversion temperature, substrate concentration, and cell concentration were 6:4, 40 °C, 12.5 g/L, and 30 g/L wet cells, respectively. Under the optimized conditions, the average PLA productivity in the aqueous/ n-octane system was 30.69% higher than that in the aqueous system, and 32.31 g/L PLA was obtained with the use of a stirred reactor (2-L scale). Taken together, our findings indicated that PLA biosynthesis was more efficient in an aqueous/n-octane biphasic system than in a monophasic aqueous system. The proposed biphasic system is an effective strategy for enhancing PLA yield and the biosynthesis of its analogues.

Comparative esterification of phenylpropanoids versus hydrophenylpropanoids acids catalyzed by lipase in organic solvent media

The esterification of phenylpropanoid and hydrophenylpropanoid acids, catalyzed by candida antarctica lipase B (CAL-B), with several alcohols has demonstrated that the substitution pattern on the aromatic ring has a very significant influence on the reactivity of the carboxyl group due, mainly, to electronic effects, when compared to the unsaturated acids with the hydrogenated acids. It is also clear that in the saturated acids there still remain some unclear effects related to the aromatic substituents.

Gama-oryzanol: un importante componente del aceite de salvado de arroz / Gama-oryzanol: an important component in rice bran oil

El gamma-Oryzanol, una mezcla de ésteres del ácido ferúlico de esterol y alcohol triterpénico, está presente en el aceite de salvado de arroz en niveles que varían entre 1-2 g/100g, donde actúa como antioxidante natural. Recientes investigaciones han demostrado que el gamma-Oryzanol causa una disminución en el nivel de colesterol en las arterias, reduciendo el riesgo de enfermedades cardiovasculares, además, también ha sido usado en Japón como antioxidante natural en alimentos, bebidas y cosméticos. Esta revisión aborda los aspectos referentes al gamma-Oryzanol, como sus propiedades físico-químicas, su presencia en el aceite de salvado de arroz, su actividad antioxidante e hipocolesterolémica, asé como los métodos de extracción, identificación y cuantificación.