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Real-time measurements of acidic trace gases (HCl, HNO3, HONO, and SO2), ammonia, and water-soluble ions in PM2.5 were conducted at Xinken, a coastal site downwind of Guangzhou, from 4 October to 4 November 2004, as part of the Pearl River Delta (PRD) intensive field campaign. The average concentrations of HCl, HONO, HNO3, SO2, and NH3 are 2.8, 2.9, 6.3, 55.4, and 7.3μgm−3, respectively, and 2.4, 7.2, 24.1, and 9.2μgm−3 for Cl−, NO3 −, SO4 2−, and NH4 + in PM2.5. The diurnal variations of both HCl and HNO3 showed higher concentrations during daytime and lower concentrations at night, and aerosol Cl− and NO3 − showed an opposite diurnal patterns to HCl and HNO3. The diurnal variation of NH3 showed the similar pattern to that of aerosol NH4 + with lower concentration during daytime and higher concentration at night. The average concentration of SO2 during daytime was higher than that at night. The transportation of urban plumes to the sampling site could explain the higher concentration of SO2 during daytime. HONO showed a clear diurnal variation with lower concentration during daytime and higher concentration at night. The HONO concentrations were positively correlated with the particle surface area concentrations, suggesting the formation of HONO through the heterogeneous conversion on particle surfaces could be significant. The ionic charge balance analysis included the cations derived from filter measurements indicates that the contribution of the cations in fine particle (PM1.8) to the charge balance is not pronounced. The theoretical equilibrium constant (K e) of NH4NO3 is higher than the observed concentration product (K m=[NH3]×[HNO3]) during daytime, and lower than K m at night. This indicates that the atmospheric conditions during the sampling period did not favor the formation of NH4NO3 during daytime. [Copyright &y& Elsevier]

Abstract: A panel of nine dibenzo[a,c]cyclooctadiene lignans, schizandrin, gomisin A, gomisin N, gomisin J, angeloylgomisin H, tigloylgomisin P, deoxyschizandrin, γ-schizandrin and wuweizisu C was examined for their effect on multidrug resistance, as well as their anti-proliferative activities. COR-L23/R, a multidrug resistant sub-line, which has been reported to over-express multidrug resistance-associated protein (MRP1), was used for the experiments together with its parent cell line COR-L23 (human lung cell carcinoma). We found that lignans deoxyschizandrin and γ-schizandrin at relatively non-toxic concentrations restored the cytotoxic action of doxorubicin to COR-L23/R cells. Deoxyschizandrin and γ-schizandrin also significantly enhanced the accumulation of doxorubicin in drug resistant cells. Both lignans alone had no effect on the cell cycle; however, when combined with sub-toxic doses of doxorubicin, they induced cell cycle arrest in the G2/M phase, which is typical for toxic doses of doxorubicin. Our results suggest that deoxyschizandrin and γ-schizandrin potentiate the cytotoxic effect of doxorubicin in doxorubicin resistant lung cancer cells COR-L23/R by increasing the accumulation of doxorubicin inside the cells. The common structural feature of both active lignans is the R-biaryl configuration and the absence of a hydroxy group at C-8. Unlike the reversal effect, the cytotoxicity of lignans with the R-biaryl configuration was similar to that observed for lignans with the S-biaryl configuration. [Copyright &y& Elsevier]

The phenolic compounds of methanolic extracts of Salvia pomifera and Salvia fruticosa were identified by liquid chromatography tandem mass spectrometry. Carnosic acid and its metabolite carnosol were the most abundant terpene phenolic compounds of S. fruticosa , while they were completely absent in S. pomifera . The main terpene phenolic constituent of S. pomifera was 12- O -methylcarnosic acid and its mass/mass fragmentation pathway was explained. The detailed mechanism of carnosic acid oxidation to carnosol was suggested. The effects of Salvia extracts and/or carnosic acid, the main diterpene phenolic component of S. fruticosa , on the proliferation and cell cycle of two melanoma cell lines (A375, Mel JuSo) and human fibroblast cell line (HFF) were investigated by MTT assay, PI-exclusion assay and flow cytometry cell cycle analysis. Extract of S. fruticosa more efficiently than S. pomifera extract reduced the proliferation of the human melanoma cells. Carnosic acid showed the most significant effect. The first evidence that carnosic acid affects microtubule dynamics and arrests the cell cycle in the G2/M phase was provided. Collectively, our results demonstrate that these two Salvia species are plants of medicinal interest with perspective for further investigation. Carnosic acid could be the compound responsible for the biological activities of S. fruticosa extracts.

Sanguinarine is a benzo[c]phenanthridine alkaloid with interesting cytotoxic properties, such as induction of oxidative DNA damage and very rapid apoptosis, which is not mediated by p53-dependent signaling. It has been previously documented that sanguinarine is reduced with NADH even in absence of any enzymes while being converted to its dihydro form. We found that the dark blue fluorescent species, observed during sanguinarine reduction with NADH and misinterpreted by Matkar et al. (Arch. Biochem. Biophys. 2008, 477, 43-52) as an anionic form of the alkaloid, is a covalent adduct formed by the interaction of NADH and sanguinarine. The covalent adduct is then converted slowly to the products, dihydrosanguinarine and NAD + , in the second step of reduction. The product of the reduction, dihydrosanguinarine, was continually re-oxidized by the atmospheric oxygen back to sanguinarine, resulting in further reacting with NADH and eventually depleting all NADH molecules. The ability of sanguinarine to diminish the pool of NADH and NADPH is further considered when explaining the sanguinarine-induced apoptosis in living cells., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The aim of the present study was to determine the structural requirements for dibenzocyclooctadiene lignans essential for P-glycoprotein inhibition. Altogether 15 structurally related lignans isolated from Schisandra chinensis or prepared by modification of their backbone were investigated, including three pairs of enantiomers. P-Glycoprotein inhibition was quantified using a doxorubicin accumulation assay in human promyelotic leukemia HL60/MDR cells overexpressing P-glycoprotein. A preliminary quantitative structure-activity relationship analysis revealed three main structural features involved in P-glycoprotein inhibition: a 1,2,3-trimethoxy moiety, a 6-acyloxy group, and the absence of a 7-hydroxy group. The most effective inhibitors, (-)-gomisin N (1) and (+)-deoxyschizandrin [(+)-2], were selected for further evaluation of their effects. Both these lignans restored the cytotoxic effect of doxorubicin in HL60/MDR cells and when combined with a subtoxic concentration of this compound increased the proportion of G2/M cells significantly, which is a usual response to treatment with this anticancer drug.

Using exhaustive chromatographic separation we have isolated (-)-tigloyl-deangeloyl-gomisin F as a novel dibenzocyclooctadiene lignan from schisandra chinensis. With the help of HPLC, we further isolated (+)-schisandrin, (+)-deoxyschisandrin, (+)-γ-schisandrin, (-)-gomisin J, (+)-gomisin A, (-)-gomisin N, (-)-tigloyl-gomisin P, (-)-wuweizisu C, (-)-gomisin D, rubrisandrin A, (-)-gomisin G, (+)-gomisin K (3) and (-)-schisantherin C. A full NMR description of (-)-schisantherin C was carried out with the aim to confirm previous reports of its structure. Compounds isolated were identified on the basis of UV, IR, (1)H- and (13)C-NMR and MS. The cytotoxicity of lignans was tested for the BY-2 cell line alone and as a synergistic effect with the cytotoxic agent camptothecin. Lignans showed various toxicity and synergistic and antagonistic effects on camptothecin-induced cytotoxicity. Cytotoxicity against colon cancer cell line LoVo was also tested., (© Georg Thieme Verlag KG Stuttgart · New York.)

A simple and rapid method for determination of six lignans found in plant cell cultures of Schisandra chinensis was developed and validated. The lignans were extracted from plant samples with methanol and the extracts were effectively cleaned by solid-phase extraction using Strata C18-E (Phenomenex) cartridges. Chromatographic separation was carried out on a Chromolith Performance RP-18e monolithic column (100 x 4.6 mm, Merck) using an isocratic mobile phase of acetonitrile and water in a 50:50 (v/v) ratio. The eluent was monitored at 220 nm. The baseline separation of schizandrin, gomisin A, deoxyschizandrin, gamma-schizandrin, gomisin N and wuweizisu C was achieved in a relatively short time period (20 min), which was made possible by the relatively high flow rate of the mobile phase (2 mL/min). The lower limit of quantitation was 0.1 mg/L for schizandrin and gomisin A, 0.3 mg/L for deoxyschizandrin, gamma-schizandrin, and gomisin N and 1 mg/L for wuweizisu C. The analysis of spiked samples containing six lignans provided absolute recoveries between 93 and 101% in all cases. The validated method was successfully applied to the determination of lignans in embryogenic plant cell cultures of Schisandra chinensis., (2010 John Wiley & Sons, Ltd.)

The in vitro antiradical activity of Schisandra chinensis lignans was investigated using DPPH, ABTS+, Fenton reaction inhibition and tyrosine-nitration inhibition assays, as were the in vivo antidiabetic activities of selected lignans in an animal model of alloxan-induced diabetes. Different degrees of antiradical activity were found, depending upon the structural parameters of the tested compounds. Unfortunately, the compounds showed no antidiabetic activity in concentration range tested.

In the summers of 2002-2003, acidic gases, ammonia and water-soluble ions in PM(10) were measured in Beijing. The mean concentrations of HCl, HONO, HNO(3), SO(2) and NH(3) are 0.6, 3.6, 1.9, 14.1 and 16.6microgm(-3), respectively, and 2.2, 14.6, 19.3 and 8.9microgm(-3) for Cl(-),NO(3)(-),SO(4)(2-)andNH(4)(+) in PM(10). The concentrations of secondary ions in PM(10) are found to have strong dependence on the pathway of trajectories. The most frequent southerly air flow is connected with high concentrations of secondary water-soluble ions during summertime. Other trajectories with northwest and north direction lead to lower concentrations of secondary ions. Hebei and Shandong Provinces and the Tianjin Municipality are the main source areas for sulfate as identified by Potential Source Contribution Function. This result emphasizes that the non-Beijing sources play an important role in the sulfate mass concentration in the urban atmosphere of Beijing and validates conclusions based on model calculations for the region.

Background: Quaternary benzo[c]phenanthridine alkaloids (QBAs) are naturally occurring compounds isolated from plants in the Fumariaceae, Papaveraceae, Ranunculaceae, and Rutaceae families. In addition to having a wide range of biological activities, they are also attractive for their fluorescent properties. We observed interesting fluorescent characteristics in the QBAs-macarpine (MA), sanguirubine (SR), chelirubine (CHR), sanguilutine (SL), chelilutine (CHL), sanguinarine (SA) and chelerythrine (CHE) after interaction with living cells., Methods: Water stock solutions of the alkaloids (10-100 microg/ml) were added to intact cells, and after a brief incubation the cells were observed. Human cell lines HL60 (human promyelocytic leukemia), HeLa (human cervix adenocarcinoma), and LEP (human lung fibroblasts), and piglet blood were used in the experiments. Blood cells were stained with MA in combination with FITC-conjugated anti-CD45 surface marker antibody. Cells were analyzed by fluorescence microscopy and by flow cytometry., Results: All tested alkaloids immediately entered living cells with MA, CHR, and SA binding to DNA. MA showed the best DNA staining properties. Fluorescence microscopy of MA, CHR, and SA stained cells described the nuclear architecture and clearly described chromosomes and apoptotic fragments in living cells. Moreover MA can rapidly represent the cellular DNA content of living cells at a resolution adequate for cell cycle analysis. QBAs were excitable using common argon lasers (488 nm) emitting at a range of 575-755 nm (i.e. fluorescence detectors FL2-5). Spectral characteristics of MA allow simultaneous surface immunophenotyping., Conclusions: It was shown that MA, CHR, and SA stain nucleic acids in living cells. They can be used as supravital fluorescent DNA probes, both in fluorescence microscopy and flow cytometry, including multiparameter analysis of peripheral blood and bone marrow. MA binds DNA stochiometrically and can provide information on DNA content., (Copyright (c) 2007 International Society for Analytical Cytology.)

Samples of 1,3- (1) and 1,5-dicaffeoylquinic acid (2) and their hexaacetate derivatives were examined using positive and negative electrospray ionization mass spectrometry and tandem mass spectrometry. Differences in the various spectra allow the discrimination of each of the isomers. Specific losses in the spectra of 2 also permit the identification of the site of substitution of one of the caffeic acid moieties as being at the 5-position. The spectra of 3,5- (3) and 4,5-dicaffeoylquinic (4) acids and their hexaacetate derivatives were compared with those of 1 and 2 and their derivatives, and differences in ion abundances or the presence/absence of specific ions can be used to identify uniquely each of the compounds., (Copyright 2004 John Wiley & Sons, Ltd.)

The content of the main flavonoids in the root of Scutellaria baicalensis Georgi cultivated in Central Europe was evaluated using the new simple RP-HPLC method with gradient of acetonitrile in mobile phase. The main components of the roots were baicalin (8.12% of dry root mass) and wogonin glucuronide (2.52%). The content of flavonoids was comparable with the content in plants cultivated in natural localities. Five main flavonoids were evaluated for their scavenging ability with DPPH radical-generating system and due to limited solubility only two flavonoids were investigated for their ability to scavenge hydroxyl radical by the aromatic hydroxylation method. The total extract was also tested in both the experimental arrangements. In experiments with DPPH, only baicalin and baicalein displayed a significant scavenging effect, while the production of OH radicals generated by UV photolysis of H(2)O(2) was considerable decreased in the presence of baicalin and wogonin glucuronide. After comparison with results obtained for the total extract, it was concluded, that the scavenging activity of the extract against DPPH is mainly derived from baicalin. On the other hand, baicalin, wogonin glucuronide and probably other flavonoids participate in scavenging OH radical., (Copyright 2003 John Wiley & Sons, Ltd.)

Possible UVC-protective properties of CA, a plant phenolic compound with antioxidant activity, were investigated on human KF1 diploid fibroblast and A431 epidermoid carcinoma cell lines. Cell populations, untreated and treated by antioxidants (CA and alpha-tocopherol), were irradiated by UVC at the wavelength of 254 nm and their proliferation activity was determined by the MTT assay. The results show a strong protective effect of CA at both concentrations used (55.5 and 166.5 microM): a significant increase of proliferation activity after UVC irradiation was detected in both cell populations growing in the presence of CA in comparison with cells in DMEM only. The described protective effect of CA was more obvious in transformed cells than in normal diploid cells. This protective ability is probably based on the antioxidant and scavenging activities of CA, which seems to be more efficient than alpha-tocopherol in protection against the cytotoxic effect caused by UVC irradiation.

Measurements in urban Atlanta of transient aerosol events in which PM2.5 mass concentrations rapidly rise and fall over a period of 3-6 hr are reported. The data are based on new measurement techniques demonstrated at the U.S. Environmental Protection Agency (EPA) Atlanta Supersite Experiment in August 1999. These independent instruments for aerosol chemical speciation of NO3-, SO4(2-), NH4+, and organic and elemental carbon (OC and EC), reconstructed the observed hourly dry PM2.5 mass to within 20% or better. Data from the experiment indicated that transient PM2.5 events were ubiquitous in Atlanta and were typically characterized by a sudden increase of EC (soot) and OC in the early morning or SO4(2-) in the late afternoon. The frequent temporal decoupling of these events provides insights into their origins, suggesting mobile sources in metro Atlanta as the main contributor to early morning PM2.5 and more regionally located point SO2 sources for afternoon PM2.5 events. The transient events may also have health implications. New data suggest that short-term PM2.5 exposures may lead to adverse health effects. Standard integrated filter-based techniques used in PM2.5 compliance monitoring networks and in most past PM2.5 epidemiologic studies collect samples over 24-hr periods and thus are unable to capture these transient events. Moreover, health-effects studies that focus on daily PM2.5 mass alone cannot evaluate the health implications of the unique and variable chemical properties of these episodes.

Aims: To provide a schematized and graduated CT reference series of the mediastinum showing CT-detectable lymph node areas of lung cancer patients to support 3-D treatment planning and documentation for adjuvant irradiation of the mediastinum., Patients and Methods: Cross sections of mediastinal structures from one male individual were schematized and overlaid with a 1 cm2 reference grid. Mediastinal CT scans of 100 consecutive patients with histologically proven lung cancer and CT-detectable lymph nodes were evaluated. For each patient the outlines of all identifiable nodes were transferred into the schematized CT series according to their localization in relation to anatomical landmarks. The outlines were centered in a predefined way into relevant squares of the reference grid. The number of patients with nodes projecting to individual CT cross sections was determined. Further, the number and percentage of patients locating to positive grid squares were analyzed., Results: A differentiated pattern of CT-detectable lymph nodes was confirmed. Along the longitudinal axis the CT-detectable nodes followed a Gaussian distribution with its maximum (89% of all patients) at the level of the tracheal bifurcation. At different transverse levels closely circumscribed central areas with node positive grid squares were identified harboring up to 72% of the patients (locating to the front of the trachea, the bifurcation and below the carina). Peripheral areas showed only sporadically node positive grid squares, usually representing less than 5% of the patients., Conclusions: These schematized and graduated CT cross sections show areas of CT-detectable lymph node spread from the view of 3-D planning. They are of additional help to individualize mediastinal target volumes and/or dose distributions, particularly when administering adjuvant irradiation to patients without mediastinal lymph node involvement. Classifying mediastinal structures by using a grid square easily allows to describe and document target volumes and dose distributions per cross section.

Micellar electrokinetic capillary chromatography (MEKC) has been developed as a promising method for the determination of lignans in plant samples. The separation conditions have been optimized with respect to the different parameters including sodium dodecyl sulfate (SDS) and acetonitrile concentration, pH of the background electrolyte, separation voltage, and capillary temperature. The background electrolyte consisting of 40 mM SDS and 35% acetonitrile in 10 mM tetraborate buffer (pH 9.3) was found to be the most suitable electrolyte for this analysis. The applied voltage of 28 kV (positive polarity) and the capillary temperature 25 degrees C gave the best separation of lignans. The interday reproducibility of the peak areas and the migration times was below 2.0%. The results of MEKC analyses were compared with those obtained by capillary electrochromatography (CEC) and reversed-phase high-performance liquid chromatography (RP-HPLC). The possibilities of using this method for the determination of lignans in drug and in serum samples were also tested.

The main constituents of artichoke extract were separated by micellar electrokinetic chromatography (MEKC), using a buffer consisting of 100 mM sodium dodecyl sulfate (SDS) in 20 mM sodium dihydrogen phosphate, 20 mM disodium tetraborate (pH 8.6) as background electrolyte. Optimum separation voltage of 28 kV (positive polarity) and a capillary temperature of 25 degrees C gave the best analysis. The UV detection was performed at 200 nm. The method was successfully used to analyze plant and drug samples as well as for the study of artichoke antioxidant activity. The quantitative MEKC results were in good agreement to those obtained previously by reversed-phase high-performance liquid chromatography (RP-HPLC).

We compared the effects of four quaternary benzo[c]phenanthridine alkaloids--chelerythrine, chelilutine, sanguinarine, and sanguilutine--and two quaternary protoberberine alkaloids-berberine and coptisine--on the human cell line HeLa (cervix carcinoma cells) and the yeasts Saccharomyces cerevisiae and Schizosaccharomyces japonicus var. versatilis. The ability of alkaloids to display primary fluorescence, allowed us to record their dynamics and localization in cells. Cytotoxic, anti-microtubular, and anti-actin effects in living cells were studied. In the yeasts, neither microtubules nor cell growth was seriously affected even at the alkaloid concentration of 100 microg/ml. The HeLa cells, however, responded to the toxic effect of alkaloids at concentrations ranging from 1 to 50 microg/ml. IC50 values for individual alkaloids were: sanguinarine IC50 = 0.8 microg/ml, sanguilutine IC50 = 8.3 microg/ml, chelerythrine IC50 = 6.2 microg/ml, chelilutine IC50 = 5.2 microg/ml, coptisine IC50 = 2.6 microg/ml and berberine IC50 > 10.0 microg/ml. In living cells, sanguinarine produced a decrease in microtubule numbers, particularly at the cell periphery, at a concentration of 0.1 microg/ml. The other alkaloids showed a similar effect but at higher concentrations (5-50 microg/ml). The strongest effects of sanguinarine were explained as a consequence of its easy penetration through the cell membrane owing to nonpolar pseudobase formation and to a high degree of molecular planarity.

Aim: To quantify the risk of second malignancies in patients with Hodgkin's disease treated at the Department of Radiotherapy, University Clinic Freiburg, with the object of comparing this risk with the international experience and as a contribution to the discussion about future treatment., Patients and Methods: Second malignancies were reviewed in 1,588 patients treated for Hodgkin's disease between 1940 and 1991. Treatment consisted of involved or extended field radiotherapy as a single modality or in combination with chemotherapy. Before the early 1970's, chemotherapy used (sequential) monodrug regimens. The mean follow-up was 8.3 years. The cumulative risk was calculated using the Kaplan-Meier method and related to the risk of a normal population taken from epidemiological data of the National Cancer Institute. An estimate of radiation dose at the site of origin of the second malignancy was obtained from representative measurements employing an Alderson phantom., Results: After 5, 10, 15 and 20 years the cumulative risk for all malignancies was 1.5%, 4.2%, 9.4% and 21%, respectively; for solid tumors it came to 1.2%, 3.1%, 7.9% and 19%; for non-Hodgkin lymphoma (NHL) the risk amounted to 0.1%, 0.9%, 1.4% and 1.9%; and for leukemia it was 0.1%, 0.3%, 0.6% and 0.6%. For the same time points the relative risk for all malignancies was calculated to be 1.1, 1.4, 1.8 and 2.5; for solid tumors it came to 1.0, 1.1, 1.6 and 2.5; for NHL it amounted to 3.3, 11.8, 9.3 and 8.0; and for leukemia it was 3.3, 3.1, 3.4 and 2.1. For combinations of radiotherapy and chemotherapy the risk for second malignancies was highest in patients receiving ABVD any time during their treatment. 51% of the second malignancies were located infield, 22% at the field border and 27% outfield. In those cases for which the cause of death was known, Hodgkin's disease accounted for 79% followed by second malignancies accounting for 8%. The results obtained in Freiburg fell within the range reported in international publications., Conclusion: The increased incidence of second malignancies in cured Hodgkin's patients is along-term risk making regular follow-up mandatory. Although part of the second malignancies are unrelated to therapy, there is a need to carefully collect the data from patients treated according to new protocols in order to detect any changes in the number or kind of second malignancies in due time. This may well lead to a reassessment of therapeutic concepts.

At the University of Freiburg, a consensus was arrived at concerning the place of external radiotherapy in the management of thyroid cancer. External irradiation is always indicated in papillary and folliculary carcinoma in the pT4 stage of pTNM classification but not in those in pT1-3 pN0 stage. In the presence of lymph-node metastases and distant metastases, an individual treatment concept is recommended, which should be set up in an interdisciplinary conference regarding all risk factors, especially the age and sex of the patient, the histology and grading of the tumor and the completeness of tumor resection. Finally, radiotherapy is usually not indicated in medullary thyroid carcinoma, whereas it is always indicated in anaplastic carcinoma.