白黄小脆柄菇发酵液中的一个新的血苋烷型倍半萜（英文）

从白黄小脆柄菇(Psathyrellacandolleana)发酵液提取物的乙酸乙酯层中分离得到一个新的血苋烷型倍半萜(1)和一个已知的没药烷型倍半萜(2)。通过质谱、核磁等方法确定化合物1的结构为15-hydroxy-drimenol。通过文献对照核磁数据确定化合物2为1α-hydroxy-bisabola-2,10-dien-4-one。     

白黄小脆柄菇发酵液中的一个新的血苋烷型倍半萜（英文）北大核心CSCD

从白黄小脆柄菇(Psathyrellacandolleana)发酵液提取物的乙酸乙酯层中分离得到一个新的血苋烷型倍半萜(1)和一个已知的没药烷型倍半萜(2)。通过质谱、核磁等方法确定化合物1的结构为15-hydroxy-drimenol。通过文献对照核磁数据确定化合物2为1α-hydroxy-bisabola-2,10-dien-4-one。     

杜松烷型倍半萜天然产物的研究进展

杜松烷型倍半萜是一类双环倍半萜,立体化学复杂,具有广泛药理活性,如抗菌、抗炎、降糖等。迄今为止,已从多种植物和微生物中分离鉴定出具有不同结构及生物活性的杜松烷型化合物,相关杜松烷型倍半萜合酶的研究也取得较大进展。本文按5种结构类型对近4年(2017–2020年)文献发表的结构新颖的124个杜松烷型化合物进行整理,并对其药理活性进行归纳总结,同时介绍了代表性杜松烷型化合物生物合成途径的解析概况,归纳了该类天然产物生物合成过程中关键杜松烷型倍半萜合酶的研究进展,并讨论了该类天然产物的研究前景和目前面临的一些问题。     

金针菇固体发酵菌丝体次级代谢产物分离鉴定

采用硅胶柱色谱、ODS柱色谱、Sephadex LH-20柱色谱、HPLC等分离方法对金针菇大米发酵乙酸乙酯提取物进行分离,根据理化性质和波谱数据鉴定化合物结构：鉴定了4个倍半萜,包括1个新的桉叶烷型倍半萜,3个侧柏烷型倍半萜,分别是flamvelutpenol A(1),aquaticol(2),enokipodin C(3),limacellone(4)。并通过与Rh2(OCOCF3)4络合的方法确定了新化合物flamvelutpenol A(1)和limacellone(4)的绝对构型。其中化合物3具有较好的抗菌活性,对耐甲氧西林金黄色葡萄球菌和枯草芽孢杆菌的MIC值分别为12.5mg/L,25mg/L。且化合物1－4均是首次从该种真菌中分离得到。     

蒿属和千里光属植物中桉烷型倍半萜的光谱特征

本文就菊科中的两个大属蒿属和千里光属植物中一类典型倍半萜成分——桉烷型倍半萜的光谱特征进行综述.     

西印度醋栗的化学成分及药理活性研究进展

西印度醋栗为大戟科叶下珠属常绿灌木或乔木,主产于泰国、越南、缅甸、老挝等地,中国云南西双版纳和元江有引种栽培。该植物果实可食用,枝叶、根茎、果实等在东南亚各国被广泛用于治疗高血压、哮喘、糖尿病、皮炎、发烧、天花等,印度尼西亚、泰国、印度等地区亦用其叶做蔬菜食用。有关其化学和药理活性研究,主要集中于根、茎和枝叶。根、茎主要含倍半萜、二萜和三萜,枝叶则主要为黄酮类成分。部分化合物显示有显著的抗乙肝病毒、抗菌、抗炎、保肝和降压等活性,其中,多个降没药烷型倍半萜对乙肝病毒(HBV)表面抗原(HBsAg)和e抗原(HBeAg)的IC₅₀值为0.8～36 μmol·L^-1,构效关系研究表明,倍半萜结构中C-5位的缩酮和C-13位的糖基取代可能对抗HBsAg和HBeAg的选择性有贡献。该文综述了1966—2020年西印度醋栗的化学成分和药理活性研究进展,为该植物的深入研究和开发利用提供科学参考和依据。     

蒿属和各里光属植物中桉烷型倍半萜的光谱特征

本文就菊科中的两个大属蒿属和千里光属植物中一类典型倍半萜成分－桉烷型倍半萜的光谱特征进行综述。     

大型担子菌中二萜化合物生物合成研究进展

大型担子菌分布广泛,种类繁多,它们是重要的食药用资源的宝库。萜类化合物是其主要活性成分之一,包括倍半萜、二萜和三萜等,这些化合物具有预防、缓解或治疗癌症、抑郁症、糖尿病和高脂血症等多种疾病的功效。目前,从担子菌中分离出的二萜类化合物基本骨架结构特征主要为鸟巢烷(cyathanes)型、截短侧耳素(pleuromutilins)型、guanacastanes型、海松烷(pimaranes)型、松香烷(abietanes)型和毛皮伞烷(crinipellins)型6大类型。本文综述了担子菌中二萜类化合物的结构特点、生物活性和生物合成的研究进展,对参与担子菌中二萜化合物生物合成的二萜合成酶进行了分类,对两种重要的二萜化合物生物合成途径进行了系统总结和论述。本文将为未知二萜化合物生物合成途径及关键基因功能解析提供参考。     

拐芹倍半萜没药烷吉酮的结构修饰及其对H~+/K~+-ATP酶的抑制作用

三峡区域药用植物拐芹的根中富含倍半萜类抗溃疡活性成分没药烷吉酮,为可开发和利用的中草药资源。本文对该化合物进行了提取分离、结构修饰和初步的构效关系研究,从拐芹根茎中提取并分离了没药烷吉酮,通过选择性还原、缩合和加成反应制备了四个没药烷吉酮氨基甲酰腙衍生物。用核磁共振波谱、质谱、红外和元素分析等方法确证了其结构,并测试了其体外对H~+/K~+-ATP酶的抑制活性和细胞毒活性。没药烷吉酮还原衍生物2及4-氯苯基取代的氨基甲酰腙衍生物4d较阳性对照药物奥美拉唑具有更好的体外抗溃疡活性(IC50<24μmol/L)。本文探明了没药烷吉酮衍生物的结构对体外H~+/K~+-ATP酶抑制活性的影响,为消化性溃疡的治疗提供了新型倍半萜类候选药物。     

拐芹倍半萜没药烷吉酮的结构修饰及其对H~+/K~+-ATP酶的抑制作用

三峡区域药用植物拐芹的根中富含倍半萜类抗溃疡活性成分没药烷吉酮,为可开发和利用的中草药资源。本文对该化合物进行了提取分离、结构修饰和初步的构效关系研究,从拐芹根茎中提取并分离了没药烷吉酮,通过选择性还原、缩合和加成反应制备了四个没药烷吉酮氨基甲酰腙衍生物。用核磁共振波谱、质谱、红外和元素分析等方法确证了其结构,并测试了其体外对H~+/K~+-ATP酶的抑制活性和细胞毒活性。没药烷吉酮还原衍生物2及4-氯苯基取代的氨基甲酰腙衍生物4d较阳性对照药物奥美拉唑具有更好的体外抗溃疡活性(IC5024μmol/L)。本文探明了没药烷吉酮衍生物的结构对体外H~+/K~+-ATP酶抑制活性的影响,为消化性溃疡的治疗提供了新型倍半萜类候选药物。     

Differences between HMG1 proteins isolated from normal and tumour cells

The properties of the non-histone chromosomal high-mobility-group 1 (HMG1) proteins from rat liver and Guerin ascites tumour cells (GAT cells) were compared and showed the following differences: (1) five spots were missing in the peptide map of HMG1 from GAT cells in comparison with that of HMG1 from rat liver; (2) HMG1 from GAT cells was about 5-times more poly(ADP)-ribosylated; (3) HMG1 from GAT cells which was found acetylated in vivo and incorporated [14C]acetate in vitro, whereas no incorporation of the label was detected in HMG1 from rat liver; (4) HMG1 from GAT cells exhibited pronounced ability to form oligomers at physiological ionic strength, while HMG1 from rat liver was predominantly in monomeric form. This property of HMG1 from GAT cells was lost upon deacetylation.     

Comparison of two β-glucosidases for the enzymatic synthesis of β-(1-6)-β-(1-3)-gluco-oligosaccharides

A domain of epiglucan was synthesized by beta-glucosidases. Two beta-glucosidases, an extracellular beta-glucosidase derived from Sclerotinia sclerotiorum grown on xylose, and a commercial lyophilized preparation of beta-glucosidase from Aspergillus niger, were used to synthesize gluco-oligosaccharides from cellobiose and, specially, beta-(1-6) branched beta-(1-3) gluco-oligosaccharides, corresponding to the structure of epiglucan. Gentiobiose, cellotriose, cellotetraose, beta-Glc-(1-3)-beta-Glc-(1-4)-Glc, beta-Glc-(1-6)-beta-Glc-(1-4)-Glc and beta-Glc-(1-6)-beta-Glc-(1-3)-Glc were synthesized from cellobiose by both enzymes. The latter compound was preferentially synthesized by the beta-glycosidase from Sclerotinia sclerotiorum. Under the best conditions, only 7 g l(-1) of beta-Glc-(1-6)-beta-Glc-(1-3)-Glc was synthesized by the beta-glycosidase from Aspergillus niger compared to 20 g l(-1) synthesized with beta-glycosidase from Sclerotinia sclerotiorum.     

Metabolism of gibberellins A1 and A3 in fruits and shoots of Prunus avium

Isotope-labelled GA metabolites were identified by GC--MS, following HPLC fractionation of extracts derived from fruits or shoots, that had been incubated with [2H]- and [3H]- GA1 or [2H]- and [3H]- GA3. GA1 (1) was converted into GA8 (10) by developing fruits and vegetative shoots of sweet cherry (Prunus avium cv. 'Stella'), while GA3 (4) was converted into GA3-isolactone (17). Other metabolites of each GA were detected but were not identified unequivocally. These included a metabolite of GA1 (1) in fruitlets that was more polar (by reverse phase HPLC) than GA8 (10) and a metabolite of similar polarity to GA87 (6), was obtained after incubating fruitlets with GA3 (4). However, no evidence was obtained to suggest that GA87 (6) was a metabolite of GA3 (4) or that GA85 (2) was a metabolite of GA1 (1) in these tissues, under the conditions used. The pattern of metabolites obtained from vegetative tissues was similar to that from fruitlets. However, the results suggested that GA1 (1) and GA3 (4) were metabolised at a greater rate in shoots from mature trees than in shoots from seedlings, and that GA1 (1) was metabolised more rapidly than GA3 (4) in juvenile and mature shoots. We conclude from these observations that GA3 (4) is not a precursor of GA87 (6) and GA32 (5), also, that GA1 (1) is not a precursor of GA85 (2) and GA86 (3) in developing fruits or in vegetative shoots of sweet cherry.     

An enzymatically produced novel cyclomaltopentaose cyclized from amylose by an alpha-(1-->6)-linkage, cyclo-{-->6)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->}

A bacterial strain AM7, isolated from soil and identified as Bacillus circulans, produced two kinds of novel cyclic oligosaccharides. The cyclic oligosaccharides were produced from amylose using a culture supernatant of the strain as the enzyme preparation. The major product was a cyclomaltopentaose cyclized by an alpha-(1-->6)-linkage, cyclo-{-->6)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->}. The other minor product was cyclomaltohexaose cyclized by an alpha-(1-->6)-linkage, cyclo-{-->6)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->4)-alpha-D-Glcp-(1-->}. We propose the names isocyclomaltopentaose (ICG5) and isocyclomaltohexaose (ICG6) for these novel cyclic maltooligosaccharides having one alpha-(1-->6)-linkage. ICG5 was digested by alpha-amylase derived from Aspergillus oryzae, cyclomaltodextrin glucanotransferase (CGTase) from Bacillus stearothermophilus, and maltogenic alpha-amylase. On the other hand, ICG6 was digested by CGTase from B. stearothermophilus and B. circulans, and maltogenic alpha-amylase. This is the first report of enzymatically produced cyclomaltopentaose and cyclomaltohexaose, which have an alpha-(1-->6)-linkage in their molecules.     

Evaluation of UASB reactor performance during start-up operation using synthetic mixed-acid waste

A start-up experiment was performed in a laboratory-scale, upflow anaerobic sludge blanket (UASB) reactor using seed sludge from a domestic waste treatment plant at 3.8-33.3gCODl(-1)day(-1) loading rates. Analysis over the height of the reactor with time showed that the VSS in the reactor was initially differentiated into active and non-active biomass at increasing gas production and upflow velocities, and specific update rates of the volatile fatty acids (VFA) components were pronounced at the bottom 10% of the reactor. During start-up, specific methanogenic activity and chemical oxygen demand (COD) uptake rate increased from 0.075 to 0.75gCOD-CH(4)(gVSS)(-1)day(-1) and from 0.08 to 0.875gCOD removed (gVSS)(-1)day(-1), respectively. When seed sludge from a distillery waste treatment plant was used, improved performance due to a predominance of active biomass was evident when the loading rate was increased from 9.4 to 28.7gCODl(-1)day(-1). The proposed start-up evaluation is an effective tool to successfully monitor performance of UASB reactors.     

Type I arabinogalactan contains beta-D-Galp-(1-->3)-beta-D-Galp structural elements

Arabinogalactan type I from potato was partially degraded by endo-galactanase from Aspergillus niger. High-performance anion-exchange chromatography revealed that several of the oligomeric degradation products eluted as double peaks. To investigate the nature of these products, the digest was fractionated by Bio-Gel P2 chromatography. The pool that contained tetramers was treated with a beta-D-Galp-(1-->4)-specific galactosidase from Bifidobacterium adolescentis to obtain a dimer with deviating linkage type, which was further purified by BioGel P2 chromatography. By obtaining all (1)H and (13)C chemical shifts and the presence of intra residual scalar coupling (HMBC) it could be concluded that the dimer contained a beta-(1-->3)-linkage instead of the expected beta-(1-->4)-linkage. Using the same NMR techniques as for the dimer, it was found that the pool of tetramers consisted of the following two galactose tetramers: beta-Galp-(1-->4)-beta-Galp-(1-->4)-beta-Galp-(1-->4)-alpha/beta-Galp-OH and beta-Galp-(1-->4)-beta-Galp-(1-->4)-beta-Galp-(1-->3)-alpha/beta-Galp-OH. The fact that the deviating beta-(1-->3)-linked galactose was found at the reducing end of the dimer showed that this deviating linkage is present within the backbone. The beta-(1-->3)-galactosyl interruption appeared to be a common structural feature of type I arabinogalactans with a frequency ranging from approximately 1 in 160 (potato, soy, citrus) to 1 in 250 (onion).     

Inhibition of wild-type and mutant human immunodeficiency virus type 1 proteases by GW0385 and other arylsulfonamides

The arylsulfonamide derivatives described herein were such potent inhibitors of human immunodeficiency virus type 1 (HIV-1) protease (enzyme, E) that values for the inhibition constants (K(i)) could not be determined by conventional steady-state kinetic techniques (i.e., the minimal enzyme concentration usable for the activity assay was much greater than the value of the dissociation constant). Consequently, two alternative methods were developed for estimation of K(i) values. The first method employed kinetic determinations of values for k(1) and k(-1), from which K(i) was determined (k(-1)/k(1)). The second method was a competitive displacement assay used to determine binding affinities of other inhibitors relative to that of GW0385. In these assays, the inhibitor of unknown affinity was used to displace [(3)H]GW0385 from E.[(3)H]GW0385. From the concentration of E.[(3)H]GW0385 at equilibrium, the concentrations of enzyme-bound and free inhibitors were calculated, and the ratio of the K(i) value of the unknown to that of GW0385 was determined (K(i,unknown)/K(i,GW0385)). The values of k(1) were calculated from data in which changes in the intrinsic protein fluorescence of the enzyme associated with inhibitor binding were directly or indirectly monitored. In the case of saquinavir, the fluorescence changes associated with complex formation were large enough to monitor directly. The value of k(1) for saquinavir was 62 +/- 2 microM(-1) s(-1). In the case of GW0385, the fluorescence changes associated with complex formation were too small to monitor directly. Consequently, the value of k(1) was estimated from a competition experiment in which the effect of GW0385 on the binding of E to saquinavir was determined. The value of k(1) for GW0385 was estimated from these experiments to be 137 +/- 4 microM(-1) s(-1). Because E.[(3)H]GW0385 was stable in the standard buffer at room temperature for greater than 33 days, the value of the first-order rate constant for dissociation of E.[(3)H]GW0385 (k(-1)) could be estimated from the time-course for exchange of E.[(3)H]GW0385 with excess unlabeled GW0385. The value of k(-1) calculated from these data was (2.1 +/- 0.1) x10(-6) s(-1) (t(1/2) = 91 h). The K(i) value of wild-type HIV-1 protease for GW0385, calculated from these values for k(1) and k(-1), was 15 +/- 1 fM. Three multidrug resistant enzymes had K(i) values for GW0385 that were less than 5 pM.     

Esterase Polymorphism and the Analysis of Genetic Diversity and Structure in Cactus Populations Descended from Cereus peruvianus Plants Regenerated In Vitro

The genetic structure of Cereus peruvianus populations descended from cultivated plants (F(1) populations) and from plants regenerated in vitro (R(1) populations) was analyzed using α- and β-esterase isozymes in native PAGE. The estimated proportion of polymorphic loci was higher (50%) in the R(1) populations than the F(1) populations (42.85%). The mean observed (0.5599) and expected (0.5620) heterozygosity in R(1) descendents was also higher than the rates in F(1) descendents (H (o)?=?0.4142; H (e)?=?0.4977). A low level of population differentiation was detected in R(1) descendents (F (st)?=?0.05). In contrast, population differentiation was high in F(1) descendents (0.2583). Esterase analysis using PAGE showed that artificial selection by silvicultural management provides high genetic diversity and a large genetic basis for C.?peruvianus, whereas in vitro selection from callus tissue culture involves an increase of heterozygosity levels in descendents from somaclones and a low level of interpopulational divergence.     

Regiospecific hydroxylation of lauric acid at the (omega-1) position by hepatic and kidney microsomal cytochromes P-450 from rainbow trout

Microsomes from liver or kidney of untreated rainbow trout hydroxylated lauric acid specifically at the (omega-1) position. Turnover numbers for liver (2.72 min-1) and kidney (14.1 min-1) were decreased seven- and twofold, respectively, following treatment with beta-naphthoflavone. Laurate hydroxylation activity from untreated trout hepatic microsomes was sensitive to inhibition by SKF-525A, but was not sensitive to metyrapone and only partially inhibited by alpha-naphthoflavone. The temperature optimum of laurate (omega-1) hydroxylation in trout liver microsomes was 25-30 degrees C. The Km and Vmax for (omega-1)- hydroxylaurate formation was 50 microM and 1.63 nmol min-1 mg-1, respectively, in liver and 20 microM and 3.95 nmol min-1 mg-1, respectively, in kidney from untreated trout microsomes. (omega-1) Hydroxylation of laurate, in both liver and kidney microsomes, was sensitive to an antibody raised against a previously purified cytochrome P-450 isozyme (LM2) of trout liver microsomes, which has been shown to be active towards aflatoxin B1. Antibody to the major isozyme of cytochrome P-450 ( LM4b , active towards benzo(a)pyrene) induced by beta-naphthoflavone did not inhibit (omega-1) hydroxylation of laurate in microsomes from untreated or beta-naphthoflavone-treated trout.     

Purification and characterization of an intracellular cycloalternan-degrading enzyme from Bacillus sp. NRRL B-21195

A novel intracellular cycloalternan-degrading enzyme (CADE) was purified to homogeneity from the cell pellet of Bacillus sp. NRRL B-21195. The enzyme has a molecular mass of 125 kDa on SDS-PAGE. The pH optimum was 7.0, and the enzyme was stable from pH 6.0 to 9.2. The temperature optimum was 35 degrees C and the enzyme exhibited stability up to 50 degrees C. The enzyme hydrolyzed cycloalternan [CA; cyclo(-->6)-alpha-d-Glcp-(1-->3)-alpha-d-Glcp-(1-->6)-alpha-d-Glcp-(-->3)-alpha-d-Glcp-(1-->)] as the best substrate, to produce only isomaltose via an intermediate, alpha-isomaltosyl-(1-->3)-isomaltose. This enzyme also hydrolyzed isomaltosyl substrates, such as panose, alpha-isomaltosyl-(1-->4)-maltooligosaccharides, alpha-isomaltosyl-(1-->3)-glucose, and alpha-isomaltosyl-(1-->3)-isomaltose to liberate isomaltose. Neither maltooligosaccharides nor isomaltooligosaccharides were hydrolyzed by the enzyme, indicating that CADE requires alpha-isomaltosyl residues connected with (1-->4)- or (1-->3)-linkages. The K(m) value of cycloalternan (1.68 mM) was 20% of that of panose (8.23 mM). The k(cat) value on panose (14.4s(-1)) was not significantly different from that of cycloalternan (10.8 s(-1)). Judging from its specificity, the systematic name of the enzyme should be cycloalternan isomaltosylhydrolase. This intracellular enzyme is apparently involved in the metabolism of starch via cycloalternan in Bacillus sp. NRRL B-21195, its role being to hydrolyze cycloalternan inside the cells.