红曲色素的两种新结构

从中国科学院微生物研究所保藏红曲菌中,筛选得到一株高产红色素的红曲菌菌株（ＡＳ．３．４６１７）。经鉴定属于红色红曲菌。通过有机溶剂的萃取和两次硅胶柱层析,从该菌株中分离得到两种色素样品,高压液相色谱测定为纯色素样品。通过元素组成分析,核磁共振谱,快离子轰击,质谱和高分辨质谱分析确定,这两种色素与已知的六种红曲菌色素不同,为新发现的红曲菌色素,它们可能的分子式为：Ｃ２５Ｈ３１Ｏ５Ｎ和Ｃ２３Ｈ２７Ｏ５     

红曲色素的两种新结构

从中国科学院微生物研究所保藏红曲菌中,筛选得到一株高产红色素的红曲菌菌株(AS.3.4617)。经鉴定属于红色红曲菌(Monascus anka Sato).通过有机溶剂的萃取和两次硅胶柱层析,从该菌株中分离得到两种色素样品,高压液相色谱测定为纯色素样品。通过元素组成分析,核磁共振谱,快离子轰击,质谱和高分辨质谱分析确定,这两种色素与已知的六种红曲菌色素不同,为新发现的红曲菌色素,它们可能的分子式为:C_(25)H_(31)O_5N和C_(23)H_(27)O_5N。     

高速逆流色谱技术分离纯化红葱中的萘醌类化合物

采用高速逆流色谱(HSCCC)技术从红葱中快速分离纯化得到红葱乙素和异红葱乙素,建立了快速分离制备红葱中萘酚类化合物的方法。首先采用95%乙醇加热回流提取得红葱提取物,再用乙酸乙酯萃取富集萘醌类成分,然后用高速逆流色谱分离纯化,以石油醚-乙酸乙酯-甲醇-水(6∶4∶5∶5,v/v)组成二元溶剂系统,上相为固定相,下相为流动相,仪器转速为850 rpm,流速为2.0 m L/min,检测波长为254 nm。从200 mg富集萘醌类成分的粗提物中,一次性分离制备得到60 mg异红葱乙素和49 mg红葱乙素,经高效液相色谱法(HPLC)分析,其纯度分别为97.3%和98.6%。通过核磁共振氢谱(~1H NMR)和核磁共振碳谱(~(13)C NMR)鉴定化合物为红葱乙素和异红葱乙素。研究结果表明,该方法快速、高效,适用于红葱中萘酚类化合物的分离纯化。     

红酵母超高压突变体的类胡萝卜素提取及特性研究

采用酸-热法破壁和丙酮为提取溶剂,在所优化的最佳组合条件下,从红酵母超高压突变株提取类胡萝卜素,平均提取率可达718.1μg/g干细胞。色素粗提物采用柱色谱分离纯化后,通过薄层色谱（TLC）、紫外光谱和HPLC进行分析,发现该酵母突变体的发酵产物至少含β-胡萝卜素、园酵母素和红酵母红素等3种色素,其中β-胡萝卜素含量最多,超过50%的比例。该色素提取物的光热稳定性好于先前报道的同类色素;体外清除自由基实验也表明该类胡萝卜素提取物具有良好的抗氧化活性。因此,利用该突变株发酵生产类胡萝卜素值得进一步研究和开发。     

云南马铃薯地方彩色品种“剑川红”和“转心乌”的花色苷主成分分析

彩色马铃薯富含花色苷,是一种天然抗氧化食品.本研究采用高效液相色谱质谱联用技术以引进品种“黑美人”为对照分析了云南马铃薯地方特色品种“剑川红”和“转心乌”花色苷的主要成分.结果表明:“剑川红”色素主要为酰化天竺葵色素类花色苷,其主要成分为天竺葵素3-[ 6-O-( 4-O-E-p-香豆酰-O-α-吡喃鼠李糖苷)-β-D-吡喃葡萄糖苷]-5-O-β-D-毗喃葡萄糖苷.“转心乌”和“黑美人”所含色素相似,主要为酰化矮牵牛色索、锦葵色素、芍药色素类衍生物,主要成分均为矮牵牛花色素3-[ 6-O-( 4-O-E-p-香豆酰-O-α-吡喃鼠李糖苷)-β-D-毗喃葡萄糖苷]-5-O-β-D-毗喃葡萄糖苷.     

广东红冬蛇菰及其内生真菌Penicillium coprophilum Mzz9的化学成分研究

本文研究了广东梅州地区产名贵中药材红冬蛇菰及其内生真菌Penicillium coprophilum Mzz9的化学成分。通过多种色谱技术和波谱学分析共分离鉴定了11个化合物。从红冬蛇菰的二氯甲烷萃取物中分离得到5个化合物:羽扇豆醇(1)、β-香树脂醇(2)、鄁桐甾醇(3)、乙酸蛇麻脂醇酯(4)和亚油酸甘油酯(5);从其内生真菌P.coprophilum Mzz9的发酵液中分离得到6个化合物:去氯灰黄霉素(6)、灰黄霉素(7)、脱氢灰黄霉素(8)、oxaline(9)、4-megastigmen-3,9-dione(10)、对羟基苯乙酮(11)。其中化合物1和5为首次从红冬蛇菰中分离得到,化合物6～11为首次从红冬蛇菰的内生真菌中分离得到。     

红背桂花化学成份研究

利用色谱技术对云南西双版纳产红背桂花(Excoecaria cochmchmensis Lour.)的化学成分进行分离纯化,从其乙醇提取物分离得到8个化合物,经理化和光谱分析,分别鉴定为:桦木酸(1)、没食子酸(2)、对羟基苯甲醛(3)、β-谷甾醇(4)、胡萝卜甙(5)、豆甾醇(6)、棕榈酸(7)、6-羟基豆甾醇(8).化合物1-8均为首次从红背桂花中分离得到.     

辽东(木匆心)木挥发油的成分

本文采用气相色谱-质谱-计算机（GC-MS-DS）联用技术,首次研究了辽东楤木根皮中的挥发性成分,鉴定了37个化合物。成分中以α-姜黄烯（α-curcumene）等为主,含量达15.32％,此外尚含有薁类和大量的萘衍生物。     

国外红曲色素的研制及应用

红曲色素是由红曲霉经固体或液体培养生产的一种天然食用色素.用以食品着色,能增加食品的美观及花色,有助于提高商品价值.近年来,由于食品卫生的研究和科学技术的发展,对食品的质量要求越来越高。在食品工业急需开发无公害天然色素的今天,用这种红曲色素来代替合成色素,对减少食品的污染,保障人体健康具有重要意义。红曲的生产和应用,始于我国,后来传到日本.据文献报道,日本从一八九○年便开始对红曲霉发酵所产生的色素进行了分离研究。一九二六年已分离出三种不同色素的结     

一种简捷的分离杜鹃花类菌根真菌的方法

目的：简化杜鹃花类菌根真菌的分离方法,快速得到菌株。方法：选择并改良马丁氏-孟加拉红培养基,调整其pH值约为5．0,0．3～0．5cm根段平铺于平板中培养分离菌株,培养条件为25℃黑暗培养12～15d。结果：得到了菌落特征有明显差异的9种类型138个菌根真菌菌株,其中7类菌株在人工条件下回接云锦杜鹃形成了菌根结构。结论：实验证明改良的分离方法操作简单快捷,是杜鹃花类菌根真菌分离的一种可靠方法。     

Jatropham derivatives and steroidal saponins from the bulbs of Lilium hansonii.

Two new jatropham derivatives and three new steroidal saponins were isolated from the fresh bulbs of Lilium hansonii, along with previously known compounds. The structures of the new compounds were elucidated, on the basis of spectroscopic data and chemical evidence, and by comparing them with those of known compounds, as (-)-5-hydroxy-3-methyl-3-pyrrolin-2-one (jatropham) 5-O-beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranoside, (2S*,4R*)-1-(3-methyl-2-oxo-3-pyrrolinyl)-4-methyl-5-oxo-2-pyrr olidinecarboxyli c acid, 26-O-beta-D-glucopyranosyl-(25R)-5 alpha-furostan-3 beta,22 zeta-diol 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)]- beta-D-glucopyranoside, (25R)-5 alpha-spirostan-3 beta,12 alpha-diol 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)]- beta-D-glucopyranoside and (25R)-spirost-5-en-3 beta,12 alpha-diol 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)]- beta-D-glucopyranoside, respectively. The stereostructure of jatropham dimer, the plain structure of which was presented previously, was confirmed by X-ray crystallographic analysis. The inhibitory activity on cyclic AMP phosphodiesterase of the steroidal saponins was evaluated.     

A new ganglioside of the lactotetraose series, GalNAc-3'-isoLM1, detected in human meconium

A monoclonal antibody produced by immunization with cells of the human glioma cell line D-54 MG reacted with ganglioside GM2. The binding epitope of the antibody was found to be GalNAc beta 1-4(NeuAc alpha 2-3)Gal. Immunological detection of glycolipid antigens on thin-layer plates with this monoclonal antibody, DMAb-1, revealed the presence of a new ganglioside. This ganglioside, co-migrating with NeuAc alpha 2-6Gal beta 1-4GlcNAc beta 1-3Gal beta 1-4Glc beta 1-1Cer(6'-LM1) and GalNAc beta 1-4(NeuAc alpha 2-3)Gal beta 1-3GalNAc beta 1-4Gla beta 1-4Glc beta 1-1Cer (GalNAc-isoGM1) at chromatographic separation was isolated from human meconium. Its structure was determined by permethylation and fast atom bombardment-mass spectometry analyses. The new ganglioside was found to be a combination of the lacto and ganglio series gangliosides, and the structure found to be GalNAc beta 1-4(NeuAc alpha 2-3)Gal beta 1-3GlcNAc alpha 1-3Gal beta 1-4Glc beta 1-1Cer(GalNAc-3'-isoLM1).     

Application of lipase-catalyzed transformations for the synthesis of insect pheromones and related compounds

This review describes efficient means of preparing optically pure insect pheromones and related compounds via lipase-catalyzed enantioselective reaction on a large scale. (1) A new synthesis of the Japanese beetle pheromone, (R,Z)-(−)-5-(1-decenyl)oxacyclopentan-2-one, established by a combination of two lipase-catalyzed transformation was demonstrated. (2) A chemico-enzymatic procedure for the syntheses of both enantiomers of cupreous chafer beetle pheromone, (R,Z)- and (S,Z)-5-(1-octenyl)oxacyclopentan-2-one, was described. (3) An optical resolution of (±)-2,3-epoxy-8-methyl-1-nonanol, the key intermediate of the synthesis of gypsy moth pheromone, was demonstrated. (4) A practical chemico-enzymatic synthesis of (+)-disparlure in large scale was demonstrated. (5) A facile synthesis of carboxyalkyl acrylate, which is special monomers in the synthesis of the new polymers, by two lipase-catalyzed regioselective reactions was described.     

浆果楝中的新木脂素

从浆果楝（Cipadessa baccifera）中分离得到两个木脂素,其化学结构通过波谱方法鉴定为：（-）-9′-O-（E）-coumarate-5,5′-dimethoxylariciresinol（1）和（＋）-9′-O-（E）-feruloyl-5,5′-dimethoxylariciresinol（2）。其中化合物1为新化合物。     

Enzyme inhibition assays using fluorescence correlation spectroscopy: a new algorithm for the derivation of kcat/KM and Ki values at substrate concentrations much lower than the Michaelis constant

A new mathematical formalism is deduced which allows for the calculation of the k(cat) over K(M) ratio based on measurements of the enzyme kinetics with substrate concentrations much lower than K(M). The equations are also applied on the action of an inhibitor on enzyme activity yielding the binding constant, K(i), of an inhibitor molecule. For practical evaluation of the new theoretical approach, the enzymatic reaction of CD45 phosphatase was used as a well-characterized model system with known inhibitors for testing the K(i) value determination scheme. The k(cat)/K(M) ratio was calulated to be 4.7 x 10(5) M(-)(1) s(-)(1), the K(i) of the inhibitor molecule PKF52-524 was estimated to be (1-2) x 10(-)(7) M and the association rate of the inhibitor PKF52-524 to CD45 phosphatase was estimated to be 59 M(-)(1) s(-)(1).     

Microbial transformation of spirolaxine, a bioactive undecaketide fungal metabolite from the basidiomycete Sporotrichum laxum

Incubation of (+)-spirolaxine (= (3R)-5-hydroxy-7-methoxy-3-{5-[(2R,5R,7R)-2-methyl-1,6-dioxaspiro[4.5]dec-7-yl]pentyl}-2-benzofuran-1(3H)-one; 1a) with Bacillus megaterium afforded two new mono- and one new dihydroxylated metabolite(s), all OH groups being introduced on the non-activated six-membered ring. In contrast, exposure of 1a to Cunninghamella echinulata gave rise to hydroxylation on the five-membered ring of the parent structure. The structures and absolute configurations of the new products 1b-e were deduced on the basis of MS and NMR data. The metabolite 1b was investigated, in comparison to 1a, for its cytotoxicity (sulforhodamin-B test) and for its antiproliferative activity towards bovine microvascular endothelial cells (BMEC).     

A new sugar chain of the proteinase inhibitor from latex of Carica papaya

The structure of a sugar chain of the proteinase inhibitor from the latex of Carica papaya was studied. Sugar chains liberated on hydrazinolysis were N-acetylated, and their reducing-end residues were tagged with 2-aminopyridine. One major sugar chain was detected on size-fractionation and reversed-phase HPLC analyses. The structure of the PA-sugar chain was determined by two-dimensional sugar mapping combined with sequential exoglycosidase digestion and partial acid hydrolysis, and by 750 MHz 1H-NMR spectroscopy. The structure found was Manalpha1-6(Manalpha1-3)Manalpha1-6(Manalpha1-3) (Xylbeta1-2)Manbeta1- 4GlcNAcbeta1-4(Fucalpha1-3)GlcNAc. This sugar chain represents a new plant-type sugar chain with five mannose residues.     

Molecular cloning and expression of a new alpha-subunit of soluble guanylyl cyclase. Interchangeability of the alpha-subunits of the enzyme.

A cDNA coding for a new subunit of soluble guanylyl cyclase with a calculated molecular mass of 81.7 kDa was cloned and sequenced. On the basis of sequence homology, the new subunit appears to be an isoform of the alpha 1-subunit and was designated alpha 2 as the new subunit is very similar to the alpha 1-subunit in the middle and C-terminal part; it is quite diverse in the N-terminal part. Preceding experiments had shown that coexpression of the alpha 1- and beta 1-subunits is necessary to obtain a catalytically active guanylyl cyclase in COS cells [(1990) FEBS Lett. 272, 221-223]. The finding that the alpha 2-subunit was able to replace the alpha 1- but not the beta 1-subunit in expression experiments demonstrates the interchangeability of the alpha-subunit isoforms of soluble guanylyl cyclase.     

Cyclooxygenase-inhibitory and antioxidant constituents of the aerial parts of Antirhea acutata.

Two new compounds, (6S)-hydroxy-29-nor-3,4-seco-cycloart-4(30),24-dien-3-oic acid (1) and 8-[1-(3,4-dihydroxyphenyl)-3-methoxy-3-oxopropyl]epicatechin (3), were isolated by bioassay-guided fractionation from the aerial parts of Antirhea acutata (DC.) Urb. (Rubiaceae). Compound 1 showed moderate inhibitory activities in cyclooxygenase-1 and -2 assays (IC(50) 43.7 and 4.7 microM, respectively), while compound 3 was active in 1,1-diphenyl-2-picrylhydrazyl free-radical and cytochrome c reduction antioxidant assays (IC(50) 29.1 and 16.3 microM, respectively). Additionally, one further new compound was isolated, (3S,24S)-25-trihydroxy-9,19-cycloartane-29-oic acid (2), but this was inactive in the bioassay systems used. Compound 1 is based on the unprecedented 29-nor-3,4-seco-cycloartane skeleton.     

Synthesis and biological evaluation of disubstituted N6-cyclopentyladenine analogues: the search for a neutral antagonist with high affinity for the adenosine A1 receptor

Novel 3,8- and 8,9-disubstituted N(6)-cyclopentyladenine derivatives were synthesised in moderate overall yield from 6-chloropurine. The derivatives were made in an attempt to find a new neutral antagonist with high affinity for adenosine A(1) receptors. N(6)-Cyclopentyl-9-methyladenine (N-0840) was used as a lead compound. Binding affinities of the new analogues were determined for human adenosine A(1) and A(3) receptors. Their intrinsic activity was assessed in [35S]GTPgammaS binding experiments. Elongation of the 9-methyl of N-0840 to a 9-propyl substituent was very well tolerated. A 9-benzyl group, on the other hand, caused a decrease in adenosine A(1) receptor affinity. Next, the 8-position was examined in detail, and affinity was increased with appropriate substitution. Most derivatives were A(1)-selective and 20 of the new compounds (6-9, 15-21, 23-26, 28, 31, 33, 35, and 36) had higher adenosine A(1) receptor affinity than the reference substance, N-0840. Compound 31 (N(6)-cyclopentyl-8-(N-methylisopropylamino)-9-methyladenine, LUF 5608) had the highest adenosine A(1) receptor affinity, 7.7 nM. In the [35S]GTPgammaS binding experiments, derivatives 5, 14, 22, 23, 25, 26, 33 and 34 did not significantly change basal [35S]GTPgammaS binding, thus behaving as neutral antagonists. Moreover, four of these compounds (23, 25, 26, and 33) displayed a 4- to 10-fold increased adenosine A(1) receptor affinity (75-206 nM) compared to N-0840 (852 nM). In summary, we synthesised a range of N-0840 analogues with higher affinity for adenosine A(1) receptors. In addition, four new derivatives, LUF 5666 (23), LUF 5668 (25), LUF 5669 (26) and LUF 5674 (33), behaved as neutral antagonists when tested in [35S]GTPgammaS binding studies. Thus, these compounds have improved characteristics as neutral adenosine A(1) receptor antagonists.