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Manilkara zapota, also known as Sapodilla, is the best-known and most widely cultivated fruit from Sapotaceae. Sapodilla is a rich source of nutrients (sugars, acids, protein, amino acids), minerals (potassium, calcium, and iron), and comprises of a myriad of bioactive compounds, which are chiefly composed of ellagitannins, gallotannins, phenolic acid, depsides, and flavonoids (anthocyanins and flavanols). Owing to the rich phytochemical profile of its edible and non-edible parts, sapodilla has an enormous potential pharmacological applications that can be understood through various biological activities. In a comprehensive analysis, this review specifically describes the nutritional profile of sapodilla fruit, and provides current evidence on the bioactive potential of the different parts (edible as well as non-edible) of the sapodilla and highlights the main biological activities involved. The bioactive properties recommend the use of bioactive components of edible as well as non-edible portions of sapodilla in the development of innovative food and pharma products. This review also gives insights into sapodilla, as a potential and novel ingredient for its versatile food and non-food applications and the latest research advancements. The nutritional profile of sapodilla fruit and phytochemical diversity of sapodilla fruit and its by-products (peels, seeds, bark, leaves) make them potential sources of nutraceutical compounds from which functional foods can be obtained. Pharmacologically, both edible and non-edible portions of sapodilla has the potential to be an antioxidant, anticancer/anti-tumor, antimicrobial, analgesic, anti-inflammatory, and hepatoprotective agent. The article aimed to comprehensively collate some of the vital information published on sapodilla and review the potentiality of tapping bioactive compounds from sapodilla fruits and by products. Thus, this review would play an important role in understanding the scope for utilization of edible as well as non-edible parts of sapodilla plant in the food, pharmaceutical and cosmetic industries. • Sapodilla is a rich source of nutrients, minerals, and a myriad of bioactive phenolic compounds. • Sapodilla fruits and byproducts are rich in various bioactive compounds and possess diverse health benefits. • This review summarizes the nutritional as well as the phytochemical profile of the Sapodilla. • Bioactive properties of the Sapodilla and their application in functional food development is discussed. [ABSTRACT FROM AUTHOR]

Abstract Three new depsides, aspergisides A-C, and one new depsidone, aspergisidone, were isolated from the soil-derived fungus Aspergillus unguis PSU-RSPG204 together with one phthalide derivative and 11 depsidones including emeguisin A, aspersidone and folipastatin. The structures were determined by spectroscopic evidence. Aspersidone and emeguisin A showed remarkably antibacterial activity against Staphylococcus aureus and methicillin-resistance S. aureus with equal MIC values of 0.5 μ g/mL. Emeguisin A, which displayed the highest activity with 87.06% inhibition of human colon carcinoma (HCT-116) cell viability, decreased numbers of live cells/numbers of dead cells in a dose-dependent manner with the IC 50 values of 34.8–84.7 μ M in a 3D culture model depending on durations of incubation. In addition, folipastatin dose-dependently inhibited forskolin-stimulated chloride secretion in human intestinal epithelial (T84) cells with an IC 50 value of 0.5 μ M. These depsidones were considered to be inactive against noncancerous Vero Cells with the IC 50 values of >10 μ M. Graphical abstract Image 1 [ABSTRACT FROM AUTHOR]

Shoot cultures of Aronia melanocarpa , A . arbutifolia and A . ×  prunifolia were maintained on Murashige and Skoog medium with 1 mg/l each of BA and NAA under monochromatic lights (far-red, red, blue lights, UV-A-irradiation), in darkness, and under white light (control). HPLC-DAD analyses of 19 phenolic acids and 11 flavonoids in methanolic extracts from the shoots revealed in all of them the presence of three depsides (chlorogenic, neochlorogenic and rosmarinic acids), protocatechuic acid, four flavonoid glycosides (cynaroside, quercitrin, hyperoside and rutoside), and additionally, in A . arbutifolia , 3,4-dihydroxyphenylacetic acid. Depending on light quality, the total amounts of these metabolites increased 1.8–5.9 times, reaching maximum values under blue light: 527.40 and 144.61 mg 100 g −1 DW ( A . melanocarpa ), 543.27 and 85.82 mg 100 g −1 DW ( A . arbutifolia ) and 1615.18 and 220.65 mg 100 g −1 DW ( A . ×  prunifolia ), respectively. The maximum total amounts were 1.3–3.6 times higher than under white light. The quantities of individual metabolites changed from 1.2 to 11.0 times, with high amounts of neochlorogenic acid and quercitrin in A . melanocarpa (243.35 and 75.64 mg 100 g −1 DW), and of chlorogenic and rosmarinic acids and quercitrin in A . arbutifolia (236.52, 219.35 and 51.01 mg 100 g −1 DW). Extremely high amounts of depsides (418.83, 644.68, 548.86 mg 100 g −1 DW) and quercitrin (165.88 mg 100 g −1 DW) were produced in cultures of the hybrid - A . ×  prunifolia . The results are potentially useful for practical applications. This is the first report documented the importance of light quality on the production of phenolic acids and flavonoids in three aronia in vitro cultures. [ABSTRACT FROM AUTHOR]

Lichens are a large group of valuable lower plants with unique features and diverse applications worldwide such as in medicine, cosmetics, food, and textile industries. They are also well known for their potential in observing climate and environmental monitoring. Their successful exploitations require reliable analytical methods to check and maintain quality and efficacy of the products based on them. This study focuses on the development of a sensitive and reliable quantification method for the analysis of important depsides, depsidones, dibenzofuran and monocyclic phenols inseven known and an unidentified lichen species. Multiple Reaction Monitoring (MRM) approach using UHPLC-QqQ-MS instrument was employed for the development of the quantitative method. Both LC and MS parameters were optimized to ensure maximum separation. High sensitivity, and selectivity. LODs and LOQs were found to be in the range of 2.1–71.5 ng/mL and 6.3–212.9 ng/mL, respectively. The accuracy (% bias) and precision (% RSD) were found to be <5% in most cases. Metabolites 1–9 were found in the range of 0.5–41429 μg/g in the analysed lichen extracts. The analysis revealed that metabolites 1 , 2 and 3 are the predominant ones. This method can be used for the identification and absolute quantification of secondary metabolites in lichen extracts, and herbal or consumer products based upon them. [ABSTRACT FROM AUTHOR]

Phytochemical investigation of the roots of Salvia miltiorrhiza led to isolations of two new depsides ( 1 – 2 ), along with thirteen known compounds ( 3 – 15 ). Their structures and relative stereochemistry were elucidated by NMR spectral ( 1 H and 13 C NMR, HSQC, HMBC), CD and HR-ESIMS data analyses. The absolute configuration of 1 was determined by comparison of the experimental and calculated ECD spectra. All the depsides ( 1 − 10 ) were found to exhibit stronger free radical scavenging capacity (ranging from 2.62 to 22.05 μM) than diterpenoids ( 11 – 15 , IC 50 > 100 μM), among which Salvianolic acid A and Salvianolic acid B were the most potent compounds. Additionally, most of depsides ( 1 , 3 , 5 , 7 , 8 , 9 , 10 ) possessed significant protective effects against H 2 O 2 -induced H9c2 apoptosis in low concentrations. The negative mode collision-induced dissociations of compound 1 and 2 were featured by the α-cleavage and β-cleavage to lose danshensu (198 Da) and caffeic acid (180 Da), respectively, while α,β-dihydroxybenzenes depsides (8-hydroxy) showed characteristic neutral elimination of H 2 O. [ABSTRACT FROM AUTHOR]

This work aimed to investigate the effect of the two main components of rosemary extracts, namely rosmarinic acid (RA) and carnosic acid (CA), on the formation of advanced glycation end-products (AGEs) in vitro . In the bovine serum albumin (BSA)/glucose model, addition of RA and CA at 400 μg/mL inhibited fluorescent AGEs by more than 90%, and carboxymethyl lysine (CML) and carboxyethyl lysine (CEL) by 82.7% and 75.2%, and 71.4% and 64.2%, respectively. Moreover, the addition of RA and CA at 400 μg/mL inhibited fluorescent AGEs by more than 90% both in the BSA/glyoxal (GO) and BSA/methylglyoxal (MGO) models, the formation of CML by 64.9% and 53.9% in BSA/GO model, and CEL by 28.9% and 24.3% in BSA/MGO model, respectively. RA and CA also significantly decreased the concentration of MGO and protein carbonylation. [ABSTRACT FROM AUTHOR]

Persistent accumulation of reactive oxygen species causes cellular oxidative stress which contributes strongly towards the induction and progression of various diseases. Therapeutic focus has therefore shifted towards the use of antioxidants, with recent interest in those of plant origin. In the current study, rosmarinic acid (RA) and its key metabolites were evaluated in non-cellular and cellular antioxidant assays, using quercetin (Q) as a positive control. The non-cellular assay was performed as scavenging of DPPH radical, whilst the cellular assay was performed as protection from an oxidant stress. Radical-scavenging activity of RA and two of its primary metabolites, CA and DHPLA, were comparable to that of Q, whilst FA was of lower potency and m -CoA was inactive. In the cellular assay, RA and CA were markedly less potent than Q, with DHPLA, FA and m -CoA being inactive, this being true in short-term (5-h) or long-term (20‐ h) exposure conditions. However, antioxidant potency of Q and methyl rosmarinate, a non-ionisable ester of RA, was similar in the non-cellular and short-term cellular assays. It is proposed that marked ionisation of organic acids such as RA and its metabolites at physiological pH greatly limits their intracellular accumulation, and so attenuates intrinsic antioxidant ability demonstrated in the non-cellular assay. This study demonstrates some of the factors that prevent well-known phytochemicals from progressing further along the drug discovery chain. [ABSTRACT FROM AUTHOR]

Chlorogenic acid (CGA), one of the most abundant dietary polyphenolic compounds, has been reported to exhibit anti-inflammatory ability. However, the hepatoprotective effects and molecular mechanisms of CGA on concanavalin A (Con A)-induced hepatitis have not been explored. In the present study, we found that pretreatment with CGA dose-dependently inhibited the elevation of plasma aminotransferases and alleviated hepatic pathological damage as well as hepatocyte apoptosis in Con A-exposed mice. Additionally, CGA markedly suppressed the production of serum tumor necrosis factor (TNF)-α and interferon (IFN)-γ, alleviated the infiltration of hepatic macrophages, neutrophils, and activated CD4 + T lymphocytes in Con A-primed mice. Moreover, CGA downregulated Con A-induced hepatic expression of adhesion molecules (ICAM-1, VCAM-1 and ELAM-1) mRNA and protein, and inhibited Con A-activated Toll-like receptor (TLR) 4 signal molecules including TLR4, p-IRAK1, p-IκB, and p-p38. Finally, our results also showed that CGA exhibited a therapeutic effect, which CGA posttreatment improved hepatic damage at 1, 3, and 6 h after Con A. Taken together, these data suggested that CGA could effectively prevent mice from Con A-induced hepatitis, which might be through suppressing the activation of TLR4 signaling, downregulating the expression of adhesion molecules, and alleviating the infiltration and activation of hepatic leukocytes and the production of pro-inflammatory cytokines. [ABSTRACT FROM AUTHOR]

Both the conventional one-factor-at-a-time (OFT) optimization, in which one of the factors is varied maintaining the other parameters fixed at constant levels, and the central composite design (CCD) optimization, in which all factors are varied simultaneously, were carried out for silk dyeing with chlorogenic acid. The CCD experiments were designed with the help of Design-Expert 10.0.3 software (trial version) and used for evaluating the interactive effects of the four most important operating variables namely pH, temperature, time and dye concentration. The colour characteristics, fastness properties, FT-IR spectra and antioxidant activity of dyed fabrics were also evaluated. The silk fabrics dyed with chlorogenic acid displayed light yellowish brown colour, and exhibited good fastness properties and excellent antioxidant activity. [ABSTRACT FROM AUTHOR]

Background Rosemary, Rosmarinus (R.) officinalis L. is a well-known plant with several useful properties such as analgesic, anti-inflammatory and anti-neurodegenerative. It has been used in folk medicine to alleviate rheumatic pain, stomachache and dysmenorrhea. Rosemary has several constituents such as rosmarinic acid which can be responsible for therapeutic properties been noted with rosemary. The aim of this study was to investigate the potential anti-inflammatory effects of R. officinalis and rosmarinic acid in a rat model of sciatic nerve chronic constriction injury (CCI)-induced neuropathic pain to verify usage of rosemary in folk medicine. Methods Rats underwent CCI, were treated with either normal saline, ethanolic extract of aerial parts of R. officinalis (400 mg/kg, i.p.) or rosmarinic acid (40 mg/kg, i.p.) from the day of surgery (day 0) for 14 days. The anti-inflammatory effects of R. officinalis extract and rosmarinic acid were evaluated by assessing the levels of some spinal inflammatory markers including cyclooxygenase-2 (COX2), prostaglandin E2 (PGE-2), interleukin 1 beta (IL-1β), matrix metallopeptidase 2 (MMP2) through western blotting and nitric oxide (NO) production via Griess reaction on days 7 and 14 post-surgery. Results CCI rats exhibited a marked expression in the levels of inflammatory markers (COX2, PGE-2, IL-1β, MMP2 and NO) on both days 7 (p < 0.001) and 14 (p < 0.001). Rosmarinic acid and ethanolic extract of R. officinalis were able to decrease amounts of mentioned inflammatory markers on both days 7 (p < 0.001) and 14 (p < 0.001). Conclusion Our data support the traditional use of R. officinalis as an effective remedy for pain relief and inflammatory disorders. It also suggests that the ethanolic extract of R. officinalis and rosmarinic acid through modulating neuro-inflammation might be potential candidates in treating neuropathic pain and different neurological disorders associated with inflammation. [ABSTRACT FROM AUTHOR]

Dracocephalum forrestii , an important plant in Tibetan medicine, was transformed with Agrobacterium rhizogenes strain A4 to obtain hairy root culture. A maximum transformation frequency of 82% after seven weeks was obtained by inoculation of internodal stem segments. Six lines of hairy roots were obtained and cultured in darkness in Woody Plant (WPM) liquid medium. The transgenic nature of the hairy roots was investigated by PCR and RT-PCR. Three main compounds: rosmarinic acid (RA), salvianolic acid B (SAB) and caffeic acid (CA) were identified in extracts of D. forrestii hairy roots by UPLC-PDA-ESI-MS analysis. Quantitative HPLC analysis showed that RA levels were greatly increased in hairy roots (max. 19.97 mg/g DW) compared with the roots of one-year-old field grown plants (4.7 mg/g DW), but SAB levels were significantly lower in transformed roots (max. 11.7 mg/g DW) than in untransformed roots (16.4 mg/g DW). Caffeic acid was detected only in transformed roots. A time course experiment with the most productive hairy root line showed that a culture period of 30 days and a medium supplemented with 3% of sucrose was optimal for biomass and production of analysed phenolic compounds. Production remained stable over at least 3.5 years of continuous subculturing of the hairy roots. [ABSTRACT FROM AUTHOR]

To shed light on colon cancer chemoprevention, natural phytochemicals attract researchers by virtue of their beneficial biological effects. The chemopreventive potential of rosmarinic acid (RA) was tested by using the colon carcinogen, 1,2-dimethylhydrazine (DMH) by evaluating the Aberrant crypt foci (ACF), tumour incidence, lipid peroxidative byproducts, phase I & II drug metabolizing enzymes, cell proliferative and apoptotic proteins. Rats were divided into six groups and received modified pellet diet. Group 1 served as control rats, group 2 rats received RA (5 mg/kg b.w. p.o.), rats in groups 3–6 received DMH (20 mg/kg b.w., s.c.) for the first fifteen weeks. In addition to DMH, groups 4–6 received RA at the dose of 5 mg/kg b.w. during initiation, post initiation stages and also for the entire study period. DMH treated rats showed an increase in the development of ACF, tumour formation and multiplicity and decrease in lipid peroxidative byproducts. Moreover, it modulates xenobiotic enzymes and reduces the expressions of proapoptotic proteins; increases expressions of anti apoptotic proteins at the end of the study. Supplementation with RA to carcinogen treated rats protected them from the above deleterious effects caused by DMH and thus RA may be used as a potent chemopreventive agent. [ABSTRACT FROM AUTHOR]

Oxidative damage is one of the hallmarks of the aging process. The current study evaluated effects of two proprietary antioxidant-based ingredients, rosemary extract and spearmint extract containing carnosic acid and rosmarinic acid, respectively, on learning and memory in the SAMP8 mouse model of accelerated aging. The two rosemary extracts contained carnosic acid (60% or 10% carnosic acid) and one spearmint extract contained 5% rosmarinic acid. Three doses of actives in each extract were tested: 32, 16, 1.6 or 0 mg/kg. After 90 days of treatment mice were tested in T-maze foot shock avoidance, object recognition and lever press. Rosemary extract containing 60% carnosic acid improved acquisition and retention in T-maze foot shock, object recognition and lever press. Rosemary extract with 10% carnosic acid improved retention in T-maze foot shock avoidance and lever press. Spearmint with 5% rosmarinic acid improved acquisition and retention in T-maze foot shock avoidance and object recognition. 4-hydroxynonenal (HNE) was reduced in the brain cortex after treatment with all three extracts (P < 0.001) compared to the vehicle treated SAMP8. Protein carbonyls were reduced in the hippocampus after administration of rosemary with 10% carnosic acid (P < 0.05) and spearmint containing 5% rosmarinic acid (P < 0.001). The current results indicate that the extracts from spearmint and rosemary have beneficial effects on learning and memory and brain tissue markers of oxidation that occur with age in SAMP8 mice. [ABSTRACT FROM AUTHOR]

Diffractaic acid (DA) is a secondary metabolite of lichens that belongs to the chemical class of depsides, and some relevant pharmacological properties are associated with this natural product, such as antioxidant, antiulcerogenic and gastroprotective effects. Considering the relevant biological activities and taking into account that the activities are intrinsically related to the structure, the main goal of this study was to elucidate the structure of diffractaic acid by single crystal X-ray diffraction as well to characterize its physicochemical properties by powder X-ray diffraction, thermal analysis and vibrational spectroscopy. It was observed that DA belongs to the monoclinic crystal system, crystallizing in the space group P 2 1 / c with the following cell parameters: a = 18.535(7) Å, b = 4.0439(18) Å, c = 23.964(6) Å, β = 91.55(3)°. The crystal packing is characterized by difractaic acid dimers, which are reflected in the vibrational spectrum. These observations were supported by quantum mechanical calculations. [ABSTRACT FROM AUTHOR]

Salvia miltiorrhiza (SM) Bunge is one of the widely-used Chinese medicinal herbs. In this study, the chemical constituents and anticancer potential of SM stems and leaves were examined with those of respective callus cultures. The callus culture for stem and leaf explants was initiated in modified Murashige and Skoog (MS) medium. Active constituents of respective extracts were analyzed by high performance liquid chromatography coupled with DAD and MS (HPLC–DAD–MS). Rosmarinic acid (RA) and salvianolic acid B (Sal B) were determined to be the main phenolic compounds. Quantitative analyses revealed that callus stem extracts produced higher amount of RA and Sal B (stem RA: 1.27 ± 0.38%; stem Sal B: 0.87 ± 0.20%) than callus leaf did (leaf RA: 0.28 ± 0.02%; leaf Sal B: 0.07 ± 0.03%). Stem and leaf callus extracts exerted cytotoxic effects towards CCRF-CEM cells (stem: 13.1 ± 0.90 μg/ml; leaf: 18.1 ± 0.33 μg/ml). As expected, stem extract with higher amount of RA and Sal B showed lower IC 50 value than leaf extract. These findings suggest the possibility to isolate bioactive constituents with anticancer properties from in vitro callus cultures of stems and leaves of SM. [ABSTRACT FROM AUTHOR]

Rosmarinic acid (RA), a compound found in several plant species, has beneficial properties, including anti-inflammatory and antibacterial effects. We investigated the toxicity, anti-inflammatory, and antifibrotic effects of RA using precision-cut liver slices (PCLS) and precision-cut intestinal slices (PCIS) prepared from human, mouse, and rat tissue. PCLS and PCIS were cultured up to 48 h in the absence or presence of RA. Gene expression of the inflammatory markers: IL-6, IL-8/CXCL1/KC, and IL-1β, as well as the fibrosis markers: pro-collagen 1a1, heat shock protein 47, α-smooth muscle actin, fibronectin (Fn2) and plasminogen activator inhibitor-1 (PAI-1) were evaluated by qPCR. RA was only toxic in murine PCIS. RA failed to mitigate the inflammatory response in most models, while it clearly reduced IL-6 and CXCL1/KC gene expression in murine PCIS at non-toxic concentrations. With regard to fibrosis, RA decreased the gene levels of Fn2 and PAI-1 in murine PCLS, and Fn2 in murine PCIS. Yet, no effect was observed on the gene expression of fibrosis markers in human and rat PCIS. In conclusion, we observed clear organ- and species-specific effects of RA. RA had little influence on inflammation. However, our study further establishes RA as a potential candidate for the treatment of liver fibrosis. [ABSTRACT FROM AUTHOR]

Phenolic acids are among the important bioactive compounds found in Salvia miltiorrhiza Bunge. Rosmarinic acid (RA) has been identified as the core structure of most phenolic acids in this widely useful herb. This work describes a comparative analysis of the expression patterns of RA biosynthetic genes in relation to different accumulation patterns of phenolic acid contents in two danshen genotypes, DS1 ( S. miltiorrhiza ) and DS2 ( S. miltiorrhiza f. alba C.Y.Li). Quantitative real-time PCR (qRT-PCR) showed that the transcriptional expression levels of most of the genes were significantly higher in DS1 than in DS2. The results indicated that the higher RA accumulation observed in DS1 might be a result of the up-regulation of several co-expressed genes in this metabolic pathway. SmPAL , SmC4H , Sm4CL and SmHPPD may serve as key genes in the regulation of RA accumulation in DS1. SmTAT might play a more important role in regulating the content of salvianolic acid B (SAB) . Overall, our results provide new information on the expression profiles of biosynthetic genes in connection with phenolic acid accumulation at the molecular level in two danshen germplasm selections. [ABSTRACT FROM AUTHOR]

Dereplication methodology using UHPLC–DAD–QTOFMS was applied during the metabolic profiling investigation of the endophyte Setophoma sp., a fungus isolated from symptomless guava fruits. The approach performed allowed a fast analysis of the microbial secondary metabolites. From this fungus, seven highly C-alkylated depsides were isolated and identified as polyketides thielavins S, T, U and V and lecanorins D, E and F. Their structures were elucidated through spectroscopic methods including NMR, HRMS and especially with assistance of HRMS/MS experiments. The compounds were tested for quorum sensing regulation activity in the virulence gene expression of Staphylococcus aureus , but no inhibitory effect was detected. Nevertheless, moderate antibacterial activity was encountered in three of tested depsides, particularly with thielavin T, whose MIC was 6.25 μg/mL against S. aureus . [ABSTRACT FROM AUTHOR]

Rosmarinic acid (RA, an ester of caffeic acid and 3,4-dihydroxyphenyllactic acid) has a number of biological activities, but little is known about anti-leukemic activities of RA combined with all-trans retinoic acid (ATRA) against acute promyelocytic leukemia (APL) cells. We examined the differentiation marker, CD11b, in bone marrow cells (BMC) of an APL patient, in NB4 cells (APL cell line), and in normal BMC and peripheral blood mononuclear cells (PBMC) of healthy subjects by flow cytometric analysis. ATRA/RA induced expression of CD11b in the BMC of the APL patient and in NB4 cells, but not in normal BMC or PBMC. Therefore, we realized that RA potentiated ATRA-induced macrophage differentiation in APL cells. Further characterization of the induced macrophages showed that they exhibited morphological changes and were able to phagocytose and generate reactive oxygen species. Th also had typical expression of C–C chemokine receptor type 1 (CCR1), CCR2, and intercellular adhesion molecule-1 (ICAM-1). Moreover, the expression of CD11b + and CD14 + cells depended on ERK-NF-κB axis activation. Together, these results indicate that RA potentiates ATRA-induced macrophage differentiation in APL cells. Thus, RA may play an important role as an appurtenant differentiation agent for functional macrophage differentiation in APL. Additionally, the differentiated macrophages might have a normal life span and, they could die. These data indicate that co-treatment with RA and ATRA has potential as an anti-leukemic therapy in APL. [ABSTRACT FROM AUTHOR]

Inhibition of hypoxia inducible factor-prolyl hydroxylase-2 (HPH), leading to activation of hypoxia inducible factor (HIF)-1 is a potential therapeutic strategy for the treatment of colitis. Rosmarinic acid (RA), an ester of caffeic acid and 3,4-dihydroxyphenyllactic acid is a naturally occurring polyphenolic compound with two catechols, a or inhibition of HPH. To improve accessibility of highly hydrophilic RA to HPH, an intracellular target, RA was chemically modified to decrease hydrophilicity. Of the less-hydrophilic derivatives, rosmarinic acid methyl ester (RAME) most potently inhibited HPH. Accordingly, RAME prevented hydroxylation of HIF-1α and consequently stabilized HIF-1α protein in cells. RAME inhibition of HPH and induction of HIF-1α were diminished by elevated doses of the required factors of HPH, 2-ketoglutarate and ascorbate. RAME induction of HIF-1α led to activation of an ulcer healing pathway, HIF-1-vascular endothelial growth factor (VEGF), in human colon carcinoma cells. RAME administered rectally ameliorated TNBS-induced rat colitis and substantially decreased the levels of pro-inflammatory mediators in the inflamed colonic tissue. In parallel with the cellular effects of RAME, RAME up-regulated HIF-1α and VEGF in the inflamed colonic tissue. Thus, lipophilic modification of RA improves its ability to inhibit HPH, leading to activation of the HIF-1-VEGF pathway. RAME, a lipophilic RA derivative, may exert anti-colitic effects via activation of the ulcer healing pathway. [ABSTRACT FROM AUTHOR]

Rosmarinic acid and salvianolic acid B are two important phenolic compounds with therapeutic properties in Salvia miltiorrhiza Bunge. The biosynthesis of rosmarinic acid is initiated by two parallel pathways, namely the phenylpropanoid pathway and the tyrosine-derived pathway. Salvianolic acid B is a structural dimer of rosmarinic acid and is believed to be derived from rosmarinic acid. In the current study, methyl jasmonate (MeJA) and hyphal extracts from fungi were used as elicitors to examine the relationship between enzymes in the two parallel pathways and accumulation of phenolic compounds in S. miltiorrhiza hairy root cultures. The results showed that accumulations of rosmarinic acid, salvianolic acid B and total phenolics were enhanced by MeJA while suppressed by fugal extracts. Responses of enzymes in the tyrosine-derived pathway, at both the gene transcript and enzyme activity levels, showed a better consistency with alterations of phenolic compounds content after the two elicitors treated. Our study implied that compared with enzymes in the phenylpropanoid pathway, enzymes in the tyrosine-derived pathway are more correlated to rosmarinic acid and salvianolic acid B biosynthesis in S. miltiorrhiza hairy roots. [Copyright &y& Elsevier]

Highlights: [•] Rosmarinic acid ameliorated increased serum creatinine and blood urea nitrogen in cisplatin-intoxicated mice. [•] The increase in renal 4-hydroxynonenal, cytochrome P450 2E1 and heme oxygenase-1 expression was significantly reduced. [•] Rosmarinic acid inhibited the expression of pro-inflammatory nuclear factor-kappaB and tumor necrosis factor-alpha. [•] Rosmarinic acid reduced the expression of p53, phosphoserine-15 p-p53 and active caspase-3 in the kidneys. [ABSTRACT FROM AUTHOR]

Abstract: Lemon balm (Melissa officinalis; Lamiaceae) plants were exposed to background ozone (O3) dosages (80ppb for 5h), because high background levels of O3 are considered to be as harmful as episodic O3 peaks. Immediately at the end of fumigation the plants appeared visually symptomless, but necrotic lesions were observed later. The biosynthesis of rosmarinic acid (RA) comprises eight enzymes, among them phenylalanine ammonia-lyase (PAL), 4-coumarate:coenzyme A ligase (4CL), tyrosine aminotransferase (TAT) and rosmarinic acid synthase (RAS). The transcript levels of these genes have been investigated by quantitative RT-PCR. There was a quick up-regulation of all genes at 3h of O3 exposure, but at 24h from beginning of exposure (FBE) only RAS and PAL were up-regulated. The specific activity of RAS was closely correlated with a decrease of RA concentration in lemon balm leaves. The specific activity of PAL increased at 12h FBE to 163% in comparison to control levels. This work provides insight into the effect of O3 stress on the formation of the main phenolic ingredient of the pharmaceutically important plant M. officinalis. [Copyright &y& Elsevier]

The reactivity of eight purified depsides obtained from six european lichens and that display as 2-oxoalkyl chain in ortho -position of the ester bond was explored. These depsides were found to lead to 1 H -Isochromen-1-ones, which exhibit a distinctive blue fluorescence at 365 nm, in the presence of a 10% aqueous solution of KOH. A mechanistic explanation, involving the formation of an enolate intermediate and intramolecular transesterification, was proposed and validated by DFT. By exploiting this fluorescent phenomenon, we conceived a chemical probe (the KUV probe) that is useful for lichen determination, as exemplified on a selection of European Porpidia species. [Display omitted] • Extraction from lichens and purification of eight depsides bearing a δ-keto ester moiety. • Intramolecular transesterification under basic conditions yield blue fluorescent 1 H -isochromen-1-ones. • Mechanistic proposition and DFT validation of this rearrangement involving an enolate intermediate. • Conception of a new chemical probe named KUV probe for lichen determination: application to European Porpidia lichens. [ABSTRACT FROM AUTHOR]

Highlights: [•] A separation methodology of rosmarinic acid (RA) using GRAS solvents was developed. [•] The recovery of rosmarinic acid from rosemary waste was assessed. [•] A process to obtain bioactive compounds from rosemary leafs was proposed. [•] The cost of manufacturing of RA from rosemary growing in Brazil was evaluated. [Copyright &y& Elsevier]

Highlights: [•] An endophytic fungus from Hintonia latiflora produces thielavins A, J and K. [•] Thielavins A, J and K are inhibitors of yeast α-glucosidase. [•] Thielavins A, J and K could bind to α-glucosidases close to the catalytic site. [•] Thielavin K decreases fasting and postprandial glucose levels in vivo. [•] Thielavin-type tridepsides represent a hitherto unknown class of α-glucosidase inhibitors. [Copyright &y& Elsevier]

Highlights: [•] EPCR shedding is involved in the vascular inflammation. [•] EPCR shedding is mediated by PMA activation. [•] RA inhibited the PMA and CLP-induced EPCR shedding by suppressing TACE expression. [•] RA reduced PMA-stimulated phosphorylation of p38, ERK1/2 and JNK. [ABSTRACT FROM AUTHOR]

Abstract: A chemical study of the lichen Ramalina siliquosa complex found in Brittany was conducted. Eight chemotypes were considered and their chemical composition was elucidated for the first time by LC–MS analysis. Ten main compounds were identified: conhypoprotocetraric acid (1), salazinic acid (2), peristictic acid (3), cryptostictic acid (4), protocetraric acid (5), stictic acid (6), norstictic acid (7), hypoprotocetraric acid (8), 4-O-demethylbarbatic acid (9), (+)-usnic acid (10) and 22 minor compounds were reported. The MS/MS fragmentation patterns of each compound of R. siliquosa complex were determined and proposed. [Copyright &y& Elsevier]

Abstract: This study was carried out to investigate the chemopreventive potential of rosmarinic acid (RA) against 1,2-dimethylhydrazine (DMH) induced rat colon carcinogenesis by evaluating the effect of RA on tumour formation, antioxidant enzymes, cytochrome P450 content, p-nitrophenol hydroxylase and GST activities. Rats were divided into six groups and fed modified pellet diet for the entire experimental period. Group 1 served as control, group 2 received RA (10mg/kgb.w.). Groups 3–6 were induced colon cancer by injecting DMH (20mg/kgb.w.) subcutaneously once a week for the first four weeks (groups 3–6). In addition, RA was administered at the doses of 2.5, 5 and 10mg/kgb.w. to groups 4–6 respectively. DMH treated rats showed large number of colonic tumours; decreased lipid peroxidation; decreased antioxidant status; elevated CYP450 content and PNPH activities; and decreased GST activity in the liver and colon. Supplementation with RA (5mgkg/b.w.) to DMH treated rats significantly decreased the number of polyps (50%); reversed the markers of oxidative stress (21.0%); antioxidant status (38.55%); CYP450 content (29.41%); and PNPH activities (21.9%). RA at the dose of 5mg/kgb.w. showed a most pronounced effect and could be used as a possible chemopreventive agent against colon cancer. [Copyright &y& Elsevier]

Abstract: A series of MMP-1 inhibitors have been identified based upon a methyl rosmarinate scaffold using structure-based drug design methods. The best compound in the series showed an IC50 value of 0.4 μM. A docking study was conducted for compound (S)-10n in order to investigate its binding interactions with MMP-1. The structure–activity relationships (SAR) were also briefly discussed. Useful SAR was established which provides important guidelines for the design of future generations of potent inhibitors against MMP-1. [Copyright &y& Elsevier]

Abstract: We herein describe the identification of four new depsides present in methanol extract of Origanum dictamnus. O. dictamnus’ (dittany) aerial parts methanol extract was subjected to semi-preparative RP-HPLC fractionation followed by identification of individual compounds in each fraction using 1D/2D NMR, MS approaches and DFT calculations. The structural data revealed that 4 of the compounds were novel hitherto unidentified molecules, whereas the other 6 corresponded to known structures belonging to the groups of monoterpenes, phenolic acids and depsides. We have additionally estimated the antioxidant capacity of the methanol extract and individual fractions using the 1,1-diphenyl-2-picrylhydrazyl (DPPHlic>in vitro assay. Methanol extract exhibited significant scavenging activity, which was attributed predominantly to the depside group of phytochemicals. The scavenging activity of the new compounds is reported herein for first time. Moreover, the antimitotic activities of the methanol extract as well as that of rosmarinic acid were examined and appeared to be several fold weaker comparing to their scavenging capacity. [Copyright &y& Elsevier]

Abstract: Lichen substances (i.e. lichen-specific carbon-based secondary compounds) are known to be involved in the uptake and immobilization of metal ions, though the biochemical mechanisms of this interaction are largely unexplained. Previous research on potential effects of lichen substances on heavy metal uptake and tolerance mostly focused on lichens in heavily polluted areas with exceptionally high metal concentrations. In the present study, we aimed at gathering information as to whether lichen substances might be involved in the fine-tuning of metal uptake even at not or low-polluted sites. Therefore, we studied lichen substance concentrations in the epiphytic lichen Hypogymnia physodes and metal concentrations in its substratum in a montane spruce forest of Germany. H. physodes produces two depsides and five depsidones, which had been shown to be involved in metal homeostasis, namely in Cu and Mn uptake, in previous laboratory experiments. The amount of lichen substances increased with increasing heavy metal concentration in the substratum, though the latter varied only in the range of a few μmolg−1 between the sample trees. Variability of lichen substance concentrations in H. physodes within the individual trees was low. Among the different lichen substances of H. physodes, the amount of the depsidone physodalic acid relative to the total of lichen substances was most closely correlated to the concentrations of Cu and Mn in the substratum, whereas the amount of the depsidone 3-hydroxyphysodic acid decreased both with increasing concentrations of these two metals and physodalic acid. Thus, our data suggest that lichen substances contribute to metal homeostasis not only in heavy metal-rich habitats, but also at not or low-polluted sites where the lichen substances apparently help to maintain constant intracellular metal concentrations despite of spatially varying availabilities of metal ions. [Copyright &y& Elsevier]

Abstract: The edible fruits of Myrciaria vexator McVaugh (Myrtaceae), from northern South America, are eaten in certain locales, either fresh or processed into jellies and drinks. Activity-guided fractionation of M. vexator resulted in identification of ellagic acid (1), cyanidin-3-O-glucoside (2), delphinidin-3-O-glucoside (3), 2-O-(3,4-dihydroxybenzoyl)-2,4,6-trihydroxyphenylacetic acid (4), and jaboticabin (5), and latter two compounds are being reported for the first time in this species. Ellagic acid was further examined, and found to inhibit cigarette smoke extract induced MMP-1 expression in vitro, and may be of significance in the treatment of chronic obstructive pulmonary (COPD). Other compounds identified for the first time from M. vexator include cyanidin-3-O-galactoside (6), cyanidin-3-O-arabinoside (7), cyanidin-3-O-rutionoside (8), petunidin (9), peonidin-3-O-galactoside (10) malvidin (11), hyperoside (12), querecetin-3-O-glucoside (13), and guajaverin (14), methyl protocatechuate (15), and protocatechuic acid (16). [Copyright &y& Elsevier]

Abstract: A new HPTLC method was envisaged to determine rosmarinic acid (RA) in different matrices with the aim of testing the influence of optimizing the main HPTLC operative parameters in view of a more stringent validation process. HPTLC LiChrospher silica gel 60 F254s, 20cm×10cm, plates with toluene:ethyl formate:formic acid (6:4:1, v/v) as the mobile phase were used. Densitometric determinations were performed in reflectance mode at 330nm. The method was validated giving rise to a dependable and high throughput procedure well suited to routine applications. RA was quantified in the range of 132–660ng with RSD of repeatability and intermediate precision not exceeding 2.0% and accuracy within the acceptance limits. The method was tested on several commercial preparations containing RA in different amounts. [Copyright &y& Elsevier]

Abstract: In this study, the influences of cultivar on the phenolic composition and antioxidant properties of 15 different basil varieties was determined. Cultivar had a statistically significant effect on total phenolic levels (p <0.001) and anthocyanin concentrations (p <0.001). Analysis of individual phenolic acid levels by high-performance liquid chromatography showed substantial variations in the phenolic acid profiles among cultivars. Rosmarinic (p <0.001), chicoric (p =0.002) and caffeic (p =0.001) acid concentrations were affected by cultivar, although caftaric acid levels (p =0.083) were not. Nine of the cultivars in this study contained chicoric acid in higher concentrations than rosmarinic acid. These are the first basil cultivars that have been identified in which rosmarinic acid is not the dominant phenolic acid. In addition, six of the cultivars in this study had caftaric and caffeic acid concentrations that were similar or higher than rosmarinic acid levels. Cultivar also had a significant impact on both FRAP (ferric reducing antioxidant power, p =0.007) and DPPH (2,2′-diphenyl-1-picrylhydrazyl, p =0.004) antioxidant capacities. For the basil cultivars in this study, the individual phenolic acid composition was found to be an important factor influencing the measured antioxidant capacity. [Copyright &y& Elsevier]

Abstract: Many lichens can cope with heavy-metal stress, however, the mechanisms of lichen tolerance are still not fully understood. Some lichen secondary metabolites (depsides and depsidones), produced in lichens by the fungal symbiont and accumulated on the outer surface of its hyphae, are supposed to play an important role in the extracellular immoblilization of heavy metals. Lichen photobionts (algal partners in the symbiosis), although surrounded by the mycobiont hyphae, may also accumulate high amounts of trace metals. This can lead to physiological disruptions and morphological damage in algal cells and hence affect the lichen physiological status. We hypothesized that lichen species/specimens living in heavily polluted sites and showing HM tolerance possess a higher content of secondary metabolites than those living in unpolluted sites. Hence, their photobionts can be better protected from the excess of metal ions and need to produce less metal-complexing phytochelatins (PCn) to combat metal toxicity. Specimens of Hypocenomyce scalaris, Cladonia furcata and Lepraria spp. sampled from Zn/Pb-polluted and control sites were compared for the accumulation of Zn/Pb and secondary metabolites, as well as for their production of phytochelatins and glutathione in response to experimental Zn or Pb exposure. Generally, the lichen specimens sampled from the HM-polluted site contained higher amounts of Zn and Pb as well as lichen substances (different depsides and depsidones) than those from the control site. A strong positive correlation was found between the accumulation of secondary metabolites and Zn/Pb accumulation (R 2 =0.98 and 0.63, respectively). For the first time, production of phytochelatins (PC2–3) in response to Zn and Pb (50–200μM) exposure was found in H. scalaris, L. elobata, L. incana and C. furcata. In both species of Lepraria also cysteine, a substrate for GSH and PCs synthesis was detected. The lichens from the polluted site produced under the same exposure conditions, or in response to higher metal concentrations, lower amounts of PCn than those sampled from the control site. It strongly suggests that less Zn and Pb ions reached the photobiont cells of the lichens containing higher amounts of secondary metabolites (lecanoric, fumarprotocetraric, stictic, constictic acids, antranorin). The results obtained support the putative role of some metabolites in heavy-metal tolerance of the lichens inhabiting metal-polluted habitats. [Copyright &y& Elsevier]

Abstract: Lemon balm (Melissa officinalis L.; Lamiaceae) is a well-known medicinal plant mainly due to two groups of compounds, the essential oil and the phenylpropanoid derivatives. The prominent phenolic compound is rosmarinic acid (RA), an ester of caffeic acid and 3,4-dihydroxyphenyllactic acid. RA shows a number of interesting biological activities. Rosmarinic acid synthase (RAS; 4-coumaroyl-CoA:hydroxyphenyllactic acid hydroxycinnamoyltransferase) catalyses the ester formation. Cell cultures of M. officinalis have been established in order to characterise the formation of RA in an important diploid medicinal plant. RAS activity as well as the expression of the RAS gene are closely correlated with the accumulation of RA in suspension cultures of M. officinalis. The RAS cDNA and gene (MoRAS) were isolated. The RAS gene was shown to be intron-free. MoRAS belongs to the BAHD superfamily of acyltransferases. Southern-blot analysis suggests the presence of only one RAS gene copy in the M. officinalis genome. The enzyme was characterised with respect to enzyme properties, substrate preferences and kinetic data in crude plant extracts and as heterologously synthesised protein from Escherichia coli. [Copyright &y& Elsevier]

Background: Depside salts from Salvia miltiorrhiza, with active components of lithospermic acid B (LSB), rosmarinic acid (RA), and lithospermic acid (LA), are a multicomponent drug marketed in China for the treatment of coronary heart disease. Objectives: The aims of this study were to determine the concentrations of LSB, RA, and LA in human plasma and urine, and to compare the pharmacokinetic properties of depside salts from S miltiorrhiza in healthy Chinese volunteers. Methods: A randomized, open-label, single-dose study was conducted in healthy Chinese volunteers. Participants were randomly assigned to receive a single intravenous infusion of 100 or 200 mg of depside salts from S miltiorrhiza. Blood was collected through a venous cannula prior to study drug administration (0 min) and at 10, 20, 30, 60, 65, 70, 80, and 90 minutes and 2, 3, 4, 6, 8, 12, and 24 hours after study drug administration. Urine samples were taken before study drug administration (0) and at 0 to 12 and 12 to 24 hours after study drug administration. LSB, RA, and LA concentrations in serum and urine were analyzed by an LC-MS/MS method. Tolerability was determined by clinical assessment; vital signs (ie, blood pressure, heart rate, breathing rate, body temperature) monitoring at baseline and at the end of the study, clinical laboratory tests (ie, hematology, blood biochemistry, hepatic function, renal function, urinalysis), 12-lead ECG measurements, and physical examinations at baseline and after completion of the study. Results: Twelve Chinese volunteers (6 males, 6 females; mean [SD] age, 25.2 [3.8] years; mean height, 165.7 [8.9] cm; mean body mass index, 21.6 [2.5] kg/m2) were enrolled in the study. Peak plasma concentrations of LSB, RA and LA were observed at 0.3 to 1 hour following the 1-hour intravenous infusion, with respective mean (SD) Cmax of 4925 (1861), 174 (61), and 361 (101) ng/mL for the 100-mg dose and 10,285 (2259), 308 (77), and 674 (85) ng/mL for the 200-mg dose. The AUClast values for LSB, RA, and LA were 4537 (1265), 129 (28), and 1229 (330) ng/mL/h, respectively, for the 100-mg dose and 10,426 (2589), 260 (53), and 2792 (729) ng/mL/h for the 200-mg dose. No significant difference in pharmacokinetic parameters was observed between male and female subjects. Three metabolites were found in the plasma with low concentrations. The urinary excretion recoveries of LSB, RA, and LA were 0.58% (0.42%), 25.21% (20.61%), and 10.02% (7.72%) for the 100-mg dose and 0.38% (0.18%), 20.11% (10.50%), and 6.34% (3.20%) for the 200-mg dose. No adverse events were reported by the subjects or found by the investigators in the analysis of vital signs, 12-lead ECG measurements, physical examinations, or clinical laboratory tests. Conclusions: Following single intravenous infusion of 100 or 200 mg of depside salts from S miltiorrhiza to healthy Chinese subjects, no statistical differences in pharmacokinetic parameters were observed between males and females. The 2 doses of depside salts from S miltiorrhiza were clinically well tolerated during the study. [Copyright &y& Elsevier]

The depsidone fumarprotocetraric acid as well as the depsides perlatolic and thamnolic acids are lichen secondary metabolites. Their first dissociation constants (pKa1) in methanol were determined to be 2.7 for perlatolic acid and 2.8 for fumarprotocetraric and thamnolic acids by UV spectroscopy. Lower pKa1 values are, so far, not known from lichen substances. Several lichens producing at least one of these compounds are known for their outstanding tolerance to acidic air pollution. This is demonstrated by evaluating published pH preferences for central European lichens. The low pKa1 values suggest that strong dissociation of the studied lichen substances is a prerequisite for the occurrence of lichens with these compounds on very acidic substrata, as protonated lichen substances of different chemical groups, but not their conjugated bases, are known to shuttle protons into the cytoplasm and thereby apparently damage lichens. [Copyright &y& Elsevier]

Abstract: Twenty-six depsides were synthesized to screen for their antibacterial activity. All of them were reported for the first time. Their chemical structures were clearly determined by 1H NMR, 13C NMR, ESI mass spectra and elemental analyses, coupled with one selected single-crystal structure. All the compounds were assayed for antibacterial activities against three Gram-positive bacterial strains (Bacillus subtilis ATCC 6633, Staphylococcus aureus ATCC 6538 and Streptococcus faecalis ATCC 9790) and three Gram-negative bacterial strains (Escherichia coli ATCC 35218, Pseudomonas aeruginosa ATCC 13525 and Enterobacter cloacae ATCC 13047) by MTT method. Compound 2-(2-methoxy-2-oxoethyl)phenyl 3-nitrobenzoate (C10) and 2-(2-ethoxy-2-oxoethyl)phenyl 3-nitrobenzoate (C23) showed powerful antibacterial activities against B. subtilis with MIC of 0.78μg/mL while compound 2-(2-methoxy-2-oxoethyl)phenyl 2-(3,4-diethoxyphenyl)acetate (C8) and 2-(2-ethoxy-2-oxoethyl)phenyl 2-(3,4-diethoxyphenyl)acetate (C21) exhibited significant antibacterial activities against E. coli with MIC of 1.562μg/mL, which were superior to the positive controls penicillin G and kanamycin B, respectively. On the basis of the biological results, structure–activity relationships were discussed. [Copyright &y& Elsevier]

Abstract: Lichens are known to produce a variety of secondary metabolites including polyketides that have diverse biological role(s). The biosynthesis of fungal polyketides is governed by type I polyketide synthases (PKS), enzymes with a multidomain structure, including the β-ketoacyl synthase (KS), acyl transferase (AT), ketoreductase (KR), dehydratase (DH), enoyl reductase (ER) and acyl carrier protein (ACP) domains. Established soredial cultures of Dirinaria applanata (Fée) producing atranorin and divaricatic acid were used to characterize a polyketide synthase gene (DnPKS). A 743bp fragment corresponding to the ketosynthase domain (KS) was isolated using degenerate primers. Complete sequence information for DnPKS (8162bp) was obtained by walking in the 5′and 3′ directions of the isolated KS domain using TAIL PCR. A translation of the DnPKS sequence identified the presence of KS, AT, two ACP and TE domains with eight intervening introns. TBLASTX analysis and comparison with other PKS sequences suggest that the coding region of DnPKS sequence is complete with the identification of putative start and stop codons and a stretch of 1226 upstream of the start codon corresponding to the putative promoter. This sequence shows the presence of putative binding sites for fungal transcription factors such as AflR, AreA and PacC. Southern blot analysis suggests that additional DnPKS-like genes may be present in the D. applanata genome. Additionally, expression of a DnPKS-like transcript was examined under different culture conditions and found to be down-regulated by sucrose and up-regulated by mannitol, UV and neutral pH. [Copyright &y& Elsevier]

Abstract: FT-Raman spectroscopy has been used for the analytical characterization of the Parmotrema tinctorum Del. Ex Nyl. lichen. Lecanoric acid, the major lichen chemical present in the total mass, has been extracted from the lichen, purified and characterized by Raman spectroscopy supported by means of theoretical DFT calculations. The calculations indicate that the aromatic ring A of the lecanoric acid structure is kept in the molecular plane by a strong hydrogen bond between the ortho-hydroxyl group of ring A and the ester group; this hydrogen bond is shorter in the C1 isomer form, which is the main feature responsible for the Gibbs free energy difference (−2.96kcal/mol) favouring the C1 isomer. In spite of the similarity of possible conformers and although many of the predicted Raman bands are found to be common for both forms, there is one Raman transition very characteristic of structure C2, centred at 1815cm−1, assigned to the stretching of the Cf the ester moiety (ν(C. For the isomer C1 this transition was predicted at 1729cm−1, with a lower frequency ascribed to the stronger hydrogen bond present in the latter conformation. In the experimental spectrum two strong bands are found at 1654 and 1638cm−1 (shoulder) attributed to the Cing mode. The analysis of the normal modes for the corresponding transitions calculated at 1742 and 1729cm−1 allowed the assignment to be made to ν(Che carboxylic acid and ester moiety, respectively. Most of the other Raman bands were also assigned by comparison with the theoretical model. The Raman spectrum obtained directly from the P. tinctorum lichen shows a remarkable similarity with the isolated lecanoric acid spectrum, as well as the presence of bands at 1529 and 1156cm−1 which are characteristic of a carotenoid species. The results confirm the potential of Raman spectroscopy for taxonomic characterization of lichen species. [Copyright &y& Elsevier]

Abstract: Secondary compounds were quantified in 75 thalli of the foliose lichen Hypogymnia physodes collected in habitats along a natural shade-sun gradient from dark spruce forests to sun-exposed sea cliffs. The irradiance in all the 75 lichen sites was estimated from hemispherical photographs. The content of lichen compounds per thallus area correlated positively with irradiance level (r 2=0.73), and the mean concentration increased from 6.7% in the spruce forest to 14.4% on sea cliffs. The medullary depsidones, physodic, physodalic and protocetraric acids, constituted >95% of the total pool of extractable secondary compounds, the cortical depsides, atranorin and chloratranorin, represented <5%. Both cortical compounds correlated well with direct and with diffuse radiation, whereas the three medullary compounds correlated better with diffuse than with direct radiation. Mentioned trends are consistent with a solar radiation screening hypothesis of both groups of these colourless compounds occuring as tiny crystals outside fungal hyphae. However, the UV-B protective hypothesis of the compounds was further tested in a lab experiment. Unnaturally high UV-B doses were required to significantly reduce the PSII efficiency (F V/F M) of symbiotic algae. Removal of the major pool of secondary compounds with acetone did not increase photobiont susceptibility to UV-B. Therefore, the main functional role of the UV-B absorbing secondary compounds in H. physodes is hardly UV-B screening. Other roles such as PAR-screening and defence against herbivores and pathogenic organisms are discussed. [Copyright &y& Elsevier]

Abstract: A new tetranuclear copper(II) complex which mimics the active site of catechol oxidase was synthesized and characterized by IR, CHN, electronic spectroscopic and 1H NMR methods. The title complex [Cu2(μ-OH)(bpbpmp-NO2)]2[ClO4]2 was employed in the construction of a novel biomimetic sensor and used in the determination of chlorogenic acid by square wave voltammetry. The performance and optimization of the resulting biomimetic sensor were studied in detail. The best response of this sensor was obtained for 75:15:10% (w/w/w) ratio of the graphite powder:nujol:Cu(II) complex, 0.1molL−1 phosphate buffer solution (pH 7.0), with frequency, pulse amplitude, and scan increment at 30Hz, 100mV, and 3.0mV, respectively. The chlorogenic acid concentration was linear in the range of 5.0×10−6 to 1.45×10−4 molL−1 (r =0.9985) with a detection limit of 8.0×10−7 molL−1. This biomimetic sensor demonstrated long-term stability (250 days; 640 determinations) and reproducibility, with a relative standard deviation of 10.0%. The recovery study of chlorogenic acid in coffee samples gave values from 93.2% to 106.1% and the concentrations determined showed good agreement when compared with those obtained using capillary electrophoresis at the 95% confidence level. [Copyright &y& Elsevier]

Abstract: An efficient microwave-assisted extraction (MAE) technique has been developed to recover chlorogenic acid from flower buds of Lonicera japonica Thunb. The yield of chlorogenic acid rapidly reached 6.14% within 5min under the optimal MAE conditions, i.e. 50% ethanol as extraction solvent, 1:10 (w/v) of the solid/liquid ratio and 60°C of extraction temperature. The MAE showed obvious advantages in terms of short duration and high efficiency to recover chlorogenic acid from raw plant materials in comparison with conventional heat-reflux extraction. The mechanism of the enhanced extraction by microwave assistance was discussed by observing cell destruction of plant material after MAE treatment by scanning electron microscopy. The results showed that the plant materials were significantly destroyed due to the cell rupture after MAE treatment. [Copyright &y& Elsevier]

Abstract: Enantiopure bis-chromanones were prepared from (S)-Binol and bromo esters via a Baylis–Hillman approach. Chiroptical studies indicate that the two-naphthyl units of the chromanone system are non-coplanar. [Copyright &y& Elsevier]

Abstract: The Flos Chrysanthemi Indici suppository, a famous traditional Chinese medicine, is marketed for the treatment of prostatitis and chronic pelvic inflammation. A simple, relatively rapid and accurate high-performance liquid chromatographic (HPLC) method was applied to the simultaneous determination of chlorogenic acid, linarin and luteolin in Flos Chrysanthemi Indici suppository. The good separation was achieved on a Hypersil ODS column by a gradient elution using the mixture of acetonitrile and aqueous 1.0% acetic acid as mobile phase within 23min. The method was validated for three active phenolic compounds with the relative standard deviations (R.S.D.) of intra- and inter-day precision below 3.0%, and the detection limits (S/N=3) of chlorogenic acid, linarin and luteolin were 0.32, 0.08 and 0.05μgml−1, respectively. This assay was successfully applied to the determination of three active phenolic compounds in Flos Chrysanthemi Indici suppository samples with the quantitative recoveries in the range of 94.7–101.8%. The results indicate that the developed HPLC method can be readily utilized as a quality control method for Flos Chrysanthemi Indici suppository and its related traditional Chinese medicinal preparations. [Copyright &y& Elsevier]

The bioavailability of chlorogenic acid, a major polyphenol of the human diet that is particularly abundant in coffee and various fruits, was explored in rats. To identify the form under which it is absorbed through the gut mucosa and the site of absorption along the gastrointestinal tract, rats were fed a diet supplemented with chlorogenic acid (0.25%, wt:wt). Chlorogenic acid and its metabolites were estimated in the stomach, small intestine and cecal contents as well as in bladder urine and plasma by HPLC with coulometric detection at several time points (1.5, 3, 4.5, and 7 h) after the beginning of the meal. Minor hydrolysis of chlorogenic acid (<1%) occurred in the stomach and small intestine contents, whereas 15-32% of ingested chlorogenic acid was hydrolyzed into caffeic acid in the cecum. Chlorogenic acid and caffeic acid appeared early (at 1.5 h) in plasma and urine, suggesting an absorption of chlorogenic acid into the upper part of the gastrointestinal tract. Gastric absorption of chlorogenic acid was further examined by infusing chlorogenic acid in the ligated stomach of food-deprived rats. After 30 min of infusion, intact chlorogenic acid was found in the gastric vein and aorta. No other metabolites could be detected by HPLC-electrospray ionization-MS-MS. These results show for the first time that chlorogenic acid is quickly absorbed in the rat stomach in its intact form. [ABSTRACT FROM AUTHOR]

Abstract: 5-Nitro-1,10-phenanthrolines react with isocyanoacetate esters in the presence of DBU in THF to give excellent yields of the corresponding phenanthrolinopyrroles. These were condensed with acetoxymethylpyrroles using catalytic quantities of p-toluenesulfonic acid in acetic acid to give dipyrrylmethanes, but these structures proved to be poorly suited for porphyrin synthesis due to the electron-withdrawing nature of the fused phenanthroline unit. However, phenanthrolinopyrrole ethyl esters could be converted to the corresponding α-unsubstituted pyrroles with KOH in ethylene glycol at 180–190°C, and these condensed with 2equiv of acetoxymethylpyrroles in refluxing acetic acid-isopropyl alcohol to give tripyrranes. In a one pot procedure, tripyrrane di-tert-butyl esters were treated with TFA at room temperature to cleave the protective groups, diluted with dichloromethane, reacted with pyrrole dialdehydes and oxidized to afford phenanthrolinoporphyrins in 52–83% yield. These conditions also allow the synthesis of porphyrins with additional fused acenaphthylene or phenanthrene rings. Although the UV–vis spectra for these porphyrins are unexceptional, the presence of an external coordination site allows many potential applications to be considered. Porphyrins with two phenanthroline units could not be prepared by the ‘3+1’ strategy. Instead, α-unsubstituted phenanthrolinopyrroles were reacted with a bis(dimethylaminomethyl)pyrrole in refluxing acetic acid to give moderate yields of the corresponding opp-diphenanthrolinoporphyrins. In one case, a triphenanthrolinoporphyrin and trace amounts of an adj-diphenanthrolinoporphyrin were formed as by-products. [Copyright &y& Elsevier]