Industrial Distillation Fractions of Garlic Essential Oil, Design, Synthesis, and Antifungal Activity Evaluation of Aliphatic Substituted Trisulfide Derivatives.

Garlic oil has a wide range of biological activities, and its broad-spectrum activity against phytopathogenic fungi still has the potential to be explored. In this study, enzymatic treatment of garlic resulted in an increase of approximately 50 % in the yield of essential oil, a feasible GC-MS analytical program for garlic oil was provided. Vacuum fractionation of the volatile oil and determination of its inhibitory activity against 10 fungi demonstrated that garlic oil has good antifungal activity. The antifungal activity levels were ranked as diallyl trisulfide (S-3)>diallyl disulfide (S-2)>diallyl monosulfide (S-1), with an EC50 value of S-3 against Botrytis cinerea reached 8.16 mg/L. Following the structural modification of compound S-3, a series of derivatives, including compounds S-4~7, were synthesized and screened for their antifungal activity. The findings unequivocally demonstrated that the compound dimethyl trisulfide (S-4) exhibited exceptional antifungal activity. The EC50 of S-4 against Sclerotinia sclerotiorum reached 6.83 mg/L. SEM, In vivo experiments, and changes in mycelial nucleic acids, soluble proteins and soluble sugar leakage further confirmed its antifungal activity. The study indicated that the trisulfide bond structure was the key to good antifungal activity, which can be developed into a new type of green plant-derived fungicide for plant protection.

Identification and Allelopathy of Green Garlic (Allium sativum L.) Volatiles on Scavenging of Cucumber (Cucumis sativus L.) Reactive Oxygen Species.

Garlic and formulations containing allicin are used widely as fungicides in modern agriculture. However, limited reports are available on the allelopathic mechanism of green garlic volatile organic compounds (VOCs) and its component allelochemicals. The aim of this study was to investigate VOCs of green garlic and their effect on scavenging of reactive oxygen species (ROS) in cucumber. In this study, green garlic VOCs were collected by HS-SPME, then analyzed by GS-MS. Their biological activity were verified by bioassays. The results showed that diallyl disulfide (DADS) is the main allelochemical of green garlic VOCs and the DADS content released from green garlic is approximately 0.08 mg/g. On this basis, the allelopathic effects of green garlic VOCs in vivo and 1 mmol/L DADS on scavenging of ROS in cucumber seedlings were further studied. Green garlic VOCs and DADS both reduce superoxide anion and increase the accumulation of hydrogen peroxide of cucumber seedlings. They can also regulate active antioxidant enzymes (SOD, CAT, POD), antioxidant substances (MDA, GSH and ASA) and genes (CscAPX, CsGPX, CsMDAR, CsSOD, CsCAT, CsPOD) responding to oxidative stress in cucumber seedlings.

Diallyl Disulfide Induces Apoptosis and Autophagy in Human Osteosarcoma MG-63 Cells through the PI3K/Akt/mTOR Pathway.

Diallyl disulfide (DADs), a natural organic compound, is extracted from garlic and scallion and has anti-tumor effects against various tumors. This study investigated the anti-tumor activity of DADs in human osteosarcoma cells and the mechanisms. MG-63 cells were exposed to DADs (0, 20, 40, 60, 80, and 100 µM) for different lengths of time (24, 48, and 72 h). The CCK8 assay results showed that DADs inhibited osteosarcoma cell viability in a dose-and time-dependent manner. FITC-Annexin V/propidium iodide staining and flow cytometry demonstrated that the apoptotic ratio increased and the cell cycle was arrested at the G2/M phase as the DADs concentration was increased. A Western blot analysis was employed to detect the levels of caspase-3, Bax, Bcl-2, LC3-II/LC3-I, and p62 as well as suppression of the mTOR pathway. High expression of LC3-II protein revealed that DADs induced formation of autophagosome. Furthermore, DADs-induced apoptosis was weakened after adding 3-methyladenine, demonstrating that the DADs treatment resulted in autophagy-mediated death of MG-63 cells. In addition, DADs depressed p-mTOR kinase activity, and the inhibited PI3K/Akt/mTOR pathway increased DADs-induced apoptosis and autophagy. In conclusion, our results reveal that DADs induced G2/M arrest, apoptosis, and autophagic death of human osteosarcoma cells by inhibiting the PI3K/Akt/mTOR signaling pathway.

Allyl methyl sulfide, a garlic active component mitigates hyperglycemia by restoration of circulatory antioxidant status and attenuating glycoprotein components in streptozotocin-induced experimental rats.

Diabetes is a major noncommunicable life-threatening chronic and pervasive condition that is consuming the world health in a petrifying rate. The circulatory system is one of the major sources of hyperglycemia-induced ROS generation. Historically, garlic has been revered as part of a healthful diet. Organosulfur compounds have been attributed to the medicinal properties and health benefits of garlic. The present study focuses on the ameliorative role of allyl methyl sulfide (AMS) in combating diabetic complications in diabetic rats. Male Wistar rats were randomly divided into four groups. Experimental diabetes was induced by a single intraperitoneal injection (i.p), of streptozotocin (STZ) (40 mg/kg b.w). STZ treated diabetic rats showed significant augment in plasma glucose level, lipidperoxidative (LPO) markers, glycoprotein components (hexose, hexosamine, sialic acid, and fucose), and significant decline in plasma insulin level, nonenzymatic antioxidants and activities of antioxidant enzymes in the circulatory system and tissues. Further, periodic acid-Schiff (PAS) staining of hepatic and renal tissues revealed positive stain accumulation and Western blot investigation of glucose transporter 2 (GLUT 2) in pancreas of STZ-induced hyperglycemic rats. Dietary intervention with AMS (100 mg/kg b.w) for 30 days demonstrated significant protective effects on all the biochemical parameters studied. Besides, biochemical findings were corroborated by histological exertion and Western blot study. The findings of current investigations recommended that AMS can ameliorate the consequences of diabetes due to their antioxidant efficacy and can be used as a potential therapeutic approach. Further studies are warranted to explore the clinical application of AMS.

Comparative functional characterization of eugenol synthase from four different Ocimum species: Implications on eugenol accumulation.

Isoprenoids and phenylpropanoids are the major secondary metabolite constituents in Ocimum genus. Though enzymes from phenylpropanoid pathway have been characterized from few plants, limited information exists on how they modulate levels of secondary metabolites. Here, we performed phenylpropanoid profiling in different tissues from five Ocimum species, which revealed significant variations in secondary metabolites including eugenol, eugenol methyl ether, estragole and methyl cinnamate levels. Expression analysis of eugenol synthase (EGS) gene showed higher transcript levels especially in young leaves and inflorescence; and were positively correlated with eugenol contents. Additionally, transcript levels of coniferyl alcohol acyl transferase, a key enzyme diverting pool of substrate to phenylpropanoids, were in accordance with their abundance in respective species. In particular, eugenol methyl transferase expression positively correlated with higher levels of eugenol methyl ether in Ocimum tenuiflorum. Further, EGSs were functionally characterized from four Ocimum species varying in their eugenol contents. Kinetic and expression analyses indicated, higher enzyme turnover and transcripts levels, in species accumulating more eugenol. Moreover, biochemical and bioinformatics studies demonstrated that coniferyl acetate was the preferred substrate over coumaryl acetate when used, individually or together, in the enzyme assay. Overall, this study revealed the preliminary evidence for varied accumulation of eugenol and its abundance over chavicol in these Ocimum species. Current findings could potentially provide novel insights for metabolic modulations in medicinal and aromatic plants.

Enantioseparation of α-Hydroxyallylphosphonates and Phosphonoallylic Carbonate Derivatives on Chiral Stationary Phases Using Sequential UV, Polarimetric, and Refractive Index Detection.

Chromatographic separation of the enantiomers of parent compounds dimethyl α-hydroxyallyl phosphonate and 1-(dimethoxyphosphoryl) allyl methyl carbonate was demonstrated by high-performance liquid chromatography (HPLC) using Chiralpak AS-H and ad-H chiral stationary phases (CSP), respectively, using a combination of UV, polarimetric, and refractive index detectors. A comparison was made of the separation efficiency and elution order of enantiomeric α-hydroxyallyl phosphonates and their carbonate derivatives on commercially available polysaccharide AS, ad, OD, IC-3, and Whelk-O 1 CSPs. In general, the α-hydroxyallyl phosphonates were resolved on the AS-H CSP, whereas the carbonate derivatives and were preferentially resolved on the ad-H CSP. The impact of aryl substitution on the resolution of analytes and was evaluated. Thermodynamic parameters determined for enantioselective adsorption hydroxyphosphonates and on the AS-H CSP and carbonate on the ad-H CSP demonstrated enthalpic control for separation of the enantiomers. Chirality 28:656-662, 2016. © 2016 Wiley Periodicals, Inc.

Diallyl Sulfide and Its Role in Chronic Diseases Prevention.

Diallyl sulfide (C6H10S, DAS) is one of the novel natural organosulfur compounds, which is mostly obtained from the genus Allium plants. Numerous studies have revealed several unique properties of DAS in terms of its health-promoting effects. DAS has proved to be anticancer, antimicrobial, anti-angiogenic, and immunomodulatory like unique functions as demonstrated by the multiple investigations. Diallyl sulfide can also impede oxidative stress and chronic inflammation as suggested by the literature. Studies also explored that DAS could thwart the development of chronic diseases like cancer, neuronal, cardiovascular disease through modulating mechanistic pathways involved in pathogenesis. In this book chapter, we have attempted to give the comprehensive view on DAS about the physiochemical and biological properties, and its preventive role in chronic diseases with a mechanistic overview.

Investigating the responses of Cronobacter sakazakii to garlic-drived organosulfur compounds: a systematic study of pathogenic-bacterium injury by use of high-throughput whole-transcriptome sequencing and confocal micro-raman spectroscopy.

We present the results of a study using high-throughput whole-transcriptome sequencing (RNA-seq) and vibrational spectroscopy to characterize and fingerprint pathogenic-bacterium injury under conditions of unfavorable stress. Two garlic-derived organosulfur compounds were found to be highly effective antimicrobial compounds against Cronobacter sakazakii, a leading pathogen associated with invasive infection of infants and causing meningitis, necrotizing entercolitis, and bacteremia. RNA-seq shows changes in gene expression patterns and transcriptomic response, while confocal micro-Raman spectroscopy characterizes macromolecular changes in the bacterial cell resulting from this chemical stress. RNA-seq analyses showed that the bacterial response to ajoene differed from the response to diallyl sulfide. Specifically, ajoene caused downregulation of motility-related genes, while diallyl sulfide treatment caused an increased expression of cell wall synthesis genes. Confocal micro-Raman spectroscopy revealed that the two compounds appear to have the same phase I antimicrobial mechanism of binding to thiol-containing proteins/enzymes in bacterial cells generating a disulfide stretching band but different phase II antimicrobial mechanisms, showing alterations in the secondary structures of proteins in two different ways. Diallyl sulfide primarily altered the α-helix and ß-sheet, as reflected in changes in amide I, while ajoene altered the structures containing phenylalanine and tyrosine. Bayesian probability analysis validated the ability of principal component analysis to differentiate treated and control C. sakazakii cells. Scanning electron microscopy confirmed cell injury, showing significant morphological variations in cells following treatments by these two compounds. Findings from this study aid in the development of effective intervention strategies to reduce the risk of C. sakazakii contamination in the food production environment and on food contact surfaces, reducing the risks to susceptible consumers.

Three new phenylpropanoids from the roots of Piper taiwanense and their inhibitory activities on platelet aggregation and Mycobacterium tuberculosis.

Bioassay-guided fractionation of the active AcOEt-soluble fraction from the roots of Piper taiwanense has led to the isolation of two new phenylpropanoids, taiwanensols A and B (1 and 2, resp.), a new natural product, taiwanensol C (3), and 3-acetoxy-4-hydroxy-1-allylbenzene (4). The compounds were obtained as two isomer mixtures (1/2 and 3/4, resp.). Their structures were elucidated by spectroscopic analyses, including 1D- and 2D-NMR spectroscopy and mass spectrometry, and by the comparison of their NMR data with those of related compounds. Compounds 1-4 were evaluated for their antiplatelet and antitubercular activities. The mixtures 1/2 and 3/4 showed potent inhibitory activities against platelet aggregation induced by collagen, with IC50 values of 35.2 and 8.8 µM, respectively. In addition, 1/2 and 3/4 showed antitubercular activities against Mycobacterium tuberculosis H37Rv, with MIC values of 30.0 and 48.0 µg/ml, respectively.

Engineering an anaerobic metabolic regime in Pseudomonas putida KT2440 for the anoxic biodegradation of 1,3-dichloroprop-1-ene.

Pseudomonas putida KT2440, a microbial cell factory of reference for industrial whole-cell biocatalysis, is unable to support biochemical reactions that occur under anoxic conditions, limiting its utility for a large number of relevant biotransformations. Unlike (facultative) anaerobes, P. putida resorts to NADH oxidation via an oxic respiratory chain and completely lacks a true fermentation metabolism. Therefore, it cannot achieve the correct balances of energy and redox couples (i.e., ATP/ADP and NADH/NAD(+)) that are required to sustain an O(2)-free lifestyle. To overcome this state of affairs, the acetate kinase (ackA) gene of the facultative anaerobe Escherichia coli and the pyruvate decarboxylase (pdc) and alcohol dehydrogenase II (adhB) genes of the aerotolerant Zymomonas mobilis were knocked-in to a wild-type P. putida strain. Biochemical and genetic assays showed that conditional expression of the entire enzyme set allowed the engineered bacteria to adopt an anoxic regime that maintained considerable metabolic activity. The resulting strain was exploited as a host for the heterologous expression of a 1,3-dichloroprop-1-ene degradation pathway recruited from Pseudomonas pavonaceae 170, enabling the recombinants to degrade this recalcitrant chlorinated compound anoxically. These results underscore the value of P. putida as a versatile agent for biotransformations able to function at progressively lower redox statuses.

Allium sativum-derived allitridin inhibits Treg amplification in cytomegalovirus infection.

This study investigated the effects of allitridin compound on murine cytomegalovirus (MCMV)-induced regulatory T cell (Treg; CD4(+) CD25(+) Foxp3(+) ) amplification in vivo and in vitro. One hundred twenty MCMV-infected mice were allocated at random into two groups for treatment with allitridin or placebo. Another 120 mock-infected mice were randomly allocated as controls for the allitridin treatment and placebo treatment groups. The mice were euthanized at various time points after infection (out to 120 days) to evaluate the effects of treatment on Treg presence and function, as well as MCMV infective load. Co-culture with mouse embryo fibroblasts (MEF) and MCMV was performed to evaluate allitridin-mediated Treg and anti-CMV effects. The maximum tolerance concentration (MTC) of allitridin was used to treat cells for 3 days. Changes in Foxp3 mRNA and protein levels, percentages of T cell subsets, and Treg-related cytokines (IL-10 and TGF-ß) were measured. Allitridin treatment did not influence Foxp3 expression and Treg proportion in uninfected mice, but did down-regulate each in infected mice during the chronic infection period. Additionally, allitridin treatment reduced the MCMV load in salivary glands. MTC allitridin treatment of co-cultures partially blocked MCMV induction of Foxp3 mRNA and protein expression. In vitro treatment with allitridin also increased significantly the percentages of Tc1, Tc2, and Th1, reduced the secreted levels of IL-10 and TGF-ß1, and significantly suppressed viral loads. In conclusion, allitridin can promote MCMV-induced Treg expansion and Treg-mediated anti-MCMV immunosuppression. Therefore, allitridin may be useful as a therapeutic agent to enhance the specific cellular immune responses against CMV.

Effect of Allium sativum and Allium cepa oils on different stages of Boophilus annulatus.

The study is aimed to investigate the acaricidal effect of Allium sativum (garlic) and Allium cepa (onion) oils on different stages of Boophilus annulatus hard tick. Engorged B. annulatus females were collected from naturally infected cattle. A number of engorged ticks were incubated at 28 °C and 85 % relative humidity to lay eggs, which were incubated to obtain larvae that were used in the study. The used garlic and onion oils were prepared by steam distillation and were analyzed by gas chromatography. These oils were dissolved in ethanol, methanol alcohols, and, partially, in water. The oils were tested in different concentrations; 1, 2, 5, 10, and 20 %. These concentrations were applied on adult ticks by adult immersion test; on larvae by larval immersion technique and on eggs. The 20, 10, and 5 % of garlic oil dilutions in ethanol and methanol killed all adult ticks and larvae within 24 h. Similar results were obtained for 10 and 20 % garlic oil dissolved in water. The effect of 10 % aqueous solution of garlic oil on embryonated eggs was clear as its addition to these eggs led to their in ability to hatch, deformity in shape, and change in color. The 10 and 20 % onion oil in ethanol and methanol alcohols killed 76-86 % of the adult ticks within 72 h post-application. While, all larvae died within 24 h postsubjected to these two concentrations. These concentrations (10 and 20 %) of onion oil in water killed 56-80 % of the treated ticks. Moreover, 10 % aqueous solution of onion oil prevented hatching of embyonated eggs. We concluded that garlic and onion oils have acaricidal effect on all stages of B. annulatus at concentrations higher than 5 %. Only garlic oil could kill 100 % of adult ticks at concentrations from 5 % in alcohols.

Cyclic sulfoxides garlicnins B2, B3, B4, C2, and C3 from Allium sativum.

Several novel sulfides, called garlicnins B2 (1), B3 (2), B4 (3), C2 (4), and C3 (5), were isolated from acetone extracts of garlic, Allium sativum L. and characterized. These garlicnins are capable of suppressing M2 macrophage activation and they have a novel skeleton of cyclic sulfoxide. The structures of the former 3 and latter of 2 were deduced to be 2-(sulfenic acid)-5-(allyl)-3,4-dimethyltetrahydrothiophene-S-oxides and 2-(allyldithiine)-5-(propenylsulfoxide)-3,4-dimethyltetrahydrothiophene-S-oxides, respectively. The mechanism of the proposed production of these compounds is discussed. The identification of these novel sulfoxides from garlic accumulates a great deal of new chemistry in the Allium sulfide field, and future pharmacological investigations of these compounds will aid the development of natural, healthy foods and anti-cancer agents that may prevent or combat disease.

Dillapiole, isolated from Peperomia pellucida, shows gastroprotector activity against ethanol-induced gastric lesions in Wistar rats.

Peperomia pellucida is a plant used in traditional medicine to treat gastric ulcers. Although this gastroprotective activity was reported, the active compounds have not been identified. Therefore, the aim herein was to identify the most active compound in the gastroprotective activity of P. pellucida using an ethanol-induced gastric ulcer experimental rat model. A gastroprotective effect was observed when the hexane and dichloromethane extracts were tested, with the higher effect being obtained with the dichloromethane extract (82.3 ± 5.6%) at 100 mg/kg. Dillapiole was identified as the most active compound in this extract. Although there have been previous reports on dillapiole, this is the first on its gastroprotective activity. Rats treated with this compound at 3, 10, 30 and 100 mg/kg showed 23.1, 56.1, 73.2 and 85.5% gastroprotection, respectively. The effect elicited by dillapiole at 100 mg/kg was not attenuated by pretreatment with indomethacin (10 mg/kg, s.c.), a prostaglandin synthesis blocker, NG-nitro-l-arginine methyl ester (70 mg/kg, i.p.), a nitric oxide (NO) synthase inhibitor, or N-ethylmaleimide (10 mg/kg, s.c.), a blocker of sulfhydryl groups. This suggests that the gastroprotective mechanism of action of dillapiole does not involve prostaglandins, NO or sulfhydryl groups.

In vitro efficacy of diallyl sulfides against the periodontopathogen Aggregatibacter actinomycetemcomitans.

The in vitro antibacterial effects of diallyl sulfide (DAS) against the Gram-negative periodontopathogen Aggregatibacter actinomycetemcomitans, the key etiologic agent of the severe form of localized aggressive periodontitis and other nonoral infections, were studied. A. actinomycetemcomitans was treated with garlic extract, allicin, or DAS, and the anti-A. actinomycetemcomitans effects of the treatment were evaluated. Garlic extract, allicin, and DAS significantly inhibited the growth of A. actinomycetemcomitans (greater than 3 log; P < 0.01) compared to control cells. Heat inactivation of the garlic extracts significantly reduced the protein concentration; however, the antimicrobial effect was retained. Purified proteins from garlic extract did not exhibit antimicrobial activity. Allicin lost all its antimicrobial effect when it was subjected to heat treatment, whereas DAS demonstrated an antimicrobial effect similar to that of the garlic extract, suggesting that the antimicrobial activity of garlic extract is mainly due to DAS. An A. actinomycetemcomitans biofilm-killing assay performed with DAS showed a significant reduction in biofilm cell numbers, as evidenced by both confocal microscopy and culture. Scanning electron microscopy (SEM) analysis of DAS-treated A. actinomycetemcomitans biofilms showed alterations of colony architecture indicating severe stress. Flow cytometry analysis of OBA9 cells did not demonstrate apoptosis or cell cycle arrest at therapeutic concentrations of DAS (0.01 and 0.1 µg/ml). DAS-treated A. actinomycetemcomitans cells demonstrated complete inhibition of glutathione (GSH) S-transferase (GST) activity. However, OBA9 cells, when exposed to DAS at similar concentrations, showed no significant differences in GST activity, suggesting that DAS-induced GST inhibition might be involved in A. actinomycetemcomitans cell death. These findings demonstrate that DAS exhibits significant antibacterial activity against A. actinomycetemcomitans and that this property might be utilized for exploring its therapeutic potential in treatment of A. actinomycetemcomitans-associated oral and nonoral infections.

Effect of allyl sulfides from garlic essential oil on intracellular ca2+ levels in renal tubular cells.

Diallyl sulfide (1), diallyl disulfide (2), and diallyl trisulfide (3), which are major organosulfur compounds of garlic (Allium sativum), are recognized as a group of potential chemopreventive compounds. In this study, the early signaling effects of 3 were examined on Madin-Darby canine kidney (MDCK) cells loaded with the Ca(2+)-sensitive dye fura-2. It was found that 3 caused an immediate and sustained increase of [Ca(2+)](i) in a concentration-dependent manner (EC(50) = 40 µM). Compound 3 also induced a [Ca(2+)](i) elevation when extracellular Ca(2+) was removed, but the magnitude was reduced by 45%. In Ca(2+)-free medium, the 3-induced [Ca(2+)](i) level was abolished by depleting stored Ca(2+) with 1 µM thapsigargin (an endoplasmic reticulum Ca(2+) pump inhibitor). Elevation of [Ca(2+)](i) caused by 3 in the Ca(2+)-containing medium was not affected by modulation of protein kinase C activity. The 3-induced Ca(2+) influx was inhibited by nifedipine and nicardipine (1 µM). U73122, an inhibitor of phospholipase C, abolished ATP (but not the 3-induced [Ca(2+)](i) level). These findings suggest that 3 induced a significant [Ca(2+)](i) elevation in MDCK renal tubular cells by stimulating both extracellular Ca(2+) influx and thapsigargin-sensitive intracellular Ca(2+) release via as yet unidentified mechanisms. Furthermore, the order of the allyl sulfide-induced [Ca(2+)](i) elevation and cell viability was 1 < 2 < 3. The differential effect of allyl sulfides on Ca(2+) signaling and cell death appears to correlate with the number of sulfur atoms in the structure of these allyl sulfides.

Studies on purification of allicin by molecular distillation.

BACKGROUND: With recent improvements in living standards, people have been giving more consideration to the healthcare effects of foods. In this respect, allicin, which is the most important organosulfur compound in garlic and plays a key role in physiological function, has been receiving much attention. RESULTS: Allicin obtained from garlic by supercritical CO(2) extraction was purified by molecular distillation (MD). The effects of operating conditions such as absolute pressure (AP), distillation temperature (DT) and feed flow rate (FFR) on allicin purity and yield were studied. The optimal AP, DT and FFR levels in first-stage MD were found to be 200 Pa, 50 °C and 15 mL min(-1) respectively. After three stages of MD the contents of allicin, diallyl disulfide (DADS) and diallyl trisulfide (DATS) were 68.04, 9.19 and 5.91% (w/w) respectively. CONCLUSION: This study has provided a safe and effective method for the purification of allicin.

Removal of organic pollutants in model water and thermal wastewater using clay minerals.

Water treatment method was developed for the removal of different anionic dyes such as methyl orange and indigo carmine, and also for thymol applying sodium bentonite and cationic surfactant - hexadecyltrimethylammonium bromide (HTAB) - or polyelectrolytes (polydiallyldimethylammonium chloride, poly-DADMAC and poly-amines). The removal efficiency of these model substrates was examined in model water using UV-Vis spectrophotometry, HPLC and TOC analysis. The clay mineral and HTAB were added in one step to the polluted model water in Jar-test experiments. The influence of the cation exchange capacity (CEC) of the applied clay mineral and the presence of polyaluminium chloride coagulant (BOPAC) were also tested for the water treatment process. The structures of the in situ produced and pre-prepared organoclay composites were compared by XRD analysis. The rapid formation of organoclay adsorbents provided very efficient removal of the dyes (65-90 % in 3-10 mg/L TOC(0) range) with 200 mg/L sodium bentonite dose, however thymol was less efficiently separated. Adsorption efficiencies of the composites were compared at different levels of ion exchange such as at 40, 60 and 100 %. In the case of thymol, the elimination of inorganic carbon from the model water before the TOC analysis resulted in some loss of the analysed volatile compound therefore the HPLC analysis was found to be the most suitable tool for the evaluation of the process. This one-step adsorption method using in situ formed organoclay was better performing than the conventional process in which the montmorillonite-surfactant composite is pre-preapared and subsequently added to the polluted water. The purification performance of this method was also evaluated on raw and artificially polluted thermal wastewater samples containing added thymol.

The anti-inflammatory activity of dillapiole and some semisynthetic analogues.

CONTEXT: Piper aduncum L. (Piperaceae) produces an essential oil (dillapiole) with great exploitative potential and it has proven effects against traditional cultures of phytopathogens, such as fungi, bacteria and mollusks, as well as analgesic action with low levels of toxicity. OBJECTIVE: This study investigated the in vivo anti-inflammatory activity of dillapiole. Furthermore, in order to elucidate its structure-anti-inflammatory activity relationship (SAR), semisynthetic analogues were proposed by using the molecular simplification strategy. MATERIALS AND METHODS: Dillapiole and safrole were isolated and purified using column chromatography. The semisynthetic analogues were obtained by using simple organic reactions, such as catalytic reduction and isomerization. All the analogues were purified by column chromatography and characterized by (1)H and (13)C NMR. The anti-inflammatory activities of dillapiole and its analogues were studied in carrageenan-induced rat paw edema model. RESULTS: Dillapiole and di-hydrodillapiole significantly (p<0.05) inhibited rat paw edema. All the other substances tested, including safrole, were less powerful inhibitors with activities inferior to that of indomethacin. DISCUSSION AND CONCLUSION: These findings showed that dillapiole and di-hydrodillapiole have moderate anti-phlogistic properties, indicating that they can be used as prototypes for newer anti-inflammatory compounds. Structure-activity relationship studies revealed that the benzodioxole ring is important for biological activity as well as the alkyl groups in the side chain and the methoxy groups in the aromatic ring.

Two new phenylpropanoid derivatives and other constituents from Illicium simonsii active against oral microbial organisms.

Bioassay-guided fractionation of the ethanol extract of the leaves and stems of Illicium simonsii led to the isolation of two new compounds, simonin A (1) and 1-hydroxyl-2- O- ß- D-6'-acetyl-glucopyranosyl-4-allylbenzene (2), along with eight known compounds. Their structures were elucidated by spectroscopic analysis. The isolates were tested for anti-oral microbial activity using a microdilution method. Compounds 1 and 3- 6 showed significant activities against oral microbial organisms (Actinomyces viscosus, Streptococcus mutans, Streptococcus sanguis, and Actinomyces naeslundii), with minimum inhibitory concentration (MIC) values ranging from 1.95 to 31.25 µg/mL in vitro.