Hydrothermal Conversion of Spent Sugar Beets into High-Value Platform Molecules.

The growing importance of bio-based products, combined with the desire to decrease the production of wastes, boosts the necessity to use wastes as raw materials for bio-based products. A waste material with a large potential is spent sugar beets, which are mainly used as animal feeds or fertilizers. After hydrothermal treatment, the produced chars exhibited an H/C ratio of 1.2 and a higher heating value of 22.7 MJ/kg, which were similar to that of subbituminous coal and higher than that of lignite. Moreover, the treatment of 25 g/L of glucose and 22 g/L of fructose by heating up to 160 °C led to a possible application of spent sugar beets for the production of 5-hydroxymethylfurfural. In the present study, the maximum concentration of 5-hydroxymethylfurfural was 3.4 g/L after heating up to 200 °C.

Simultaneous Determination of Six Compounds in Destructive Distillation Extracts of Hawthorn Seed by GC-MS and Evaluation of Their Antimicrobial Activity.

Hawthorn seed can be used to produce various bioactive compounds through destructive distillation. In this study, an accurate and feasible analytical method based on a gas chromatography mass spectrometer (GC-MS) was developed for simultaneous determination of six major compounds (contributing to more than 3% in total peak area) in destructive distillation extracts of hawthorn seed collected at different temperatures ranging from 150 to 270 °C. Then, a broth microdilution method coupled with grey correlation analysis was engaged in the evaluation of their antimicrobial activities and the screening of primarily active compounds. Results indicate that the extract collected from 211 to 230 °C had the highest content of six major compounds (furfural, 2-methoxyphenol, 2-methoxy-4-methylphenol, 4-ethyl-2-methoxyphenol, 2,6-dimethoxyphenol, and 5-tertbutylpyrogallol) and the strongest antibacterial activity. Besides, 2,6-dimethoxyphenol was found to be a potential compound in inhibiting the growth of vaginitis pathogens. This study provided an optimum temperature for the destructive distillation of hawthorn seed, reducing the waste of energy, and saving the cost of production in the hawthorn industry.

2-Furaldehyde diethyl acetal from tender coconut water (Cocos nucifera) attenuates biofilm formation and quorum sensing-mediated virulence of Chromobacterium violaceum and Pseudomonas aeruginosa.

The aim of this study was to evaluate the anti-biofilm and quorum sensing inhibitory (QSI) potential of tender coconut water (TCW) against Chromobacterium violaceum and Pseudomonas aeruginosa. TCW significantly inhibited the QS regulated violacein, virulence factors and biofilm production without affecting their growth. qRT-PCR analysis revealed the down-regulation of autoinducer synthase, transcriptional regulator and virulence genes. Mass-spectrometric analysis of a petroleum ether extract of the TCW hydrolyte revealed that 2-furaldehyde diethyl acetal (2FDA) and palmitic acid (PA) are the major compounds. In vitro bioassays confirmed the ability of 2FDA to inhibit the biofilm formation and virulence factors. In addition, the combination of PA with 2FDA resulted in potent inhibition of biofilm formation and virulence factors. The results obtained strongly suggest that TCW can be exploited as a base for designing a novel antipathogenic drug formulation to treat biofilm mediated infections caused by P. aeruginosa.

Identification of Aroma-active Compounds in Essential Oil from Uncaria Hook by Gas Chromatography- Mass Spectrometry and Gas Chromatography-Olfactometry.

The chemical composition of essential oil extracted from Uncaria Hook ("Chotoko" in Japanese), the branch with curved hook of the herbal medicine Uncaria rhynchophylla has been investigated by GC and GC-MS analyses. Eighty-four compounds, representing 90.8% of the total content was identified in oil obtained from Uncaria Hook. The main components i were (E)-cinnamaldehyde (13.4%), α-copaene (8.0%), methyl eugenol (6.8%), δ-cadinene (5.3%), and curcumene (3.6%). The important key aroma-active compounds in the oil were detected by gas chromatography-olfactometry (GC-O) and aroma extract dilution analysis (AEDA), using the flavor dilution (FD) factor to express the odor potency of each compounds. Furthermore, the odor activity value (OAV) has been used as a measure of the relative contribution of each compound to the aroma of the Uncaria Hook oil. The GC-O and AEDA results showed that α-copaene (FD = 4, OAV = 4376), (E)-linalool oxide (FD = 64, OAV = 9.1), and methyl eugenol (FD = 64, OAV = 29) contributed to the woody and spicy odor of Uncaria Hook oil, whereas furfural (FD = 8, OAV = 4808) contributed to its sweet odor. These results warrant further investigations of the application of essential oil from Uncaria Hook in the phytochemical and medicinal fields.

A versatile, stability-indicating and high-throughput ultra-fast liquid chromatography method for the determination of isoflavone aglycones in soybeans, topical formulations, and permeation assays.

There is a growing interest in the pharmaceutical field concerning isoflavones topical delivery systems, especially with regard to their skin care properties and antiherpetic activity. In this context, the present work describes an ultra-fast liquid chromatography method (UFLC) for determining daidzein, glycitein, and genistein in different matrices during the development of topical systems containing isoflavone aglycones (IA) obtained from soybeans. The method showed to be specific, precise, accurate, and linear (0.1 to 5 µg mL(-1)) for IA determination in soybean acid extract, IA-rich fraction obtained after the purification process, IA loaded-nanoemulsions, and topical hydrogel, as well as for permeation/retention assays in porcine skin and porcine esophageal mucosa. The matrix effect was determined for all complex matrices, demonstrating low effect during the analysis. The stability indicating UFLC method was verified by submitting IA to acidic, alkaline, oxidative, and thermal stress conditions, and no interference of degradation products was detected during analysis. Mass spectrometry was performed to show the main compounds produced after acid hydrolysis of soybeans, as well as suggest the main degradation products formed after stress conditions. Besides the IA, hydroxymethylfurfural and ethoxymethylfurfural were produced and identified after acid hydrolysis of the soybean extract and well separated by the UFLC method. The method's robustness was confirmed using the Plackett-Burman experimental design. Therefore, the new method affords fast IA analysis during routine processes, extract purification, products development, and bioanalytical assays.

Two new furaldehyde compounds from the rhizomes of Gastrodia elata.

Two new compounds 5-[4'-(4″-hydroxybenzyl)-3'-hydroxybenzyloxymethyl]-furan-2-carbaldehyde (1) and 5-[4'-(4″-hydroxybenzyl)-3'-hydroxybenzyl]-furan-2-carbal-dehyde (2), together with two known 5-(4-hydroxbenzyloxymethyl)-furan-2-carbaldehyde] (3) and 5-(hydroxymethyl)-2-furaldehyde (4), were isolated from the rhizome of Gastrodia elata. Their structures were elucidated by spectroscopic analysis and comparison of their spectral data with those reported previously. All compounds exhibited weak or no cytotoxicity against human colon carcinoma cell line (HT-29) and human chronic myelogenous leukemia cell line (K-562).

5-Hydroxymethylfurfural, an antioxidant agent from Alpinia oxyphylla Miq. improves cognitive impairment in Aß 1-42 mouse model of Alzheimer's disease.

5-Hydroxymethylfurfural (5-HMF) is a main effective compound of Alpinia oxyphylla Miq. ethanol extract, which showed memory improvement activity against Alzheimer's disease in previous study. In order to identify a potential therapeutic agent, the neuroprotective effects of 5-HMF on impairment of cognition and memory function induced by intracerebroventricular (ICV) injection of Aß 1-42 were investigated in vivo. The mice were treated with 5-HMF at dose of 15 µg/kg and 150 µg/kg (ICV) for five consecutive days after ICV-Aß 1-42. The results showed that 5-HMF significantly ameliorated learning and memory impairment evaluated by the locomotor activity, Y-maze test, and Morris water maze test. Furthermore, 5-HMF significantly inhibited the ß-secretase activity, decreased the content of Aß 1-42 and malondialdehyde (MDA), and increased the antioxidative enzyme activities including superoxide dismutase (SOD) and glutathione peroxidase (GPx). Results of hippocampus slices showed that neuronal were integrated and regularly arranged in the groups which were administered along with 5-HMF, indicating that 5-HMF could mitigate the degree of neuronal damage. The present study indicated that 5-HMF may serve as a potential therapeutic agent for the treatment of Alzheimer's disease.

[Chemical constituents of Fortunella margarita fruits].

OBJECTIVE: To study the chemical constituents of the fruits of Fortunella margarita. METHODS: The constituents were isolated and purified on silica gel column and other column chromatography, and their structures were determined by means of spectral techniques and physicochemical data. RESULTS: 11 compounds were isolated and identified as fortunellin (1), naringenin (2), phloridzin (3), nicotinflorin (4), rhoifolin (5), 4'-methoxy vitexin-2"-O-alpha-L-rhamnopyranoside (6), 4'-methoxy isovitexin-2"-O-alpha-L-rhamnopyranoside (7), rutin (8), phloretin-3', 5'-di-C-beta-glucopyranoside (9), 5-hydroxymethyl-furaldehyde (10) and beta-sitosterol (11). CONCLUSION: Compound 2 - 4,7 and 10 are isolated from the plant for the first time.

[Chemical constituents from root bark of Dictamnus dasycarpus].

OBJECTIVE: To isolate and identify the chemical constituents from the root bark of Dictamnus dasycarpus. METHODS: Silica gel, Sephadex LH-20, ODS and PTLC were employed for the isolation and purification of chemical constituents. The structures were identified on the basis of spectral data and physicochemical examination. RESULTS: Thirteen compounds were isolated and identified as follows: rutaevin (1), obacunone (2), fraxinellone (3), limonin (4), dictamnine (5), beta-sitosterol (6), 5-hydroxylmethylfuraldehyde (7), daucosterol (8), 3beta-hydroxy-cholesta-5-ene (9), fraxinellonone (10), rutin (11), quercetin (12) and scopoletin (13). CONCLUSION: Compounds 7 and 9 are isolated from this genus for the first time.

Effects of 5-hydroxymethyl furfural extracted from Rehmannia glutinosa Libosch on the expression of signaling molecules relevant to learning and memory among hippocampal neurons exposed to high concentration of corticosterone.

OBJECTIVE: To determine the effects of 5-hydroxymethyl furfural (5-HMF), an extract of Rehmannia glutinosa Libosch, on several down-regulated signaling molecules involved in learning and memory in hippocampal neurons. METHODS: After cultured for 7 days, primary hippocampal neurons were divided into 5 groups: normal, corticosterone model, RU38486, 5-HMF, and donepezil group. Neuron survival rates were calculated 24 h later using SYTO13-PI double-fluorescence staining and an 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. ß-galactosidase activity was also assayed. Protein expressed by the glucocorticoid receptor (GCR), brainderived neurotrophic factor (BDNF), and N-methyl-D-aspartate receptor 2B (NR2B), as well as phosphorylationcyclic adenosine monophosphate (cAMP) response element binding protein (p-CREB), phosphorylation-extracellular signal-regulated kinase (p-ERK), and phosphorylation-synapsin (p-synapsin) were quantified with Western blot. RESULTS: Hippocampal neuron survival rates and the above-mentioned proteins were dramatically decreased (P<0.05), ß-galactosidase activity was significantly increased in the model group. but the effect was reversed by 5-HMF, RU38486, and to a lesser extent by donepezil (P<0.05). CONCLUSION: 5-HMF extracts from the Chinese herb Rehmannia glutinosa Libosch could protect hippocampal neurons from glucocorticoid injury and from down-regulated signaling molecules in the GCR-BDNF-NR2B-p-ERK-p-CREB-p-synapsin signal transduction pathway.

Isolation of bioactive phytoconstituent from Alpinia galanga L. with anti-hyperlipidemic activity.

The present study was undertaken to explore the antihyperlipidemic effect of ethanolic extract of rhizomes of Alpinia galanga L. and its chloroform fraction in Triton-induced hyperlipidemic rats. Bioactivity guided fractionation was followed by chromatographic studies. Flash chromatography was done for the most active fraction resulting in the isolation of 5-(hydroxymethyl) furfural. Animals were administered with i.p. injection of Triton WR 1339 at dose of 400 mg/kg body weight. After 24 hr of Triton administration, the ethanolic extract and its fraction were administered orally at doses of 200 and 400 mg/kg body weight in rats. The treatment was continued for 5 days with a view to see the effect on lipid profile. Serum samples were subjected to biochemical analysis. The study dose dependently inhibited the total cholesterol (TC), triglycerides (TG), low-density lipoprotein (LDL) level, and significantly increased high-density lipoprotein (HDL) level. Phytochemical screening revealed the presence of tannins, coumarins, flavanoids, sterols, and glycosides. Phytochemical investigation of the chloroform fraction of A. galanga L. resulted in the isolation of 5-(hydroxymethyl) furfural. UV λmax was found to be 276 nm for the isolated component. Acute treatment caused a stimulatory effect on the HDL level and inhibition in TC and TG elevation induced by triton.

Isolation, structural elucidation, and biological evaluation of a 5-hydroxymethyl-2-furfural derivative, asfural, from enzyme-treated asparagus extract.

A novel 5-hydroxymethyl-2-furfural (HMF; 1) derivative, which is named asfural (compound 2), was isolated from enzyme-treated asparagus extract (ETAS) along with HMF (1) as a heat shock protein 70 (HSP70) inducible compound. The structure of compound 2 was elucidated on the basis of its spectroscopic data from HREIMS and NMR, whereas the absolute configuration was determined using chiral HPLC analysis, compared to two synthesized compounds, (S)- and (R)-asfural. As a result, compound 2 derived from ETAS was assigned as (S)-(2-formylfuran-5-yl)methyl 5-oxopyrrolidine-2-carboxylate. When compound 2, synthesized (S)- and (R)-asfural, and HMF (1) were evaluated in terms of HSP70 mRNA expression-enhancing activity in HL-60 cells, compound 2 and (S)-asfural significantly increased the expression level in a concentration-dependent manner. HMF (1) also showed significant activity at 0.25 mg/mL.

[Chemical constituents from the roots of Angelica polymorpha Maxim].

Angelica polymorpha Maxim. is a plant of the Angelica genus (Umbelliferae). The root and stem of this plant is a folk medicine known to have the actions of relieving rheumatism and cold and subsiding swelling and pains. To investigate the chemical constituents in the root of A. polymorpha Maxim., seven compounds were isolated from an 80% ethanol extract by column chromatography. Their structures were elucidated according to the spectroscopic analysis. Compound 1 is a new sesquiterpene, named as bisabolactone. Its absolute configuration was determined by 1D NOESY and CD analysis. The others were identified as 5-hydroxymethylfurfural (2), hycandinic acid ester 1 (3), ferulic acid (4), isooxypeucedanin (5), noreugenin (6) and cimifugin (7). Compound 2 and 3 were isolated from this genus for the first time and compound 4 was isolated from this plant for the first time.

Dry vs soaked wood: modulating the volatile extractible fraction of oak wood by heat treatments.

The aim of this study was to analyze the impact of the water content of wood on the concentrations of volatile compounds which can be extracted after heat treatments. Head Space-Solid Phase Micro Extraction Gas Chromatography coupled to Mass Spectrometry (HS-SPME GC-MS) has been used to compare the concentrations of six aroma compounds (vanillin, furfural, eugenol, guaïacol and cis- and trans-whisky lactones) in hydroalcoholic extracts of heated oak wood samples either previously soaked in hot water or not. Except for eugenol, concentrations of extracted aromas appeared to be lower in soaked woods than in dry woods for temperatures up to 200 °C. If a delaying effect of water could explain such overall lower extracted concentrations from soaked woods, a PCA analysis revealed that for the longer duration (25 min of heat treatment), the adsorbed water could promote a higher impact of furfural, eugenol and both whisky lactones on the composition of hydroalcoholic extracts, suggesting that alternative mechanisms of thermal modifications of the wood macromolecular network could exist at high temperatures in presence of adsorbed water.

[Chemical constituents of ethyl acetate extract from Polygonum perfoliatum].

OBJECTIVE: To study the chemical constituents of Polygonum perfoliatum. METHODS: The chemical constituents of Polygonum perfoliatum were isolated and purified by chromatography on silica gel, Sephadex LH-20 and Semi-preparative HPLC. The structures of compounds were elucidated and identified by physicochemical properties, H-NMR, 13C-NMR and ESI-MS. RESULTS: Ten compounds were isolated and identified as 5-hydroxymethyl-2-furaldEhyde (1), methyl caffeoate (2), protocatechuic aldehyde (3), quercetin (4), pinocernbrin (5), catechin (6), taxifolin (7), taxifolin-3-O-beta-D-xylopyranoside (8), 13-epitorulosal (9), coumarin-7-O-beta-D-glucose glycosidic (10). CONCLUSION: [corrected] Compounds 6-9 are isolated from this plant for the first time.

[Binding mechanism of traditional Chinese medicine active component 5-hydroxymethyl-furfural and HSA or BSA].

A combination of spectral experiment and molecular modeling techniques has been used to characterize the binding mechanism between an active component 5-hydroxymethyl-furfural (5-HMF) of traditional Chinese medicine and human serum albumin (HSA) or bovine serum albumin (BSA). The interaction mechanism of 5-HMF binding with HSA/BSA is analyzed. Although the drug can bind with HSA/BSA to form stable complexes, there are some differences in the bond strength. The values of binding distances (r) are different and low, which indicated the occurrence of energy transfer. The drug had conformational effect on HSA/BSA, which resulted in different changes of hydrophobic environment of the binding domain in HSA/BSA. The 'phase diagram' of fluorescence revealed that the changes on the conformational pattern of proteins have been affected by drug conformed to the "all-or-none" pattern. The interactions between drug and protein influenced by Co(II) were also discussed. Its effects acting on 5-HMF-HSA/BSA interactions are different. The computational modeling method was used to study the interaction between 5-HMF and HSA/BSA. The results of molecular model studies revealed that the binding modes for drug-serum albumin systems are mainly hydrophobic interactions and hydrogen bonding. These results are in accordance with spectral results. The research results have given a better theoretical reference for the study of pharmacological mechanism of 5-hydroxymethyl-furfural.

Separation of two constituents from purple sweet potato by combination of silica gel column and high-speed counter-current chromatography.

It is known that the choice of solvent system for high speed counter-current chromatography separation is of utmost importance. In this study, a simple and rapid thin layer chromatograph coupling with fluorometric (TLC-F) method has been used to determine the partition coefficient of target compounds in HSCCC solvent system. Two components, 6,7-dimethoxycoumarin and 5-hydroxymethyl-2-furfural were successfully separated from purple sweet potato extracts by successive sample injection for the first time, using n-hexane-ethyl acetate-methanol-water (1:2:1:1, v/v/v/v) as the solvent system. Additionally, statistical analysis showed that there was no significant difference in partition coefficient obtained by the TLC-F method and by HPLC, which demonstrated the usefulness of TLC-F method.

[Study on chemical constituents of Carthamus tinctorius].

OBJECTIVE: To investigate the chemical constituents in water-soluble fraction of Carthamus tinctorius. METHODS: Compounds were isolated and purified by macroporus resin, silica gel, Sephadex LH-20 column chromatography and preparative HPLC. The structures were identified by spectral analysis. RESULTS: Twelve compounds were isolated and identified as 4-Hydroxybenzaldehyde (1); E-1-(4'-hydroxypheny) -but-1-en-3-one (2); 3-Formylindole (3); 2-Acetyl-5-hydroxymethylfuran (4); p-Hydroxycinnamic acid (5); (6R, 7E, 9R) -9-hydroxy-4,7-megastigmandien-3-one (6); 4-hydroxyacetophenone (7); 5-(hydroxymethyl) -2-furaldehyde (8); 4-Hydroxybenzoic acid (9); Stigmasterol-3-O-beta-D-glucopyranoside (10); Daucosterol (11); beta-sitosterol (12). CONCLUSION: Compounds 1 - 4, 6, 7, 10 are isolated from this plant for the first time.

[Influence of different processing method and mature stage on main chemical constituents of Schisandra chinensis].

OBJECTIVE: To study different processing method and mature stage on the quantity of the Schisandra chinensis in the Xinbin region of Liaoning. METHOD: The schisantherin A and 5-hydroxymethylufrurfal (5-HMF) content in S. chinensis was determined by using the HPLC method. The organic acids content was determined by potentiometric titration. The polysaccharide content was determined by oxidation reduction titration. The volatile oil content was determined by steam distillation. RESULT: The quantity of S. chinensis was different due to different processing method and mature stage. CONCLUSION: The different processing method and mature stage have significant influence on the quantity of S. chinensis.

Comparative analyses of chromatographic fingerprints of the roots of Polygonum multiflorum Thunb. and their processed products using RRLC/DAD/ESI-MS(n).

The dried roots of Polygonum multiflorum Thunb. (Heshouwu) and their processed products (Zhi-heshouwu) are widely used in traditional Chinese medicine, yet their therapeutic effects are different. Previous investigations focused mainly on the differences between Heshouwu and Zhi-heshouwu in the contents of several known compounds. In this study, a rapid resolution liquid chromatography-diode array detection/electrospray ionization tandem mass spectrometry (RRLC/DAD/ESI-MS(n)) method was developed for the comparative analysis of the components of Heshouwu and Zhi-heshouwu. A total of 23 compounds were identified or tentatively characterized. We found that 16 batches of Heshouwu and 15 batches of Zhi-heshouwu samples shared eight compounds, including gallic acid; 3,5,4'-tetrahydroxylstilbene-2,3-di-O-glucoside, CIS-2,3,5,4'-tetrahydroxylstilbene-2-O- ß-D-glucoside, trans-2,3,5,4'-tetrahydroxylstilbene-2-O- ß-D-glucoside, emodin-8-O- ß-D-glucoside, physcion-8-O- ß-D-glucoside, emodin, and physcion. Nevertheless, the relative amounts of gallic acid, emodin, and physcion were very high in Zhi-heshouwu samples compared to those in Heshouwu samples. Six compounds disappeared after processing and were unique for Heshouwu: catechin, flavanol gallate dimer, polygonimitin B, emodin-1-O-glucoside, emodin-8-O-(6'-O-malonyl)-glucoside, and physcion-8-O-(6'-O-malonyl)-glucoside. Three compounds were unique for Zhi-heshouwu: hydroxymaltol, 2,3-dihydro-3,5-dihydroxy-6-methyl-4(H)-pyran-4-one, and 5-hydroxymethyl furfural. These results suggest that the types and relative amounts of the chemical components of Heshouwu and Zhi-heshouwu are different.