Seco-cyclic phorbol derivatives and their anti-HIV-1 activities.

Phorbol esters are recognized for their dual role as anti-HIV-1 agents and as activators of protein kinase C (PKC). The efficacy of phorbol esters in binding with PKC is attributed to the presence of oxygen groups at positions C20, C3/C4, and C9 of phorbol. Concurrently, the lipids located at positions C12/C13 are essential for both the anti-HIV-1 activity and the formation of the PKC-ligand complex. The influence of the cyclopropane ring at positions C13 and C14 in phorbol derivatives on their anti-HIV-1 activity requires further exploration. This research entailed the hydrolysis of phorbol, producing seco-cyclic phorbol derivatives. The anti-HIV-1 efficacy of these derivatives was assessed, and the affinity constant (Kd) for PKC-δ protein of selected seco-cyclic phorbol derivatives was determined through isothermal titration calorimetry. The findings suggest that the chemical modification of cyclopropanols could affect both the anti-HIV-1 activity and the PKC binding affinity. Remarkably, compound S11, with an EC50 of 0.27 µmol·L-1 and a CC50 of 153.92 µmol·L-1, demonstrated a potent inhibitory effect on the intermediate products of HIV-1 reverse transcription (ssDNA and 2LTR), likely acting at the viral entry stage, yet showed no affinity for the PKC-δ protein. These results position compound S11 as a potential candidate for further preclinical investigation and for studies aimed at elucidating the pharmacological mechanism underlying its anti-HIV-1 activity.

Effects of pectin methyl-esterification on intestinal microbiota and its immunomodulatory properties in naive mice.

Pectins are dietary fibers that are attributed with several beneficial immunomodulatory effects. Depending on the degree of esterification (DE), pectins can be classified as high methoxyl pectin (HMP) or low methoxyl pectin (LMP). The aim of this study was to investigate the effects of pectin methyl-esterification on intestinal microbiota and its immunomodulatory properties in naive mice. Supplementation of the diet with LMP or HMP induced changes in the composition of the intestinal microbiota in mice toward Bacteroides, which was mainly promoted by HMP. Metabolome analysis of stool samples from pectin-fed mice showed a different effect of the two types of pectin on the levels of short-chain fatty acids and bile acids, which was consistent with highly efficient in vivo fermentation of LMP. Analysis of serum antibody levels showed a significant increase in IgG and IgA levels by both pectins, while FACS analysis revealed a decrease of infiltrating inflammatory cells in the intestinal lamina propria by HMP. Our study revealed that the structural properties of the investigated pectins determine fermentability, effects on microbial composition, metabolite production, and modulation of immune responses. Consumption of HMP preferentially altered the gut microbiota and suppressed pro-inflammatory immune responses, suggesting a beneficial role in inflammatory diseases.

Comparison on emulsifying and emulgelling properties of low methoxyl pectin with varied degree of methoxylation from different de-esterification methods.

Low methoxyl pectin (LMP) with different degree of methoxylation (DM, 40-50 %, 20-30 % and 5-10 %) were prepared from commercially available citrus pectin using high hydrostatic pressure assisted enzymatic (HHP-pectin) and traditional alkaline (A-pectin) de-esterification method. The results showed that both de-esterification methods and DM exhibited LMPs with varied physicochemical, structural, and functional properties. As the DM decreased, LMP showed a decrease in molecular weight (Mw), while an increase in negative charges and rhamnogalacturonan I (RG-I) ratio, accompanied with better emulsion stability, emulsion gel strength and water-holding properties. Relative to A-pectin, HHP-pectin had higher Mw and lower RG-I side chain ratio, contributing to its better thermal stability, apparent viscosity, and emulgelling properties. HHP-pectin with lower DM (5-10 %) showed superior thickening, emulsifying and emulgelling properties, while that with higher DM (40-45 %) had superior thermal stability, which provided alternative for de-esterification and targeted structural modification of pectin.

A new integrated strategy for high purity pinolenic acid production from Pinus koraiensis Sieb. et Zucc seed oil and evaluation of its hypolipidemic activity in vivo.

Pinolenic acid is a polyunsaturated fatty acid present only in Pinus koraiensis Sieb. et Zucc seed oil. In order to solve the structural instability problem of polyunsaturated fatty acids, pinolenic acid of P. koraiensis seed oil was effectively isolated and purified by the integrated strategy of ethyl esterification followed by urea inclusion for the first time. Under the optimal conditions after the Box-Benhnken Design experimental, ethyl pinolenate with high purity 94.95% could be obtained, and the average content of PNAEE can still reach 86.18%. Then ethyl pinolenate was characterized by Gas chromatography-mass spectrometry, Fourier transform infrared, and Nuclear magnetic resonance spectra, results showed that ethyl pinolenate was successfully prepared. In addition, the hypolipidemic activity of ethyl pinolenate had been tested in vivo and showed that ethyl pinolenate had obvious hypolipidemic activity. The new strategy for high purity ethyl pinolenate production from P. koraiensis seed oil possesses great potential in food healthy field in the future.

In vitro batch fermentation of (un)saturated homogalacturonan oligosaccharides.

Pectin, predominantly present within plant cell walls, is a dietary fiber that potentially induces distinct health effects depending on its molecular structure. Such structure-dependent health effects of pectin-derived galacturonic acid oligosaccharides (GalA-OS) are yet largely unknown. This study describes the influence of methyl-esterification and ∆4,5-unsaturation of GalA-OS through defined sets of GalA-OS made from pectin using defined pectinases, on the fermentability by individual fecal inocula. The metabolite production, OS utilization, quantity and size, methyl-esterification and saturation of remaining GalA-OS were monitored during the fermentation of GalA-OS. Fermentation of all GalA-OS predominantly induced the production of acetate, butyrate and propionate. Metabolization of unsaturated GalA-OS (uGalA-OS) significantly increased butyrate formation compared to saturated GalA-OS (satGalA-OS), while satGalA-OS significantly increased propionate formation. Absence of methyl-esters within GalA-OS improved substrate metabolization during the first 18 h of fermentation (99 %) compared to their esterified analogues (51 %). Furthermore, HPAEC and HILIC-LC-MS revealed accumulation of specific methyl-esterified GalA-OS, confirming that methyl-esterification delays fermentation. Fermentation of structurally distinct GalA-OS results in donor specific microbiota composition with uGalA-OS specifically stimulating the butyrate-producer Clostridium Butyricum. This study concludes that GalA-OS fermentation induces highly structure-dependent changes in the gut microbiota, further expanding their potential use as prebiotics.

Methyl oleate for plant protection products formulations: Enzymatic synthesis, reaction kinetics and application testing.

This study presents a solvent-free enzymatic approach for the synthesis of fatty acid methyl esters (FAMEs), such as methyl oleate, for their application as adjuvant in plant protection products (PPP) formulations. The direct esterification between free fatty acid and methanol was optimized to achieve 98% acid conversion. The kinetics of this conversion was accurately described by a simple second order mechanism and non-linear regression was applied to calculate the rate constants of the forward and backward reactions based on full progress curves data. The rate constant of the forward reaction (synthesis) was one order of magnitude higher than the backward reaction (hydrolysis) and favored formation of the target methyl ester product, rendering the removal of water unnecessary. Enzymatically synthesized methyl oleate was benchmarked against the chemically synthesized compound, showing matching results in terms of stability, spreadability and emulsifying capacity in plant care formulations. The enzymatic synthesis of FAMEs under solvent free conditions allows to achieve a safer and more sustainable character for carrier solvents in PPP formulations.

The Resistance of Maize to Ustilago maydis Infection Is Correlated with the Degree of Methyl Esterification of Pectin in the Cell Wall.

Common smut caused by Ustilago maydis is one of the dominant fungal diseases in plants. The resistance mechanism to U. maydis infection involving alterations in the cell wall is poorly studied. In this study, the resistant single segment substitution line (SSSL) R445 and its susceptible recurrent parent line Ye478 of maize were infected with U. maydis, and the changes in cell wall components and structure were studied at 0, 2, 4, 8, and 12 days postinfection. In R445 and Ye478, the contents of cellulose, hemicellulose, pectin, and lignin increased by varying degrees, and pectin methylesterase (PME) activity increased. The changes in hemicellulose and pectin in the cell wall after U. maydis infection were analyzed via immunolabeling using monoclonal antibodies against hemicellulsic xylans and high/low-methylated pectin. U. maydis infection altered methyl esterification of pectin, and the degree of methyl esterification was correlated with the resistance of maize to U. maydis. Furthermore, the relationship between methyl esterification of pectin and host resistance was validated using 15 maize inbred lines with different resistance levels. The results revealed that cell wall components, particularly pectin, were important factors affecting the colonization and propagation of U. maydis in maize, and methyl esterification of pectin played a role in the resistance of maize to U. maydis infection.

Pectin from sunflower by-products obtained by ultrasound: Chemical characterization and in vivo evaluation of properties in inflammatory bowel disease.

Inflammatory bowel disease (IBD) is a public health challenge and the use of pectin for symptom amelioration is a promising option. In this work, sunflower pectin has been extracted without (CHP) and with assistance of ultrasound (USP) using sodium citrate as a food-grade extracting agent. At optimal conditions (64 °C, 23 min) the highest yield was obtained with ultrasound application (15.5 vs. 8.1 %). Both pectins were structurally characterized by 1H NMR, HPSEC-ELSD, FT-IR and GC-FID. Unlike CHP, USP showed a lower molecular weight, higher galacturonic acid, lower degree of methyl-esterification and, overall, higher viscosity. These characteristics could affect the anti-inflammatory activity of pectins, evaluated using DSS-induced IBD model mice. So, USP promoted the defence (ICAM-1) and repair of the gastrointestinal mucosa (TFF3, ZO-1) more effectively than CHP. These results demonstrate the potential amelioration of acute colitis in IBD mice through USP supplementation. Taking into account the biomarkers analysed, these results demonstrate, for the first time, the positive impact of sunflower pectin extracted by ultrasound under very soft conditions on inflammatory bowel disease that might open up new possibilities in the treatment of this serious pathology.

Controlled release of Lactiplantibacillus plantarum by colon-targeted adhesive pectin microspheres: Effects of pectin methyl esterification degrees.

The aim of this study is to report the preparation of pectin microspheres by varying degrees of methyl esterification (DM) cross-linked with divalent cationic calcium to encapsulate Lactiplantibacillus plantarum STB1 and L. plantarum LJ1, respectively. Scanning electron microscopy revealed the compact and smooth surface of pectin of DM 28 %, and the stochastic distribution of L. plantarum throughout the gel reticulation. And the pectin of DM 28 % considerably increased probiotics tolerance after continuous exposure to stimulated gastrointestinal tract conditions, with viable counts exceeding 109 CFU/mL. This data indicated that low methoxy-esterification pectin was more efficient to improve the targeted delivery of probiotics in GIT. Additionally, the controlled release of microspheres was dependent on various pH levels. At pH 7.4, the release rates of L. plantarum STB1 and L. plantarum LJ1 reached up to 97.63 % and 95.33 %, respectively. Finally, the Caco-2 cell adhesion model was used to evaluate the cell adhesion rate after encapsulation, which exhibited better adhesion at DM of 60 %.

Metabolic, toxicological, chemical, and commercial perspectives on esterification of dietary polyphenols: a review.

Molecular modifications have been practiced for more than a century and nowadays they are widely applied in food, pharmaceutical, or other industries to manipulate the physicochemical, bioactivity, metabolic/catabolic, and pharmacokinetic properties. Among various structural modifications, the esterification/O-acylation has been well-established in altering lipophilicity and bioactivity of parent bioactive compounds, especially natural polyphenolics, while maintaining their high biocompatibility. Meanwhile, various classic chemical and enzymatic protocols and other recently emerged cell factory technology are being employed as viable esterification strategies. In this contribution, the main motivations of phenolic esterification, including the tendency to replace synthetic alkyl phenolics with safer alternatives in the food industry to improve the bioavailability of phenolics as dietary supplements/pharmaceuticals, are discussed. In addition, the toxicity, metabolism, and commercial application of synthetic and natural phenolics are briefly introduced. Under these contexts, the mechanisms and reaction features of several most prevalent chemical and enzymatic esterification pathways are demonstrated. In addition, insights into the studies of esterification modification of natural phenolic compounds and specific pros/cons of various reaction systems with regard to their practical application are provided.

Future Antimicrobials: Natural and Functionalized Phenolics.

With incidence of antimicrobial resistance rising globally, there is a continuous need for development of new antimicrobial molecules. Phenolic compounds having a versatile scaffold that allows for a broad range of chemical additions; they also exhibit potent antimicrobial activities which can be enhanced significantly through functionalization. Synthetic routes such as esterification, phosphorylation, hydroxylation or enzymatic conjugation may increase the antimicrobial activity of compounds and reduce minimal concentrations needed. With potent action mechanisms interfering with bacterial cell wall synthesis, DNA replication or enzyme production, phenolics can target multiple sites in bacteria, leading to a much higher sensitivity of cells towards these natural compounds. The current review summarizes some of the most important knowledge on functionalization of natural phenolic compounds and the effects on their antimicrobial activity.

Solid state malic acid esterification on fungal α-amylase treated corn starch: Design of a green dual treatment.

For the first time, the current work applied fungal α-amylase treated corn starch in granular form to produce solid state malate-esterified starch (MES). The pores and channels created on the granules after the enzymatic modification could provide more possibilities for malic acid to esterify the starch, resulting in the increase of substitution degree (0.084) and reaction efficiency (86.6%) compared to NS. Based on the obtained results, the dual treatment significantly increased solubility, amylose content, and syneresis, but reduced transparency, viscosity, digestibility rate, and swelling power compared to those of NS. The occurrence of esterification onto starch chains was confirmed by FT-IR at 1720 cm-1. Other techniques including SEM, XRD, and DSC were employed to examine changes in the structure of starch granules after applying each treatment. Also, the greenness of the combined modification (score: 77) was proved by using a new methodology named Eco-Scale.

Kinetic studies on the extraction of oil from a new feedstock (Chukrasia tabularis L. seed) for biodiesel production using a heterogeneous catalyst.

This study has identified a new feedstock Chukrasia tabularis L. (C. tabularis) seed for the production of biodiesel. Oil was extracted from the seeds with and without autoclave-assisted ultrasonic homogenization (AUH) pretreatment using different solvents. The solvent n-hexane with AUH pretreatment yielded a maximum oil yield of 32 wt%. The kinetics and thermodynamics of the extraction process were studied in a batch. The data showed that extraction followed first-order kinetics with a rate constant of 1.4 × 10-4 min-1, activation energy of 63.604 kJ mol-1 and pre-exponential factors of 66.66 × 104 s-1. The physiochemical properties of the oil were determined from which it was identified that C. tabularis oil has high free fatty acid (FFA) content, requiring a single-step esterification cum transesterification reaction to produce biodiesel economically. The modified aryl diazonium salt reduction process was used to synthesize a heterogeneous acid catalyst (HAC) from activated carbon precursor and was used to catalyze biodiesel reaction. Furthermore, HAC was characterized by different analytical techniques and it was found that it had an acid site density of 1.02 mmol g-1 and a specific surface area of 602 m2 g-1. The parameters affecting the biodiesel process were studied to obtain a maximum biodiesel conversion of 98.5% at 6 wt% catalyst loading, 15:1 methanol to oil molar ratio, 120 min reaction time, 70 ºC reaction temperature, and 500 rpm stirring rate. Reusability studies were performed which showed that HAC can be recycled up to five cycles with a conversion above 90% in the fifth cycle. Moreover, the fuel properties of biodiesel were determined using standard methods and were compared with ASTM D6751 and EN14241 standards.

Physicochemical and functional properties of pectin extracted from the edible portions of jackfruit at different stages of maturity.

BACKGROUND: The physicochemical and functional properties of pectin (JFP) extracted from edible portions (including pericarp and seed) of raw jackfruit (an underutilized tropical fruit) at four different maturity stages (referred to as stages I, II, III, and IV) were characterized in terms of extraction yields, chemical composition, molecular weight, and antioxidant properties to evaluate its potential use in foods. RESULT: The JFP yield increased from 9.7% to 21.5% with fruit maturity, accompanied by an increase in the galacturonic acid content (50.1%, 57.1%, 63.6%, and 65.2%) for stages I-IV respectively. The molecular weight increased from 147 kDa in stage I to 169 kDa in stage III, but decreased to 114 kDa in stage IV, probably due to cell-wall degradation during maturation. The JFP was of the high methoxyl type and the degree of esterification increased from 65% to 87% with fruit maturity. The functional properties of JFP were similar to or better than those reported for commercial apple pectin, thus highlighting its potential as a food additive. Although the phenolics and flavonoids content of JFP decreased with fruit maturity, their antioxidant capacity increased, which may be correlated with the increased content of galacturonic acid upon fruit development. Gels prepared from JFP showed viscoelastic behavior. Depending on the maturity stage in which they were obtained, different gelation behavior was seen. CONCLUSION: The study confirmed the potential of pectin extracted from edible parts of jackfruit as a promising source of high-quality gelling pectin with antioxidant properties, for food applications. © 2022 Society of Chemical Industry.

Characterize the physicochemical properties and microstructure of pectin from high-pressure and thermal processed cloudy hawthorn (Crataegus pinnatifida) juice based on acid heating extraction.

Physicochemical properties and morphological features of pectin in high-pressure-processing (JHPP) and thermal-processing (JTP) treated cloudy hawthorn juice were investigated based on acid heating extraction. Pectin from hawthorn juice was identified as low methoxy pectin (41.77%), which was significantly reduced to 34.56%-39.51% from JHPP, while pectin esterification degree (DE) from JTP increased to 45.58%, which can also be confirmed by Fourier transform infrared spectroscopy. In comparison to control, pectin linearity of JHPP and JTP significantly decreased with more highly branched-chains. However, no significate difference was observed in thermostability, crystallinity and main functional groups. Interestingly, a large number of aggregations was observed in JHPP pectin, and the intermodular distance of JTP pectin was enhanced, which was consistent with the results of viscosity, molecular weight and DE. These findings provided insights into utilization of hawthorn pectin and application of high-pressure processing (HPP) for improving quality property of fruit products by pectin modification.

Novel iron sand-derived α-Fe2O3/CaO2 bifunctional catalyst for waste cooking oil-based biodiesel production.

The main aim of this work was to develop a heterogeneous Fe2O3/CaO2 bifunctional catalyst prepared from iron sand and 3 different CaO2 sources (CaCO3, Ca (OH)2, and limestone) using wet impregnation and calcination methods for biodiesel production. The effects of different CaO2 sources and Fe/Ca ratio in the catalyst were investigated to provide insight into the catalyst character and biodiesel yield. X-ray diffraction, X-ray fluorescence, and scanning electron microscopy analyses were used to characterize the catalyst. CaCO3 was concluded as the best CaO2 source, while the best Fe/Ca configuration was found to be 1:4, giving the highest biodiesel yield (97.0401%) with no diglycerides. Greater addition of Fe loading would result in an amorphous structure, and all catalysts were relatively crystalline. Fe was concluded to favor the esterification reaction and biodiesel formation, while CaO2 was seen to favor the transesterification reaction and fatty acid methyl ester (FAME) formation. The catalyst mechanism was also established in this study, where esterification of free fatty acid (FFA) and glycerol took place on the acid site to produce diglyceride and transesterification of triglyceride by methanol occurred on the basic site.

Development of Galloyl Antioxidant for Dispersed and Bulk Oils through Incorporation of Branched Phytol Chain.

In this study, a novel galloyl phytol antioxidant was developed by incorporating the branched phytol chain with gallic acid through mild Steglich esterification. The evaluation of the radical scavenging activity, lipid oxidation in a liposomal model, and glycerol trioleate revealed its superior antioxidant activities in both dispersed and bulk oils. Then, the antioxidant capacity enhancement of galloyl phytol was further explored using thermal gravimetry/differential thermal analysis (TG/DTA), transmission electron microscopy (TEM), and molecular modeling. The EC50 values of GP, GPa, and GE were 0.256, 0.262, and 0.263 mM, respectively, which exhibited comparable DPPH scavenging activities. These investigations unveiled that the branched aliphatic chain enforced the coiled molecular conformation and the unsaturated double bond in the phytol portion further fixed the coiled conformation, which contributed to a diminished aggregation tendency and enhanced antioxidant activities in dispersed and bulk oils. The remarkable antioxidant performance of galloyl phytol suggested intriguing and non-toxic natural antioxidant applications in the food industry, such as effectively inhibiting the oxidation of oil and improvement of the quality and shelf life of the oil, which would contribute to the use of tea resources and extending the tea industry chain.

Glycerol-Based Retrievable Heterogeneous Catalysts for Single-Pot Esterification of Palm Fatty Acid Distillate to Biodiesel.

The by-product of the previous transesterification, glycerol was utilised as an acid catalyst precursor for biodiesel production. The crude glycerol was treated through the sulfonation method with sulfuric acid and chlorosulfonic acid in a reflux batch reactor giving solid glycerol-SO3H and glycerol-ClSO3H, respectively. The synthesised acidic glycerol catalysts were characterised by various analytical techniques such as thermalgravimetric analyser (TGA), infrared spectroscopy, surface properties adsorption-desorption by nitrogen gas, ammonia-temperature programmed desorption (NH3-TPD), X-ray diffraction spectroscopy (XRD), elemental composition analysis by energy dispersive spectrometer (EDX) and surface micrographic morphologies by field emission electron microscope (FESEM). Both glycerol-SO3H and glycerol-ClSO3H samples exhibited mesoporous structures with a low surface area of 8.85 mm2/g and 4.71 mm2/g, respectively, supported by the microscopic image of blockage pores. However, the acidity strength for both catalysts was recorded at 3.43 mmol/g and 3.96 mmol/g, which is sufficient for catalysing PFAD biodiesel at the highest yield. The catalytic esterification was optimised at 96.7% and 98.2% with 3 wt.% of catalyst loading, 18:1 of methanol-PFAD molar ratio, 120 °C, and 4 h of reaction. Catalyst reusability was sustained up to 3 reaction cycles due to catalyst deactivation, and the insight investigation of spent catalysts was also performed.

Quercetin Fatty Acid Monoesters (C2:0-C18:0): Enzymatic Preparation and Antioxidant Activity.

Quercetin monoesters were prepared via a one-step enzymatic transesterification. The main acylation products were eight quercetin ester derivatives, respectively, consisting of varying acyl groups ranging from 2 to 18 carbon atoms (acetate, butyrate, caproate, caprylate, caprate, laurate, myristate, and stearate). The purified quercetin esters were structurally characterized by LC-ESI-ToF and NMR HSQC. Meanwhile, several classical chemical (DPPH, ABTS, FRAP, and Fe2+ chelation assays), food (ß-carotene bleaching assay), and biological (LDL and DNA oxidation assays) models were constructed to evaluate and systematically compare their antioxidant efficacy. O-Acylation increased the lipophilicity of quercetin derivatives, and lipophilicity increased with the increasing chain length of the acyl group. The dual effect of the acyl chain length on biasing quercetin monoesters' antioxidant efficacies has been summarized and verified. Overall, the results imply that the acylated quercetin have great potential as functional/health-beneficial ingredients for use in lipid-based matrices of cosmetics, supplements, and nutraceuticals.

Mini-Review on the Enzymatic Lipophilization of Phenolics Present in Plant Extracts with the Special Emphasis on Anthocyanins.

Different plant extracts have the potential to be important sources of phenolic compounds. Their antibacterial, antifungal and antioxidant properties are of interest to researchers due to various possibilities for use in the pharmacy, cosmetic and food industries. Unfortunately, the direct application of phenolics in food is limited because of their hydrophilic nature and low solubility. The review is devoted to the recent advances in the methods of lipophilization of phenolic extracts along with the use of enzymes. The concept of extract modification instead of single compound modification is based on the expected synergistic effect of many phenolic compounds. The main focus is on the phenolic compounds found in fruits, flowers and leaves of different common and underutilized as well as medicinal, folk-medicinal or endemic plants. The compiled papers point to the great interest in the modification of anthocyanins, highly active but often unstable phenolics. Some examples of other flavonoids are also outlined. The possible applications of the lipophilized plant extracts are presented for improving the stability of edible oils, decreasing the content of acrylamide, exhibiting higher color stability in thermal processing and increasing the nutritional value.