Chemical composition of shallot (Allium ascalonicum Hort.)

An extensive phytochemical analysis of the polar extracts from bulbs of shallot, Allium ascalonicum Hort., led to the isolation of two new furostanol saponins, named ascalonicoside A1/A2 (1a/1b) and ascalonicoside B (4), respectively, along with compounds 2a and 2b, most likely extraction artifacts. On the basis of 2D NMR and mass spectrometry data, the structures of the novel compounds were elucidated as furost-5(6)-en-3beta,22alpha-diol 1beta-O-beta-D-galactopyranosyl 26-O-[alpha-L-rhamnopyranosyl-(1-->2)-O-beta-D-glucopyranoside] (1a), its epimer at position 22 (1b), and furost-5(6),20(22)-dien-3beta-ol 1beta-O-beta-D-galactopyranosyl 26-O-[alpha-L-rhamnopyranosyl-(1-->2)-O-beta-D-glucopyranoside] (4). This is the first report of furostanol saponins in A. ascalonicum. High concentrations of quercetin, isorhamnetin, and their glycosides were also isolated and described.     

Two novel dicarboxylic Acid derivatives and a new dimeric hydrolyzable tannin from walnuts

In addition to the 16 previously reported polyphenols including 3 new ellagitannins, 2 novel dicarboxylic acid derivatives, glansreginins A (1) and B (2), and a new dimeric hydrolyzable tannin, glansrin D (3), were isolated, together with 15 known compounds from walnuts, the seeds of Juglans regia. The structures of the new compounds were elucidated on the basis of 1D- and 2D-NMR analyses and chemical data. The antioxidant effect of these isolates was also evaluated by SOD-like and DPPH radical scavenging activities.     

A Novel Compound with Antioxidant Activity Produced by Serratia ureilytica TKU013

The secondary metabolites from the cultured supernatant of Serratia ureilytica TKU013 with squid pen as the sole carbon/nitrogen source were isolated and ascertained the mechanism of biological activity. The EtOAc layer, which has high DPPH scavenging activity, was applied to silica gel column chromatography with a gradient of CH(2)Cl(2)/MeOH solvent system, to yield A-H and MeOH fractions. The DPPH scavenging activity and cytotoxic activities against Doay and HEp-2 cell lines of these fractions were examined. The active fractions were further applied to purification by RP-HPLC, to obtain seven compounds, including a novel compound, serlyticin-A (1), together with six known compounds, serranticin (2), serratamolide A (3), thymine (4), (4-hydroxyphenyl)acetic acid (5), methyl p-hydroxybenzoate (6), and uracil (7). Their structures were determined by physical and extensive spectral analyses such as 1D and 2D NMR data, as well as comparison with literature values. Furthermore, the major secondary metabolites of EtOAc extract of the cultured supernatant were examined by the fingerprinting data of the HPLC system.     

Seven new aminoacyl sugars in Ipomoea batatas

An analysis of the polar extracts from sweet potato Ipomoea batatas (Convolvulaceae) led to the isolation of seven unknown aminoacyl sugars. On the basis of 1D, 2D NMR, and mass spectrometry data, the structures of the compounds were elucidated as: beta-D-fructofuranosyl-(2 --> 1)-alpha-D-[2-O-valyl]-glucopyranoside (1), beta-D-fructofuranosyl-(2 --> 1)-alpha-D-[2-O-tyrosyl]-glucopyranoside (2), beta-D-fructofuranosyl-(2 --> 1)-alpha-D-[2-O-threonyl]-glucopyranoside (3), beta-D-fructofuranosyl-(2 --> 1)-alpha-D-[2-O-hystidyl]-glucopyranoside (4), 2-beta-D-fructofuranosyl-(2 --> 1)-alpha-D-[2-O-alanyl]-glucopyranoside (5), beta-D-fructofuranosyl-(2 --> 1)-alpha-D-[2-O-tryptophanyl]-glucopyranoside (6), and beta-D-fructofuranosyl-(2 --> 1)-alpha-D-[2-O-glycyl]-glucopyranoside (7).     

Antioxidant xanthones from the pericarp of Garcinia mangostana (Mangosteen)

As part of ongoing research on cancer chemopreventive agents from botanical dietary supplements, Garcinia mangostana L. (commonly known as mangosteen) was selected for detailed study. Repeated chromatography of a CH2Cl2-soluble extract of the pericarp led to the isolation of two new highly oxygenated prenylated xanthones, 8-hydroxycudraxanthone G (1) and mangostingone [7-methoxy-2-(3-methyl-2-butenyl)-8-(3-methyl-2-oxo-3-butenyl)-1,3,6-trihydroxyxanthone, 2], together with 12 known xanthones, cudraxanthone G (3), 8-deoxygartanin (4), garcimangosone B (5), garcinone D (6), garcinone E (7), gartanin (8), 1-isomangostin (9), alpha-mangostin (10), gamma-mangostin (11), mangostinone (12), smeathxanthone A (13), and tovophyllin A (14). The structures of compounds 1 and 2 were elucidated by spectroscopic data analysis. Except for compound 2, which was isolated as a minor component, the antioxidant activities of all isolates were determined using authentic and morpholinosydnonimine-derived peroxynitrite methods, and compounds 1, 8, 10, 11, and 13 were the most active. Alpha-mangostin (10) inhibited 7,12-dimethylbenz[alpha]anthracene-induced preneoplastic lesions in a mouse mammary organ culture assay with an IC50 of 1.0 microg/mL (2.44 microM).     

Analysis of technical lignins by two- and three-dimensional NMR spectroscopy

Modern multidimensional NMR spectroscopic methods were applied to investigate the effects of kraft pulping and oxygen delignification on lignin side-chain structures. In addition to the two-dimensional HSQC measurements, the three-dimensional HSQC-TOCSY technique was utilized to elucidate the (1)H-(1)H and (1)H-(13)C correlations of individual spin systems and thus indicate a certain lignin side-chain structure. Unlike earlier, nonlabeled samples were used for 3D measurements. According to 2D and 3D NMR spectra, most of the structures identified in milled wood lignin (MWL) are still present in technical lignins after kraft pulping and oxygen delignification. Although the main reaction during kraft pulping is the cleavage of beta-O-4 linkages, these structures are still left in spent liquor lignin as well as in residual lignin. The amount of coniferyl alcohol and dihydroconiferyl alcohol end groups, as well as some unidentified saturated end groups, is higher in technical lignins than in MWL. Contrary to our earlier observations, no diphenylmethane structures were observed in any technical lignins. Vinyl aryl ether structures could not be detected in technical lignins either.     

Protopanaxatriol-type ginsenosides from the root of Panax ginseng

Ginseng, the root of Panax ginseng C. A. Meyer (Araliaceae), is one of the most important traditional medicines and functional foods. A detailed phytochemical investigation on the roots of P. ginseng led to the isolation of 6 new natural protopanaxatriol (PPT)-type ginsenosides, ginsenosides Re(1)-Re(6) (compounds 1-6), along with 10 known PPT-type ginsenosides. Their structures were elucidated on the basis of chemical and spectroscopic analyses, including high-resolution mass spectrometry (HRMS) and 1D and 2D nuclear magnetic resonance (NMR). The unusual α-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl sugar chain, as found in compounds 1 and 2, is reported in the genus Panax for the first time.     

Triterpenoid saponins from the shells of Argania spinosa seeds

Two new oleanene saponins were isolated from the MeOH extract of the shell of Argania spinosa.They possess protobassic acid and 16alpha-protobassic acid as aglycons. The disaccharide moiety linked to C-3 of the aglycon is made up of two glucose units; the pentasaccharide moiety linked to C-28 is made up of arabinose, xylose, and three rhamnose units. Their structures were elucidated by 1D and 2D NMR experiments including (1)H-(1)H (DQF-COSY, 1D TOCSY, and 2D HOHAHA) and (1)H-(13)C (HSQC and HMBC) spectroscopy along with mass spectrometry.     

Withanolides from the rhizomes of Dioscorea japonica and their cytotoxicity

Edible yams are tropical crops that serve as important staple foods in many parts of the world. The rhizome of Dioscorea japonica , well-known as "Japanese yam", is a food and medicinal source known as "San Yak" in Korea. Bioassay-guided fractionation and chemical investigation of the extract of this yam resulted in the identification of two new withanolides, named dioscorolide A (1) and dioscorolide B (2). The structures of these new compounds were determined by spectroscopic methods, including 1D and 2D nuclear magnetic resonance (NMR) techniques, high-resolution mass spectrometry (HRMS), and chemical methods. The cytotoxic activities of the isolates (1 and 2) were evaluated by determining their inhibitory effects on four human tumor cell lines (A549, SK-OV-3, SK-MEL-2, and HCT15) and a human normal cell line (HUVEC) using a sulforhodamine B (SRB) bioassay. Compounds 1 and 2 showed cytotoxicity against tumor cell lines (A549, SK-OV-3, SK-MEL-2, and HCT15) with IC(50) values ranging from 6.3 to 26.9 μM and exhibited lower activity against the normal cell line (HUVEC) with IC(50) values ranging from 27.1 to 28.8 μM, suggesting selective toxicity among tumor and normal cells.     

New cyclic peptides from the seeds of Annona squamosa L. and their anti-inflammatory activities

Two new cyclic peptides, cyclosquamosin H ( 1) and I ( 2), together with six known cyclic peptides, squamin A ( 3), squamin B ( 4), cyclosquamosin A ( 6), cyclosquamosin D ( 7), cyclosquamosin E ( 8), and cherimolacyclopeptide B ( 9), were isolated from the seeds of Annona squamosa. All structures were confirmed by 2D nuclear magnetic resonance, chemical evidence, and electrospray ionization-mass spectromotry/mass spectrometry (ESI-MS/MS). Compound 9 was isolated from this plant for the first time. In the anti-inflammatory assay, compound 7 showed an inhibitory effect on the production of pro-inflammatory cytokines within lipopolysaccharide and Pam3Cys-stimulated J774A.1 macrophages.     

Identification of antioxidative flavonols and anthocyanins in Sicana odorifera fruit peel

Ten flavonols and three anthocyanins were identified in the fruit peel of melo?n de olor (Sicana odorifera), and their structures were established by spectrometric and spectroscopic (ESI-MS and NMR) techniques. One of the identified flavonols, quercetin 3-O-(6'-O-malonyl)-β-D-glucopyranoside 4'-O-β-D-glucopyranoside, has not been reported before in the plant kingdom. Although quercetin-3-O-α-L-rhamnopyranosyl-(1→6)-β-d-glucopyranoside-4'-O-β-D-glucopyranoside had been reported before in literature and structure elucidation was done by comparison of NMR data with published data, to the best of our knowledge complete 1D and 2D NMR data have not been not delineated so far. Moreover, the antioxidant activity of pure compounds was measured by ABTS assay. It was established that quercetin 3-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside, quercetin-3-O-(6'-malonyl)-glucopyranoside, quercetin-3-O-β-D-glucopyranoside, and quercetin-3-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside-4'-O-β-D-glucopyranoside contribute significantly to the antioxidant activity exhibited by the fruit peel methanolic extract.     

融合高光谱图像技术与MS-3DCNN的小麦种子品种识别模型

小麦品种的纯度和小麦产量密切相关,为了实现小麦种子品种的快速识别,该研究利用高光谱图像技术结合多尺度三维卷积神经网络（Multi-Scale 3D Convolutional Neural Network,MS-3DCNN）提出了一种小麦种子的品种识别模型。首先,利用连续投影算法（Successive Projections Algorithm,SPA）对原始高光谱图像进行波段选择,以减少MS-3DCNN模型的输入图像通道数量,降低网络训练参数规模;其次,利用多尺度三维卷积模块提取特征图的图像特征和不同特征图之间的耦合特征;最后,以6个品种小麦共6 000粒种子的高光谱图像（400～1 000 nm）为研究对象,基于SPA算法选择了22个波段高光谱数据,利用MS-3DCNN、支持向量机（Support Vector Machine,SVM）分别构建了识别模型。试验结果表明,MS-3DCNN模型取得了96.72%的测试集识别准确率,相较于光谱特征SVM识别模型和融合特征SVM识别模型分别提高了15.38%和9.50%。进一步比较了MS-3DCNN与基于二维卷积核、三维卷积核、多尺度二维卷积核构建的多个识别模型性能,结果表明多尺度三维卷积核能提取多种尺度的信息,其识别模型的准确率提高了1.34%～2.70%,可为小麦种子高光谱图像品种识别提供一种可行的技术途径。     

Isolation of two bioactive ent-kauranoids from the leaves of Isodon xerophilus

Isodon xerophilus has been used as a herbal cold tea for the prevention and treatment of sore throat and inflammation in southernwestern China. A phytochemical study on the ethyl acetate (EtOAc) soluble fraction of I. xerophilus leaves led to the isolation of two new ent-kauranoids, xerophinoids A (1) and B (2), together with 14 known diterpenoids. The structures of xerophinoids A (1) and B (2) were illustrated using spectroscopic methods including 1D and 2D NMR analyses. To study their biological activities, the effects of xerophinoids A (1) and B (2) on nitrite production, tumor necrosis factor (TNF)-alpha and interleukin (IL)-1beta were examined. In addition, xerophinoids A (1) and B (2) also exhibited potent cytotoxicity against several human tumor cell lines (IC50 < 11 microM), but they had no toxicity on human T-lymphocyte (C8166).     

Reactivity of anthocyanins and pyranoanthocyanins. Studies on aromatic hydrogen-deuterium exchange reactions in methanol

Reactivity studies involving anthocyanin structures and their equilibrium forms will lead to better understanding of the properties of these antioxidants. Hydrogen-deuterium (H --> D) exchange reactions at various sites of the 3-glucosides of delphinidin (1), petunidin (2), malvidin (3), and the corresponding 3-glucosides of carboxypyranodelphinidin (4), carboxypyranopetunidin (5), carboxypyranomalvidin (6), and the flavonol quercetin 3-O-(6-alpha-rhamnopyranosyl-beta-glucopyranoside)(7) have been examined at room temperature in pure CD 3OD and in CD 3OD acidified with CF 3CO 2D. The H --> D exchange rate constants of H-6 and H-8 of 2 determined from (1)H NMR integration data were found to be independent upon pigment concentration (up to 4 x 10 (-2) M) and trifluoroactic acid concentration (0-15%, v/v), respectively. This suggest that these reactions follow first-order kinetics and unexpectedly to be independent of the acid concentration. H-6 and H-8 of the flavylium cation A-rings of 1- 3, and in the corresponding hydrogens of the hemiketal forms, exchanged with half-lives of approximately 100 h ( 1) and approximately 50 h ( 2 and 3), respectively. The pyranoanthocyanins (4-6) experienced no H --> D exchange for the analogous hydrogens, but H --> D exchange of H-beta (H-4)(t 1/2 approximately 25 h) for these compounds was observed. Only H-8 underwent significant H --> D exchange in 7. It is concluded that a stabilization of the sigma-complexes, assumed to be the intermediates in the reactions, takes place for the common anthocyanins (1-3) contrary to the pyranoanthocyanins (4-6).     

Isolation, structure determination, and sensory activity of mouth-drying and astringent nitrogen-containing phytochemicals isolated from red currants (Ribes rubrum)

Application of chromatographic separation and taste dilution analyses recently revealed, besides a series of flavon-3-ol glycosides and (E)/(Z)-aconitic acid, four nitrogen-containing phytochemicals as the key astringent and mouth-drying compounds in red currants (Ribes rubrum). The isolation and structure determination of the astringent indoles 3-carboxymethyl-indole-1-N-beta-D-glucopyranoside (1) and 3-methylcarboxymethyl-indole-1-N-beta-D-glucopyranoside (2), as well as the astringent, noncyanogenic nitriles 2-(4-hydroxybenzoyloxymethyl)-4-beta-D-glucopyranosyloxy-2(E)-butenenitrile (3) and 2-(4-hydroxy-3-methoxybenzoyloxymethyl)-4-beta-D-glucopyranosyloxy-2(E)-butenenitrile (4) by means of 1D/2D NMR, LC-MS/MS, and UV-vis spectroscopy are reported. The structures of compounds 1 and 2 were confirmed by synthesis. Using the recently developed half-tongue test, human recognition thresholds for the astringent and mouth-drying nitrogen compounds were determined to be between 0.0003 and 5.9 micromol/L (water). In particular, the extraordinarily low threshold of 0.0003 micromol/L evaluated for the indole 1 represents the lowest recognition threshold of any astringent phytochemical reported to date.     

New dammarane-type saponins from the galls of Sapindus mukorossi

Five new dammarane-type saponins, 3beta,7beta,20(S),22-tetrahydroxydammar-24-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, 3beta,7beta,20(S),22,23-pentahydroxydammar-24-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, 3beta,7beta,20(S),22,25-pentahydroxydammar-23-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, 25-methoxy-3beta,7beta,20(S),22-tetrahydroxydammar-23-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, and 25-methoxy-3beta,7beta,20(R)-trihydroxydammar-23-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, named sapinmusaponins A (1), B (2), C (3), D (4), and E (5), respectively, together with three known phenylpropanoid glycosides (6-8), were isolated from the galls of Sapindus mukorossi. The structures of these saponins were elucidated on the basis of spectroscopic analyses and chemical methods. Preliminary bioassay data revealed that saponins 1 and 3-5 showed moderate cytotoxic activity (ED50 approximately 9-18 microg/mL) against human tumor cell lines (Hepa59T/VGH, NCI, HeLa, and Med) and that 1-5 were inactive in vitro against HIV replication in H9 lymphocytes.     

小麦代换系幼苗根系对低磷胁迫的生理响应暗示的染色体效应

【目的】 以 CS (Chinese Spring,中国春) -Synthetic 6x 代换系为材料,研究小麦代换系幼苗根系对低磷胁迫的生理响应,并对相关性状进行染色体定位,为小麦耐低磷基因型的遗传改良提供理论依据。 【方法】 将母本中国春、父本 Synthetic 6x 以及代换系种子放于培养皿,于光照培养箱中培养 5 d,选择长势一致的健壮幼苗去掉胚乳,移入 Hoagland 营养液 (pH = 6.0)中培养。两叶一心时进行处理,设置正常供磷为对照 (磷浓度为2 mmol/L) 和低磷胁迫 (磷浓度为 20 μmol/L) 两个处理,四叶一心时对不同磷处理下代换系幼苗的根冠比、根系活力、酸性磷酸酶 (APase) 和核糖核酸酶 (RNase) 活性等生理指标进行测定。 【结果】 低磷胁迫下,小麦代换系苗期根冠比显著升高,APase 和 RNase 活性增强,根系活力降低;与母本中国春相比,4A、4B、6B、1D、2D 和 7D 代换系根冠比和相对根冠比显著或极显著升高,1A、2A、3A、5A、3B、7B、2D、3D、5D 和 7D 代换系的根系活力和相对根系活力显著或极显著增高,4A、1D 和 4D 代换系根系的酸性磷酸酶活性及相对磷酸酶活性均显著或极显著升高,2A、6B、4D 代换系根系的 RNase 活性和相对 RNase 活性显著或极显著增高。 【结论】 低磷胁迫下,Synthetic 6x 的 4A、4B、6B、2D 和 7D 染色体上可能存在诱导根冠比升高的基因;1A、2A、3A、5A、3B,7B、2D、3D、5D 和 7D 染色体上可能存在诱导根系活力增强的基因;4A、1D 和 4D 染色体上可能存在诱导根系酸性磷酸酶活性增强的基因;2A、6B 和 4D 染色体上可能存在诱导根系 RNase 活性增强的基因。即 Synthetic 6x 的第四染色体 (4A、4B、4D) 上可能存在调控根系相关特性的关键基因。      

同化AMSR2数据提高HYDRUS-1D模型土壤湿度模拟精度

同化遥感监测数据提高土壤剖面湿度模拟精度,对区域农业发展等实践与理论领域具有重要意义。该文结合了集合卡尔曼滤波(ensemble Kalman filter,EnKF)方法与HYDRUS-1D模型,同化降尺度后的AMSR2(advanced microwave scanningradiometer2)微波土壤湿度数据,开展榆社、荫城2个实验站点的土壤剖面湿度模拟。结果表明:在2个实验站点,与直接使用HYDRUS-1D模型相比,同化具有一定误差的AMSR2土壤湿度数据对不同深度土壤湿度的模拟精度提高都发挥了作用,尤其是对于同化前模拟方案S1(4月1日站点实测含水量)与S4(4月1日遥感含水量),由于HYDRUS-1D模拟时输入了较少数量的土壤湿度数据,数据同化效果与土壤湿度模拟精度提高更为显著;同化前后不同深度的土壤湿度精度对比结果表明,同化效果随深度增加而逐渐减弱。     

Near‐Infrared Spectroscopy for Determination of Protein and Amylose in Rice Flour Through Use of Derivatives

The use of the derivative method for near‐infrared (NIR) calibration was investigated to determine protein and amylose content in rice flour. Samples for two years, 1996 and 1999, were combined to give a wide range of the constituents for development of the calibration model. The NIR spectral data were transformed with Savitzky‐Golay derivative with multiplicative scatter correction. To develop the best derivative models, the polynomial fits (quadratic, cubic, and quartic), convolution intervals (3–11 points for protein, 3–17 points for amylose), and derivative orders (1st derivative D1; 2nd derivative D2) were investigated. For the protein analysis, all polynomial fits with 3–11 points were acceptable to develop both the D1 and D2 models. However, the three‐point quadratic and five‐point quartic fits were not acceptable for the D1 model, and the three‐point quadratic fit was not acceptable for D2. For the amylose analysis, the D1 model produced generally better results than D2. Higher convolution intervals were required for the D2 model, whereas the D1 model was not affected by convolution intervals. A quadratic (or cubic) fit with 17‐point convolution interval was acceptable for the amylose D2 model, and the quadratic fit with 5–11 points and cubic (or quartic) fit with 7–17 points were suitable for the D1 model. Based on the standard error of cross‐validation (SECV), the calibration models developed using data for two years resulted in good precision with an SECV of 0.23% for protein using four factors and an SECV of 1.0% for amylose using 10 factors.     

Anthogorgienes A-O, new guaiazulene-derived terpenoids from a Chinese gorgonian Anthogorgia species, and their antifouling and antibiotic activities

Fifteen new guaiazulene-based terpenoids designated anthogorgienes A-O (1-15) were isolated from a Chinese gorgonian Anthogorgia sp., together with eight known analogues (16-23). The structural patterns were classified into monomers, dimers, and trimers, which were supposed to be generated from a precursor guaiazulene and followed by side-chain and nucleus oxidation and oxidative rearrangement. The structures of new compounds were elucidated on the basis of extensive spectroscopic (IR, MS, and 1D and 2D NMR) data analysis. A possible biogenetic relationship of the isolated compounds was postulated. Some of the compounds showed potent antifouling activities against the larval settlement of barnacle Balanus amphitrite , whereas their antibiotic activities were also evaluated.