The metal — Metal interactions in biological systems Part III. Daphnia magna

The toxicity of single metal ions: Al, Co(II), Cr(III), Cu(II), Fe(III), Mg, Mn(II), Mo(VI), Ni(II), Se(VI), V(V) and Zn and the following pairs of them: Al-Co, Al-Mg, Al-Mo, Al-Se, Al-Zn, Cr-Co, Cr-Mg, Cr-Mo, Cr-Se, Cr-Zn, Cu-Co, Cu-Mg, Cu-Mo, Cu-Se, Cu-Zn, Fe-Co, Fe-Mg, Fe-Mo, Fe-Se, Fe-Zn, Mn-Co, Mn-Mg, Mn-Mo, Mn-Se, Mn-Zn, Ni-Co, Ni-Mg, Ni-Mo, Ni-Se, Ni-Zn, V-Co, V-Mg, V-Mo, V-Se, V-Zn, Zn-Co, Zn-Mg, Zn-Mo, and Zn-Se on Daphnia magna was examined. The most prominent antagonism in the toxicity was observed in the following ion pairs: Al-Mo(VI), Cr(III)-Co(II), Cr(III)-Mg, Cr(III)-Mo(VI), Cr(III)-Se(VI), Cr(III)-Zn, Fe(III)-Se(VI), Mn(II)-Mg, Mn(II-Se(VI), Zn-Mg and Zn-Mo(VI). The strong synergism was found for the following ion systems: Cr(III)-Se(VI), Cr(III)-Zn, Fe(III)-Se(VI), Mn(II)-Zn, Mn(II)-Se(VI), Ni(II)-Co(II), Ni(II)-Mo(VI), Ni(II)-Se(VI), Ni(II)-Zn, V(V)-Co(II), V(V)-Mo(VI), V(V)- Se(VI), and V(V)-Zn. Synergism and antagonism in toxicity were dependent on water hardness as well as on the ion concentration. Adaptive procesess of the animals to the toxic environment could also be observed. Thus, the toxicity of the single ions and their pairs was not linear with respect to time.     

Direct aqueous injection liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry analysis of water for atrazine, simazine, and their chlorotriazine metabolites

A method is reported for the determination of atrazine, simazine, and their respective dealkylated chlorotriazine metabolites in ground, surface, and finished drinking water. Water samples are diluted 1:4 in an injection vial prior to analysis using liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry (LC/ESI-MS/MS). The lower limit of method validation is 0.10 microg/L (ppb) for 2-chloro-4-(ethylamino)-6-isopropylamino)-s-triazine (atrazine, G-30027), 2-chloro-4, 6-(diethylamino)-s-triazine (simazine, G-27692), 2-amino-4-chloro-6-(isopropylamino)-s-triazine (deethylatrazine, DEA, or G-30033), 2-amino-4-chloro-6-(ethylamino)-s-triazine (deisopropylatrazine, DIA, or G-28279), and 2,4-diamino-6-chloro-s-triazine (didealkylatrazine, DDA, or G-28273). The overall mean procedural recoveries (and % relative standard deviations) for atrazine, simazine, DEA, DIA, and DDA are 98 (4.4), 102 (3.6), 99 (4.8), 103 (4.0), and 109% (4.8%), respectively, in finished drinking water; 108 (2.7), 104 (5.4), 113 (4.5), 111 (5.2), and 105% (5.3%), respectively, in groundwater; and 96 (6.9), 103 (4.2), 102 (4.4), 102 (5.2), and 102% (8.2%), respectively, in surface water. The method validation was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160.     

MINERAL ELEMENT DISTRIBUTION AND ACCUMULATION PATTERNS WITHIN TWO BARLEY CULTIVARS

Growth stage effects on distribution of mineral nutrients or beneficial elements phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), chloride (Cl), iron (Fe), zinc (Zn), manganese (Mn), copper (Cu), molybdenum (Mo), sodium (Na), silicon (Si) and nickel (Ni), and the elements bromine (Br), rubidium (Rb), strontium (Sr), barium (Ba), lanthanum (La), cerium (Ce), and uranium (U) in two barley (Hordeum vulgare L.) cultivars and how the distribution of these elements changed were determined during the 2006–2007 growing season in a field experiment. Barley plants were sampled from the field at shooting, heading, soft dough, hard dough and harvest stages, and mineral nutrients and other elements concentrations of spike, flag leaf, old leaf, and stem samples were determined by polarized energy dispersive X-ray fluorescence (PEDXRF). Distribution patterns varied considerably from element to element. At the end of the season much of the Ca, Mg, S, Si, Fe, Mn, Cu, Ni, Sr, Ba, La, Ce, and U were located in the spikes. However, much of the P, K, Zn, Cl, Na, Br, and Rb remained in the old leaves or stem.     

Maple syrup phytochemicals include lignans, coumarins, a stilbene, and other previously unreported antioxidant phenolic compounds

Twenty-three phenolic compounds were isolated from a butanol extract of Canadian maple syrup (MS-BuOH) using chromatographic methods. The compounds were identified from their nuclear magnetic resonance and mass spectral data as 7 lignans [lyoniresinol (1), secoisolariciresinol (2), dehydroconiferyl alcohol (3), 5'-methoxy-dehydroconiferyl alcohol (4), erythro-guaiacylglycerol-β-O-4'-coniferyl alcohol (5), erythro-guaiacylglycerol-β-O-4'-dihydroconiferyl alcohol (6), and [3-[4-[(6-deoxy-α-l-mannopyranosyl)oxy]-3-methoxyphenyl]methyl]-5-(3,4-dimethoxyphenyl)dihydro-3-hydroxy-4-(hydroxymethyl)-2(3H)-furanone (7)], 2 coumarins [scopoletin (8) and fraxetin (9)], a stilbene [(E)-3,3'-dimethoxy-4,4'-dihydroxystilbene (10)], and 13 phenolic derivatives [2-hydroxy-3',4'-dihydroxyacetophenone (11), 1-(2,3,4-trihydroxy-5-methylphenyl)ethanone (12), 2,4,5-trihydroxyacetophenone (13), catechaldehyde (14), vanillin (15), syringaldehyde (16), gallic acid (17), trimethyl gallic acid methyl ester (18), syringic acid (19), syringenin (20), (E)-coniferol (21), C-veratroylglycol (22), and catechol (23)]. The antioxidant activities of MS-BuOH (IC50>1000 μg/mL), pure compounds, vitamin C (IC50=58 μM), and a synthetic commercial antioxidant, butylated hydroxytoluene (IC50=2651 μM), were evaluated in the diphenylpicrylhydrazyl (DPPH) radical scavenging assay. Among the isolates, the phenolic derivatives and coumarins showed superior antioxidant activity (IC50<100 μM) compared to the lignans and stilbene (IC50>100 μM). Also, this is the first report of 16 of these 23 phenolics, that is, compounds 1, 2, 4-14, 18, 20, and 22, in maple syrup.     

长期施肥对小麦-玉米作物系统土壤腐殖质组分碳和氮的影响

通过对华北平原小麦–玉米轮作农田生态系统18年田间施肥试验,研究了长期不同施肥处理对耕层（0—20 cm）土壤腐殖质及活性腐殖质组分碳和氮的影响。试验设化肥NPK不同组合（NPK、NP、NK、PK）,全部施用有机肥（OM）,一半有机肥+化肥NPK（1/2OMN）及不施肥（CK）共7个处理。结果表明,各施肥处理均能在不同程度上增加土壤腐殖质（胡敏酸、富里酸和胡敏素）及活性腐殖质（活性胡敏酸和活性富里酸）组分碳和氮含量,提高可浸提腐殖质（胡敏酸和富里酸）及活性腐殖质组分碳和氮分配比例;但施肥对土壤活性腐殖质组分碳和氮含量的增加率均分别高于腐殖质组分碳和氮。各处理土壤腐殖质及活性腐殖质组分碳和氮含量均为OM处理最高,且有机肥与化肥NPK配施高于单施化肥各处理;而化肥处理中NPK均衡施用效果最好。说明施用有机肥、有机肥与化肥NPK配施及化肥NPK均衡施用是增加土壤腐殖质及活性腐殖质组分碳和氮的关键;活性腐殖质组分碳和氮较腐殖质组分碳和氮对施肥措施的响应更灵敏。     

Simultaneous quantification of ginsenosides in American ginseng (Panax quinquefolium) root powder by visible/near-infrared reflectance spectroscopy.

Near-infrared reflectance spectroscopy (NIRS) was examined as a possible alternative to high-performance liquid chromatography (HPLC) for the analysis of ginsenosides from American ginseng (Panax quinquefolium) root powder (n = 26). NIR spectra were collected over 400-2500 nm. For each sample and individual ginsenoside quantified by HPLC, spectral data were regressed against the chemical data to develop prediction equations. The spectral prediction equations produced high correlation coefficient (1-VR) values and low standard errors of cross validation (SECV) values for the determination of individual and total ginsenosides. The contents of individual ginsenosides, Rb(1), Rb(2), Rc, Rd, Re, Rg(1), Ro, m-Rb(1), m-Rb(2), m-Rc, m-Rd, and total ginsenosides (X +/- SECV) were (1.29+/-0.18)%, (0.273+/-0.096)%, (0.298+/-0.052)%, (0.091+/-0.027)%, (1. 015+/-0.114)%, (0.116+/-0.018)%, (0.25+/-0.040)%, (0.776+/-0.116)%, (0.197+/-0.074)%, (0.239+/-0.083)%, (0.143+/-0.042)%, and (4.393+/-0.283)%, respectively. The (1-VR) values of cross validation were 0.877, 0.872, 0.955, 0.834, 0.899, 0.919, 0.325, 0.849, 0.902, 0.877, 0.871, and 0.963, respectively. Results indicated that the NIRS method could be used for the analysis of the major ginsenosides, Rb(1), Re, and m-Rb(1), as well as the total ginsenosides in American ginseng.     

In Situ Measurement of Soil Chemical Composition by Near-Infrared Spectroscopy: A Tool Toward Sustainable Vineyard Management

This study evaluated an in-field near-infrared (NIR) instrument to predict the contents of total nitrogen (TN), organic carbon (OC), potassium (K), sulfur (S), phosphorus (P), pH, and electric conductivity (EC) in soil vineyard samples (n = 70) sourced from three wine regions of Australia. Samples were analyzed using a portable NIR spectrophotometer (ASD FieldSpec III, 350–1800 nm). Partial least squares (PLS) regressions yield a coefficient of determination in calibration (R2) and a standard error in cross validation (SECV) of 0.74 (0.03) for TN, 0.92 (2.19) for S, 0.81 (0.42) for OC, 0.70 (109.2) for K, 0.84 (0.03) for EC, 0.83 (0.44) for pH, and 0.69 (24.6) for P, respectively. This study showed that it is possible to measure soil chemical properties in the vineyard, and the main advantages of this approach will be the speed, low cost, and ability to better manage and monitor soil fertility.     

Sequestering Ability of Phytate toward Biologically and Environmentally Relevant Trivalent Metal Cations

Quantitative parameters for the interactions between phytate (Phy) and Al(3+), Fe(3+), and Cr(3+) were determined potentiometrically in NaNO(3) aqueous solutions at I = 0.10 mol L(-1) and T = 298.15 K. Different complex species were found in a wide pH range. The various species are partially protonated, depending on the pH in which they are formed, and are indicated with the general formula MH(q)Phy (with 0 ≤ q ≤ 6). In all cases, the stability of the FeH(q)Phy species is several log K units higher than that of the analogous AlH(q)Phy and CrH(q)Phy species. For example, for the MH(2)Phy species, the stability trend is log K(2) = 15.81, 20.61, and 16.70 for Al(3+), Fe(3+), and Cr(3+), respectively. The sequestering ability of phytate toward the considered metal cations was evaluated by calculating the pL(0.5) values (i.e., the total ligand concentration necessary to bind 50% of the cation present in trace in solution) at different pH values. In general, phytate results in a quite good sequestering agent toward all three cations in the whole investigated pH range, but the order of pL(0.5) depends on it. For example, at pH 5.0 it is pL(0.5) = 5.33, 5.44, and 5.75 for Fe(3+), Cr(3+), and Al(3+), respectively (Fe(3+) < Cr(3+) < Al(3+)); at pH 7.4 it is pL(0.5) = 9.94, 9.23, and 8.71 (Al(3+) < Cr(3+) < Fe(3+)), whereas at pH 9.0 it is pL(0.5) = 10.42, 10.87, and 8.34 (Al(3+) < Fe(3+) < Cr(3+)). All of the pL(0.5) values, and therefore the sequestering ability, regularly increase with increasing pH, and the dependence of pL(0.5) on pH was modeled using some empirical equations.     

Antiinflammatory flavonoids from Artocarpus heterophyllus and Artocarpus communis

The antiinflammatory activities of the isolated flavonoids, including cycloartomunin (1), cyclomorusin (2), dihydrocycloartomunin (3), dihydroisocycloartomunin (4), cudraflavone A (5), cyclocommunin (6), and artomunoxanthone (7), and cycloheterohyllin (8), artonins A (9) and B (10), artocarpanone (11), artocarpanone A (12), and heteroflavanones A (13), B (14), and C (15) from Artocarpus communis and A. heterophyllus, were assessed in vitro by determining their inhibitory effects on the chemical mediators released from mast cells, neutrophils, and macrophages. Compound 4 significantly inhibited the release of beta-glucuronidase and histamine from rat peritoneal mast cells stimulated with P-methoxy-N-methylphenethylamine (compound 48/80). Compound 11 significantly inhibited the release of lysozyme from rat neutrophils stimulated with formyl-Met-Leu-Phe (fMLP). Compounds 8, 10, and 11 significantly inhibited superoxide anion formation in fMLP-stimulated rat neutrophils while compounds 2, 3, 5, and 6 evoked the stimulation of superoxide anion generation. Compound 11 exhibited significant inhibitory effect on NO production and iNOS protein expression in RAW 264.7 cells. The potent inhibitory effect of compound 11 on NO production in lipopolysaccharide (LPS)-activated macrophages, probably through the suppression of iNOS protein expression.     

Four new steroidal saponins from the seeds of Allium tuberosum

Four new steroidal saponins, 26-O-beta-D-glucopyranosyl-(25S,20R)-20-O-methyl-5alpha-furost-22(23)-en-2alpha,3beta,20,26-tetraol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside (1); 26-O-beta-D-glucopyranosyl-(25S,20R)-5alpha-furost-22(23)-en-2alpha,3beta,20,26-tetraol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L- rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside (2); 26-O-beta-D-glucopyranosyl-(25S,20S)-5alpha-furost-22(23)-en-2alpha,3beta,20,26-tetraol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L- rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside (3); and 26-O-beta-D-glucopyranosyl-(25S,20S)-5alpha-furost-22(23)-en-3beta,20,26-triol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside (4), have been isolated from the seeds of Allium tuberosum. Their structures were established by spectroscopic studies such as MS, IR, NMR, and 2D-NMR and the results of acid hydrolysis and named tuberosides F, G, H, and I, respectively.     

不同浓度钙营养液对烟草矿质营养吸收与积累的影响

本文采用温室水培的方法,研究了不同的钙素供应水平对烟草各种矿质养分的吸收与积累的影响。结果表明,在其它养分形态与浓度一致条件下,随着钙浓度从75mgL-1提高到900mgL-1,烟草生长量呈抛物线型变化。钙浓度为150mgL-1时烟株干物质量最大。超过150mgL-1,随钙的增加而下降,当钙素达900mgL-1(K/Ca为1/6)时,烟株生长严重受抑。随着供钙水平由低到高,烟株氮、磷、钾、锌、锰含量均呈抛物线型变化,含钙量呈直线上升关系,而镁和铜含量则随钙浓度提高而显著下降。烟株各养分积累量均随营养液钙浓度提高呈抛物线型变化,但不同养分出现最大积累量时的营养液钙浓度却不相同。不同供钙水平上烟叶中各元素含量的变化特征与全株的结果基本一致。在低钙浓度范围(75~300mgL-1),钙对钾有协合关系,增钙促进提钾,大于300mgL-1后有拮抗作用,提钙导致降钾。钙与镁、锌、铜、锰间也存在明显的交互作用。烟叶中各元素含量与积累量的变化趋势与整株基本一致。     

Inositol hexaphosphate hydrolysis by Baker's yeast. Capacity, kinetics, and degradation products

Phytases hydrolyze myo-inositol 1,2,3,4,5,6-hexaphosphate (IP(6)), yielding lower inositol phosphates and inorganic orthophosphate. Two commercial strains of baker's yeast (Saccharomyces cerevisiae), Y(1) and Y(2), were able to express phytase activity. This was determined by the capacity to grow in a synthetic medium with IP(6) as the sole phosphorus source. IP(6) hydrolysis was rapid for both strains, and after 24 h, all IP(6) was degraded. Control cultures contained inorganic orthophosphate (P(i)) and no IP(6). Growth rate in IP(6) medium was for both strains essentially identical to growth in P(i) medium, indicating a well-adapted metabolism for utilization of phosphorus from IP(6). There was some difference in growth yield (milligrams of biomass per milligram of glucose) between the two strains: 0.95 (Y(1)) and 1.35 (Y(2)) in IP(6) medium and 1.03 and 1. 35, respectively, in P(i) medium. The phytases were of the 3-phytase type, forming mainly DL-Ins(1,2,4,5,6)P(5), DL-Ins(1,2,5,6)P(4), and DL-Ins(1,2,6)P(3).     

Mulberrofuran G and Isomulberrofuran G from Morus alba L.: Anti-hepatitis B Virus Activity and Mass Spectrometric Fragmentation

Mulberrofuran G (1) and isomulberrofuran G (2), a pair of isomeric Diels-Alder-type adducts, were isolated from the root bark of Morus alba L. Isomulberrofuran G (2) as a new IIB-type Diels-Alder-type adduct, was elucidated by extensive (1)H, (13)C, and two-dimensional (2D) nuclear magnetic resonance (NMR) and mass spectrometry (MS) spectroscopic analyses. A fragmentation study on compounds 1 and 2 was performed by high-resolution electrospray ionization (ESI) multistage tandem mass spectrometry linked with ion-trap (IT) and time-of-flight (TOF) mass analyzers (ESI-MS(n)/IT-TOF) in negative mode, which resulted in obviously different fragmentations. In the MS(2) experiments, the characteristic ions at m/z 451 and 439 could be revealed as their respective diagnostic ions. Mulberrofuran G (1) showed moderate activity, inhibiting hepatitis B virus (HBV) DNA replication with the IC(50) value of 3.99 μM, according to the anti-HBV assay on the HepG 2.2.15 cell line in vitro.     

Influence of pollution and acidification on metal concentrations in Finnish Lapland lake sediments

Fifteen Finnish Lapland lakes have been investigated to study pollution levels and possible acidification effects on nickel (Ni), copper (Cu), cobalt (Co), zinc (Zn), cadmium (Cd), lead (Pb), manganese (Mn), iron (Fe), potassium (K), sodium (Na), calcium (Ca), magnesium (Mg) and aluminium (Al) concentrations in sediments. Four lakes have average water pH lower than 6.0 and alkalinity lower than 0.050 meq/1. Contamination factor (C_f, ratio of metal concentrations in the uppermost to the deepest layers for a given lake sediment core) of Pb is high, particularly for acidic and acidifying lakes (C_f=5.2–10.4). Ni, Cu, Co, Zn and Cd concentrations increase insignificantly towards sediment surface of some lakes (with a neutral pH) with the rare exception. The influence of passible lake acidification consists of decreasing Cu, Cd, Al, Zn concentrations and organic material contents (loss on ignition) towards the sediment surface. The buffer capacity index (BCI), determined as the ratio of the sum of alkaline and alkaline-earth metals (K, Na, Ca, Mg) to Al, is lower for acidic lakes (from 0.12 to 0.36), whereas for the other lakes the BCI values are higher (from 0.42 to 1.34). Thus, BCI-values, decreased contents of Al, Cd, Zn and Cu, as well as organic matter contents (OMC in the upper lake sediment suggest acidification of freshwater environments.     

Aroma-active components of nonfat dry milk.

Application of aroma extract dilution analysis (AEDA) on the volatile components of low-, medium-, and high-heat-treated nonfat dry milks (NDM) revealed aroma-active compounds in the log(3) flavor dilution (log(3) FD) factor range of 1 to 6. The following compounds contributed the highest log(3) FD factors to overall NDM flavor: 2,5-dimethyl-4-hydroxy-3(2H)-furanone [(Furaneol), burnt sugar-like]; butanoic acid (rancid); 3-(methylthio)propanal [(methional), boiled potato-like]; o-aminoacetophenone (grape-like); delta-decalactone (sweet); (E)-4,5-epoxy-(E)-2-decenal (metallic); pentanoic acid (sweaty); 4,5-dimethyl-3-hydroxy-2(5H)-furanone [(sotolon), curry]; 3-methoxy-4-hydroxybenzaldehyde [(vanillin), vanilla]; 2-acetyl-1-pyrroline and 2-acetyl-2-thiazoline (popcorn-like); hexanoic acid (vinegar-like); phenylacetic acid (rose-like); octanoic acid (waxy); nonanal (fatty); and 1-octen-3-one (mushroom-like). The odor intensities of Furaneol, butanoic acid, methional, o-aminoacetophenone, sotolon, vanillin, (E)-4,5-epoxy-(E)-2-decenal, and phenylacetic acid were higher in high-heat-treated samples than others. However, the odor intensities of lactones, 2-acetyl-1-pyrroline, and 2-acetyl-2-thiazoline were not affected by heat treatment. Sensory evaluation results also revealed that heat-generated flavors have a major impact on the flavor profile of NDM.     

Puerins A and B, two new 8-C substituted flavan-3-ols from Pu-er tea

Pu-er tea is a special treated fermented tea produced from crude green tea, which is prepared from the leaves of Camellia sinensis var. assamica. It is a traditional beverage having been used in China, particularly the southern areas, for a long time. Chemical investigation led to the identification of two new 8-C substituted flavan-3-ols, puerins A (1) and B (2), and two known cinchonain-type phenols, epicatechin-[7,8-bc]-4alpha-(4-hydroxyphenyl)-dihydro-2(3H)-pyranone (3) and cinchonain Ib (4), together with other seven known phenolic compounds, 2,2',6,6'-tetrahydroxydiphenyl (5), (-)-epicatechin-8-C-beta-d-glucopyranoside (6), (-)-epicatechin (EC) (7), (-)-epigallocatechin (EGC) (8), (+/-)-gallocatechin (GC) (9), gallic acid (10), and myricetin (11), in addition to caffeine (12). Their structures were determined by spectroscopic methods. The compounds 1-5, which might be formed in the postfermentative process of Pu-er tea, were isolated from tea and theaceous plants for the first time.     

Foliage Age and Pollution Alter Content of Phenolic Compounds and Chemical Elements in Pinus nigra Needles

Changes of phenolics and chemical elements [nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), manganese (Mn), iron (Fe), boron (B), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd), chromium (Cr), nickel (Ni) and cobalt (Co)] content in needles of black pine ( Pinus nigra) as dependent on age of needles (5–6 classes) and pollution were examined. The content of ortho-diphenols (o-dPh) and total phenols (TPh) was significantly higher at a polluted site than at a control one. It increased with age of needles at both sites. At the polluted site contents of N, K, Mg in black pine needles were lower and of Fe, Ni and F were higher than at the control site. An increase of content with age of needles at both sites was detected for Ca, Fe, B and F, and a decrease for N, P, K, Cu and Ni. The content of elements in different age classes of needles is connected with their mobility. The content of phenolics is negatively correlated with main nutrients and positively with some toxic elements.     

半干旱地区海涂海水灌溉菊芋盐肥耦合效应的研究

在山东莱州海涂采用正交试验设计进行田间试验,研究了不同浓度海水灌溉下菊芋盐肥耦合效应。结果表明:(1)综合肥水情况下,在25%海水(W2)灌溉下菊芋块茎和地上部分生物产量与淡水处理(W1)没有显著差异,在50%(W3)和75%(W4)海水灌溉下产量均显著下降,与淡水比较,下降幅度达32%、76%和25%、60%;N3(150 kg hm-2)水平与N1(0 kg hm-2)水平相比,菊芋块茎产量可以显著提高77%,同样地上部分生物产量也提高了37%,而N4(225 kg hm-2)处理比在N3情况下低,但仍高于N2(75 kg hm-2)处理;P3(60 kg hm-2)水平与P1(0 kg hm-2)水平相比,菊芋块茎产量可以显著提高97%,同样地上部分生物产量也提高了39%,在P4(90 kg hm-2)处理下,菊芋块茎和地上部分生物产量分别比在P3处理下低19%和11%。(2)各浓度海水浇灌下,随着施氮、磷量的增加菊芋主茎普遍增长和增粗。(3)经过对海水与N肥及P肥的交互作用分析,可以看出W2N3和W2P3是优化组合;处理因子分析表明,影响菊芋产量的主要因素是不同浓度海水灌溉,N肥和P肥次之,其优化组合为W2N3P3。     

Profiling and characterization by LC-MSn of the galloylquinic acids of green tea, tara tannin, and tannic acid

Green tea, tara tannin, and tannic acid have been profiled for their contents of galloylquinic acids using LC-MS8. These procedures have provided evidence for the first observation of (i) 1-galloylquinic acid (11), 1,3,5-trigalloylquinic acid (22), 4-(digalloyl)quinic acid (28), 5-(digalloyl)quinic acid (29), and either 3-galloyl-5-(digalloyl)quinic acid (32) or 3-(digalloyl)-5-galloylquinic acid (33) from any source; (ii) 4-galloyl-5-(digalloyl)quinic acid (34), 5-galloyl-4-(digalloyl)quinic acid (35), 3-(digalloyl)-4,5-digalloylquinic acid (41), 4-(digalloyl)-3,5-digalloylquinic acid (40), 5-(digalloyl)-3,4-digalloylquinic acid (39), and 1,3,4-trigalloylquinic acid (21) from tara tannin; and (iii) 3-galloylquinic acid (12) and 4-galloylquinic acid (14) from green tea. The first mass spectrometric fragmentation data are reported for galloylquinic acids containing between five and eight gallic acid residues. For each of these mass ranges at least two isomers based on the 1,3,4,5-tetragalloylquinic acid core (25) and at least three based on the 3,4,5-trigalloylquinic acid core (24) were observed. Methanolysis of tara tannin yielded methyl gallate, methyl digallate, and methyl trigallate, demonstrating that some of these galloylquinic acids contained at least one side chain of up to four galloyl residues.     

Hydroxycinnamoylmalic acids and their methyl esters from pear (Pyrus pyrifolia Nakai) fruit peel

Two novel caffeoylmalic acid methyl esters, 2-O-(trans-caffeoyl)malic acid 1-methyl ester (6) and 2-O-(trans-caffeoyl)malic acid 4-methyl ester (7), were isolated from pear (Pyrus pyrifolia Nakai cv. Chuhwangbae) fruit peels. In addition, 5 known hydroxycinnamoylmalic acids and their methyl esters were identified: 2-O-(trans-coumaroyl)malic acid (1), 2-O-(cis-coumaroyl)malic acid (2), 2-O-(cis-coumaroyl)malic acid 1-methyl ester (3), 2-O-(trans-coumaroyl)malic acid 1-methyl ester (4), and 2-O-(trans-caffeoyl)malic acid (phaselic acid, 5). The chemical structures of these compounds were determined by spectroscopic data from ESI MS and NMR. Of all the isolated compounds, five hydroxycinnamoylmalic acids and their methyl esters (2-4, 6, 7) were identified in the pear for the first time.