Magnetic molecularly imprinted polymers using ternary deep eutectic solvent as novel functional monomer for hydroxytyrosol separation.

In this work, magnetic molecularly imprinted polymers (MIPs) for specific recognition of Hydroxytyrosol (HT) were designed by vinyl-modified magnetic particles (Fe3O4@SiO2@VTEOs) as carrier, ternary deep eutectic solvent (DES) as functional monomer, while ethylene glycol dimethacrylate (EGDMA) as crosslinker. The optimum amount of DES was obtained by adsorption experiments (molar ratio, caffeic acid: choline chloride: formic acid = 1:6:3) which were 140 µL in total. Under the optimized amount of DES, the maximum adsorption capacity of the MIPs particles was 42.43 mg g-1, which was superior to non-imprinted polymer (4.64 mg g-1) and the imprinting factor (IF) is 9.10. Syringin and Oleuropicrin were used as two reference molecules to test the selectivity of the DES-MIPs particles. The adsorption capacity of HT was 40.11 mg g-1. Three repeated experiments show that the polymer has high stability and repeatability (RSD = 5.50).

Characterization and Anti-Ultraviolet Radiation Activity of Proanthocyanidin-Rich Extracts from Cinnamomum camphora by Ultrasonic-Assisted Method.

The ultrasonic-assisted extraction (UAE) method was employed to separate Cinnamomum camphora proanthocyanidin-rich extracts (PCEs). This extraction process was optimized by the Box-Behnken design, and the optimal conditions, on a laboratory scale, were as follows: an ethanol concentration of 75%, a liquid-to-solid ratio of 24 mL/g, an ultrasonic time of 39 min, and an ultrasonic power of 540 W. Under the obtained conditions, the PCE yield extracted by UAE was higher than that from heat reflux extraction and soaking extraction. An ultra-performance liquid chromatography-tandem mass spectrometry analysis was employed to characterize the phloroglucinolysis products of the C. camphora PCEs, by which epigallocatechin, catechin, epicatechin, and (-)-epigallocatechin-3-O-gallate were identified as the terminal units; epigallocatechin, epicatechin, and (-)-epigallocatechin-3-O-gallate were recognized as extension units. The C. camphora PCEs possessed higher anti-ultraviolet activity in vitro compared with the commercially available sunscreen additive of benzophenone with respect to their ethanol solutions (sun protection factor of 27.01 ± 0.68 versus 1.96 ± 0.07 at a concentration of 0.09 mg/mL) and sunscreens (sun protection factor of 17.36 ± 0.62 versus 14.55 ± 0.47 at a concentration of 20%). These results demonstrate that C. camphora PCEs possess an excellent ultraviolet-protection ability and are promising green sunscreen additives that can replace commercial additives.

Application of an aqueous enzymatic-ultrasound cavitation method for the separation of Sapium sebiferum seed kernel oil.

An aqueous enzymatic-ultrasound cavitation extraction (AEUCE) method was developed to separate Sapium sebiferum seed kernel oil. In this process, neutral proteinase was screened as the propriate enzyme. The Plackett-Burman and Box-Behnken designs were employed to optimize AEUCE. We determined the optimal extraction conditions, producing an oil yield of 84.22 ± 3.17 %. Gas chromatography-mass spectrometry (GC-MS) analysis indicated that the S. sebiferum seed kernel oil was abundant in unsaturated fatty acids (>92 %) and that the compositions of the fatty acid profiles extracted by AEUCE were similar to those obtained from Soxhlet extraction, but their contents were slightly different. The physicochemical properties analysis showed that the oil extracted by AEUCE was comparable to that obtained from Soxhlet extraction. The results showed that the developed AEUCE is an efficient technique that can separate high-quality plant oils. The S. sebiferum seed kernel oil obtained from this extraction method is a promising substitute for vegetable oils used in biodiesel production.

Application of a Combined Homogenate and Ultrasonic Cavitation System for the Efficient Extraction of Flavonoids from Cinnamomum camphora Leaves and Evaluation of Their Antioxidant Activity In Vitro.

A free-of-dust pollution extraction method combined-homogenate and ultrasonic cavitation system, namely, homogenate-combined ultrasonic cavitation synergistic extraction (HUCSE), was proposed for the efficient extraction of flavonoids from Cinnamomum camphora leaves. Response surface methodology of Box-Behnken design was employed to optimize the HUCSE process, and the optimum operation conditions attained with an extraction yield of 7.95 ± 0.27 mg/g were ethanol concentration 76%, homogenate/ultrasonic time 25 min, solvent-to-solid ratio 22 mL/g, and ultrasonic power 240 W. A second-order kinetic mathematical methodology was performed to depict the behaviors of HUCSE and heat reflux extraction method. The results suggested that the developed HUCSE is an efficient and green method for the extraction of C. camphora flavonoids or other plant natural products, where the obvious higher parameters of extraction capacity at saturation, second-order extraction rate constant, and original extraction rate were obtained when compared to the heat reflux method. The antioxidant activity assays in vitro showed that the C. camphora flavonoids possessed strong antioxidant activity and are promising to be applied as a natural alternative antioxidant.

Sulfonated carbon derived from the residue obtained after recovery of essential oil from the leaves of Cinnamomum longepaniculatum using Brønsted acid ionic liquid, and its use in the preparation of ellagic acid and gallic acid.

A Brønsted acid ionic liquid, 3-methyl-1-(4-sulfonylbutyl) imidazolium hydrogensulfate ([HO3S(CH2)4mim]HSO4), was used for the first time for the preparation of a sulfonated carbon catalyst. The catalyst was prepared from the residue obtained after recovery of the essential oil from the leaves of Cinnamomum longepaniculatum. The sulfonated carbon catalyst with an amorphous structure attained high acidic efficiency at a sulfonation temperature of 200 °C for 2 h of sulfonation time, and was characterised. SEM morphologies revealed that the carbon catalyst consisted of uniform carbon microspores. FTIR analysis, elemental analysis, and X-ray photoelectron spectroscopy revealed that the sulfonic acid group was successfully introduced on the surface of the sulfonated carbon catalyst. The result of TG analysis showed that the obtained sulfonated carbon catalyst has high thermal stability. Good acid and catalytic activity of the obtained sulfonated carbon catalyst were observed for the preparation of ellagic acid and gallic acid, which is comparable to those of diluted sulfuric acid and a sulfonated carbon catalyst that had been prepared with concentrated sulfuric acid. The excellent reusability of the sulfonated carbon catalyst was also confirmed by repeated experimental trials. In summary, the sulfonated catalyst derived from the residue obtained after recovery of essential oil from the leaves of C. longepaniculatum is an economic, eco-benign and promising substitute for traditional mineral acid catalysts for acidic catalysis in industrial applications.

Antisolvent precipitation for the preparation of high polymeric procyanidin nanoparticles under ultrasonication and evaluation of their antioxidant activity in vitro.

An improved method of ultrasonic antisolvent precipitation was used to prepare micronized high polymeric procyanidins (HPC). Response surface methodology (Plackett-Burman and Box-Behnken design) was employed to predict the optimal preparation conditions and satisfactory mean particle size. Among seven parameters, three parameters (i.e., ultrasonic irradiation power, ultrasonic-stirring time, and stirring speed) were identified as the most significant variables using Plackett-Burman design; thus, these three parameters were further optimized using Box-Behnken design. The optimal preparation conditions for micronized HPC were obtained as follows: dropping speed of 4 mL/min, HPC solution concentration of 0.3 mg/mL, ratio of antisolvent and solvent of 5 mL/mL, precipitation temperature of 10 °C, ultrasonic-stirring time of 14 min, ultrasonic irradiation power of 620 W, and stirring speed of 760 r/min. A minimum mean particle size of 96 ±â€¯2 nm was achieved under the aforementioned conditions. The obtained micronized HPC was analysed by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric and X-ray powder diffraction patterns. Micronized HPC enjoyed the higher quantity dissolved and exhibited stronger antioxidant activity in compared to the unprocessed HPC. These results demonstrated that the improved method has great potential for the production of micronized particles.

Efficient approach for the extraction of proanthocyanidins from Cinnamomum longepaniculatum leaves using ultrasonic irradiation and an evaluation of their inhibition activity on digestive enzymes and antioxidant activity in vitro.

Proanthocyanidins were separated for the first time from Cinnamomum longepaniculatum leaves. An experiment-based extraction strategy was used to research the efficiency of an ultrasound-assisted method for proanthocyanidins extraction. The Plackett-Burman design results revealed that the ultrasonication time, ultrasonic power and liquid/solid ratio were the most significant parameters among the six variables in the extraction process. Upon further optimization of the Box-Behnken design, the optimal conditions were obtained as follows: extraction temperature, 100°C; ethanol concentration, 70%; pH 5; ultrasonication power, 660 W; ultrasonication time, 44 min; liquid/solid ratio, 20 mL/g. Under the obtained conditions, the extraction yield of the proanthocyanidins using the ultrasonic-assisted method was 7.88 ± 0.21 mg/g, which is higher than that obtained using traditional methods. The phloroglucinolysis products of the proanthocyanidins, including the terminal units and derivatives from the extension units, were tentatively identified using a liquid chromatography with tandem mass spectrometry analysis. Cinnamomum longepaniculatum proanthocyanidins have promising antioxidant and anti-nutritional properties. In summary, an ultrasound-assisted method in combination with a response surface experimental design is an efficient methodology for the sufficient isolation of proanthocyanidins from Cinnamomum longepaniculatum leaves, and this method could be used for the separation of other bioactive compounds.

A process to preserve valuable compounds and acquire essential oils from pomelo flavedo using a microwave irradiation treatment.

A microwave pretreatment method was developed to preserve pectin, naringin, and limonin contents in pomelo flavedo to allow for longer storage times and subsequent extraction of pomelo essential oil. In terms of the essential oil, microwave pretreatment performed better than hydrodistillation with respect to extraction efficiency (1.88±0.06% in 24min versus 1.91±0.08% in 240min), oxygenation fraction (48.59±1.32% versus 29.63±1.02%), energy consumption (0.15kWh versus 1.54kWh), and environmental impact (123.20g CO2 versus 1232g CO2). Microwave-pretreated samples retained higher amounts of pectin, naringin, and limonin compared with non-pretreated samples. No obvious change in the degree of pectin esterification was observed. This study shows that the proposed process is a promising methodology for both preserving valuable compounds in pomelo flavedo during storage and acquiring essential oils.

Brönsted acidic ionic liquid based ultrasound-microwave synergistic extraction of pectin from pomelo peels.

3-Methyl-1-(4-sulfonylbutyl) imidazolium hydrogensulfate, [HO3S(CH2)4mim]HSO4, was applied as an extractant in an ultrasound-microwave synergistic extraction approach to substitute conventional solvent for the extraction of pectin from the albedo part of pomelo peels. The analysis of variance (ANOVA) test and response surface method were employed for the optimization of the extraction conditions. A pectin yield of 328.64±4.19mg/g was achieved using the obtained optimal conditions, which was significantly higher than yields of conventional methods with reference solvents. Pectin samples extracted with [HO3S(CH2)4mim]HSO4 and hydrochloric acid solutions were tested by ANOVA and showed no significant differences in total carbohydrate content and degree of esterification; while galacturonic acid content was significantly different for the pectin from each extraction solvents. The differences revealed from images of atomic force microscopy and scanning electron microscope, Fourier transform infrared spectroscopy, and thermogravimetric analysis suggested the physiochemical properties of pectin could be affected by the extraction solvent. The [HO3S(CH2)4mim]HSO4 proved to be a promising alternative to conventional solvents and the proposed method is efficient for the extraction of pectin from the albedo of pomelo peels.

An approach of ionic liquids/lithium salts based microwave irradiation pretreatment followed by ultrasound-microwave synergistic extraction for two coumarins preparation from Cortex fraxini.

Ionic liquids/lithium salts solvent system was successfully introduced into the separation technique for the preparation of two coumarins (aesculin and aesculetin) from Cortex fraxini. Ionic liquids/lithium salts based microwave irradiation pretreatment followed by ultrasound-microwave synergy extraction (ILSMP-UMSE) procedure was developed and optimized for the sufficient extraction of these two analytes. Several variables which can potentially influence the extraction yields, including pretreatment time and temperature, [C4mim]Br concentration, LiAc content, ultrasound-microwave synergy extraction (UMSE) time, liquid-solid ratio, and UMSE power were optimized by Plackett-Burman design. Among seven variables, UMSE time, liquid-solid ratio, and UMSE power were the statistically significant variables and these three factors were further optimized by Box-Behnken design to predict optimal extraction conditions and find out operability ranges with maximum extraction yields. Under optimum operating conditions, ILSMP-UMSE showed higher extraction yields of two target compounds than those obtained by reference extraction solvents. Method validation studies also evidenced that ILSMP-UMSE is credible for the preparation of two coumarins from Cortex fraxini. This study is indicative of the proposed procedure that has huge application prospects for the preparation of natural products from plant materials.

Development of an ionic liquid-based microwave-assisted method for the extraction and determination of taxifolin in different parts of Larix gmelinii.

An ionic liquid-based microwave-assisted extraction method (ILMAE) was successfully applied for the extraction of taxifolin from Larix gmelinii. Different kinds of 1-alkyl-3-methylimidazolium ionic liquids with different kinds of cations and anions were studied and 1-butyl-3-methylimidazolium bromide was chosen as the optimal solvent for taxifolin extraction. The optimal conditions of ILMAE were determined by single factor experiments and Box-Behnken design as follows: [C4mim]Br concentration of 1.00 M, soaking time of 2 h, liquid-solid ratio of 15:1 mL/g, microwave irradiation power of 406 W, microwave irradiation time of 14 min. No degradation of taxifolin had been observed under the optimum conditions as evidenced from the stability studies performed with standard taxifolin. Compared with traditional solvent and methods, ILMAE provided higher extraction yield, lower energy and time consumption. The distribution of taxifolin in different parts of larch and the influences of age, orientation, and season on the accumulation of taxifolin were analyzed for the sufficient utilization of L. gmelinii.

Preparation and characterization of Tripterygium wilfordii multi-glycoside nanoparticle using supercritical anti-solvent process.

The aim of this study was to prepare nanosized Tripterygium wilfordii multi-glycoside (GTW) powders by the supercritical antisolvent precipitation process (SAS), and to evaluate the anti-inflammatory effects. Ethanol was used as solvent and carbon dioxide was used as an antisolvent. The effects of process parameters such as precipitation pressure (15-35 MPa), precipitation temperature (45-65 °C), drug solution flow rates (3-7 mL/min) and drug concentrations (10-30 mg/mL) were investigated. The nanospheres obtained with mean diameters ranged from 77.5 to 131.8 nm. The processed and unprocessed GTW were characterized by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy and thermal gravimetric analysis. The present study was designed to investigate the beneficial effect of the GTW nanoparticles on adjuvant-induced arthritis in albino rats. The processed and unprocessed GTW were tested against Freund's complete adjuvant-induced arthritis in rats. Blood samples were collected for the estimation of interleukins (IL-1α, IL-1ß) and tumor necrosis factor-α (TNF-α). It was concluded that physicochemical properties and anti-inflammatory activity of GTW nanoparticles could be improved by physical modification, such as particle size reduction using supercritical antisolvent (SAS) process. Further, SAS process was a powerful methodology for improving the physicochemical properties and anti-inflammatory activity of GTW.