Gas separation properties of aromatic polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 3,5-diaminobenzic acid or its esters

The gas transport properties of a series polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) with 1,3-phenylenediamine or 3,5-diaminobenzic acid (DBA) or its esters are reported. The effects of carboxylic group (-COOH) and carboxylic ether groups (-COOR), at five positions of 1,3-phenylenediamine moiety, on H-2, CO2, O-2, and N-2 permeability, diffusivity, and solubility of the polyetherimides were investigated. The gas permeability, diffusion, and solubility coefficients of the polyetherimides containing COOR are bigger than those of HQDPA-PDA, but the ideal separation factors and ideal diffusivity selectivity factors are much smaller than that of HQDPA-PDA because COOR decreases chain segmental packing efficiency and increases chain segmental mobility. The permeability coefficients of HQDPA-DBA to H-2, CO2, and O-2 are bigger than those of HQDPA-PDA; the ideal separation factors for gas pairs H-2/N-2, CO2/N-2, and O-2/N-2 are also much bigger than those of HQDPA-PDA. Both the diffusion coefficients of CO2 and O-2 and the ideal diffusivity selectivity factors for CO2/N-2 and O-2/N-2 are bigger than those of HQDPA-PDA because COOH decreases both chain segmental packing efficiency and chain segmental mobility. The copolyimides, which were prepared from 3,5-diaminobenzic acid and 3,5-diaminobenzic esters, have both high permeability and high permselectivity. (C) 1997 John Wiley & Sons, Inc.

Resolution of 3,3 '-dioxo-1,1 '(3H,3 ' H)spirobi[isobenzofuran]-5,6,5 ' 6 '-tetracarboxylic acid and Optically active Polyimides thereof

3,3'-Dioxo-1.1'(3H.3'H)spirobi[isobenzofuran]-5,6,5',6 acid 1 was resolved successfully and the corresponding optically active polyimides PI were synthesized. The properties of the optically active PI and the racemic one were investigated. The results showed that the specific rotation of(-)-PI was about two times to that of the: (+)-PI, and the regularity of the optically active PI was higher than that of the racemic one.

Relationship between the allelopathic activity and molecular structure of hydroxyl derivatives of benzoic acid and their effects on cyanobacterium Microcystis aeruginosa

The antialgal activities of benzoic acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid (gallic acid) were studied on the growth of two strains of Microcystis aeruginosa (toxic FACHB 942 and non-toxic 469). The results showed that the sequence of 50% growth inhibition concentration (ErC50) of 6- compounds for both strains of M. aeruginosa followed the same order: gallic acid > 3,5-dihydroxybenzoic acid > 4-hydroxybenzoic acid > salicylic acid > 3-hydroxybenzoic acid > benzoic acid. The position and the numbers of hydroxy groups between the hydroxy group and carboxyl influenced the antialgal effects of phenolic acids. We also investigated the joint effects of benzoic acid, 4-hydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid on the growth of M. aeruginosa ( toxic FACHB 942). The mixture of phenolic allelochemicals showed the synergistic effects.

Establishment and characterization of dual-species biofilms formed between a 3,5-dinitrobenzoic-degrading strain and bacteria with high biofilm-forming capabilities

In this study, the possibility of establishing a dual-species biofilm from a bacterium with a high biofilm-forming capability and a 3,5-dinitrobenzoic acid (3,5-DNBA)-degrading bacterium, Comamonas testosteroni A3, was investigated. Our results showed that the combinations of strain A3 with each of five strains with a high biofilm-forming capability (Pseudomonas sp. M8, Pseudomonas putida M9, Bacillus cereus M19, Pseudomonas plecoglossicida M21 and Aeromonas hydrophila M22) presented different levels of enhancement regarding biofilm-forming capability. Among these culture combinations, the 24-h dual-species biofilms established by C. testosteroni A3 with P. putida M9 and A. hydrophila M22 showed the strongest resistance to 3,5-DNBA shock loading, as demonstrated by six successive replacements with DMM2 synthetic wastewater. The degradation rates of 3,5-DNBA by these two culture combinations reached 63.3-91.6% and 70.7-89.4%, respectively, within 6 h of every replacement. Using the gfp-tagged strain M22 and confocal laser scanning microscopy, the immobilization of A3 cells in the dual-species biofilm was confirmed. We thus demonstrated that, during wastewater treatment processes, it is possible to immobilize degrader bacteria with bacteria with a high biofilm-forming capability and to enable them to develop into the mixed microbial flora. This may be a simple and economical method that represents a novel strategy for effective bioaugmentation.

5-氨基乙酰丙酸对日光温室番茄生长发育和产量品质的影响

为外源5-氨基乙酰丙酸(ALA)在日光温室蔬菜上的应用提供科学依据。【方法】研究了不同浓度ALA处理对日光温室番茄生产的影响。【结果】ALA以及ALA+N叶面施用均明显提高了番茄植株株高、叶绿素相对含量和果实产量,并改善了番茄果实品质;与对照相比,外源ALA各处理植株株高、叶绿素相对含量和单株生物产量均有明显提高,其中D处理(ALA1号肥料第1次2 kg/hm2,第2~4次1 kg/hm2)效果最佳,植株株高、叶绿素相对含量及单株生物产量分别提高27.18%,17.75%和13.93%;外源ALA对番茄果实产量和品质也有明显的提高和改善作用,其中处理B(ALA1号肥料第1次0.5 kg/hm2,第2~4次0.3 kg/hm2)对果实产量效果最明显,处理E(ALA3号肥料第1次2.5 kg/hm2,第2~4次1.5 kg/hm2)对果实品质效果最佳。【结论】处理E(ALA3号肥料第1次2.5 kg/hm2,第2~4次1.5 kg/hm2)既有利于番茄生长发育,又能增加产量并改善品质,为最佳的ALA施用量及方法。

The effect of acidity on olefin aromatization over potassium modified ZSM-5 catalysts

The transformation of olefin to aromatics over ZSM-5 catalysts with different K-loadings has been investigated both in a continuous flow fixed-bed reactor and in a pulse microreactor. Investigation of variation of olefin aromatization activity with K-loadings shows that strong acid sites are indispensable for the converting of olefin to aromatics. As intermediates of olefin aromatization process, butadiene and cyclopentene not only show much higher aromatization activity than mono-olefins, but also can be transformed into aromatics over relatively weak acid sites of K/ZSM-5. A proposal is put forward, stating that among all the steps experienced in olefins aromatization, the formation of diene or cycloolfin from mono-olefins through hydrogen transfer is the key step and can be catalyzed by strong acid sites.

New process for the preparation of 3,5-dihydroxy-1-pentylbenzene

A new process for the preparation of 3,5-dihydroxy-1-pentylbenzene, which is used as medicinal intermediate and raw material for the synthesis of HIV restrainer, is proposed in this paper. Technical 3,5-dimethoxybenzoic acid reacted with lithium hydride to form a salt (I) which acylated n-butyllithium directly to give 1-(3,5-dimethoxyphenyl)-1-pentanone (II) in 85.06% yield. Then (II) was reduced through a Wolff-K-Huangminglong reaction at 210 degrees C to give 3,5-dimethoxy-1-pentylbenzene (III). Finally, (III) refluxed with melt pyridine hydrochloride at 200 degrees C for 2 h to afford the target product 3,5-dihydroxy-1-pentylbenzene (IV). The total yield of (IV) amounted to 61.50% and its mass percentage was 98.22%. The products were characterized by means of IR, H-1-NMR, GC and HLPC-MS. The results indicated that this synthetic route was feasible, characterized by simple process and higher yield, and superior to the published ones.

Hydrogen-bonded lamellar network of pyromellitic acid pillared by 8-hydroxyquinoline

8-Hydroxyquinoline (8-q) salt of pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid, H(4)bta) forms robust lamellar structure where [H(2)bta](2-) anions build up sheets through strong hydrogen bonds in two dimensions and [H-8-q](+) cations act as pillars to afford an extended three dimensional network.

Simultaneous determination of microcystin-LR and its glutathione conjugate in fish tissues by liquid chromatography-tandem mass spectrometry

A sensitive and selective liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous quantitative determination of microcystin-LR (MC-LR) and its glutathione conjugate (MC-LR-GSH) in fish tissues. The analytes were extracted from fish liver and kidney using 0.01 M EDTA-Na-2-5% acetic acid, followed by a solid-phase extraction (SPE) on Oasis HLB and silica cartridges. High-performance liquid chromatography (HPLC) with electrospray ionization mass spectrometry, operating in selected reaction monitoring (SRM) mode, was used to quantify MC-LR and its glutathione conjugate in fish liver and kidney. Recoveries of analytes were assessed at three concentrations (0.2, 1.0, and 5 mu g g(-1) dry weight [DW]) and ranged from 91 to 103% for MC-LR, and from 65.0 to 75.7% for MC-LR-GSH. The assay was linear within the range from 0.02 to 5.0 mu g g(-1) DW, with a limit of quantification (LOQ) of 0.02 mu g g(-1) DW. The limit of detection (LOD) of the method was 0.007 mu g g(-1) DW in both fish liver and kidney. The overall precision was determined on three different days. The values for within- and between-day precision in liver and kidney were within 15%. This method was applied to the identification and quantification of MC-LR and its glutathione conjugate in liver and kidney of fish with acute exposure of MC-LR. (c) 2007 Elsevier B.V. All rights reserved.

野桂花的化学成分研究

首次从野桂花（Osmanthus yunnanensis Fr. P. S. Green）地上部分95%乙醇提取物中通过色谱分离得到20个化合物, 其中化合物20为新化合物。基于波谱数据它们被鉴定为(E)-阿魏酸二十烷基酯(1)、β-谷甾醇(2)、羽扇豆醇(3)、齐墩果酸(4)、7-oxo-β-sitosterol(5)、乙酰齐墩果酸(6)、(6′-O-palmitoyl)-sitosterol 3-O-β-D-glucoside(7)、rotundioic acid(8)、地榆糖甙Ⅱ(9)、27-O-(E)-对羟基肉桂酰-28-齐墩果酸(10)、27-O-(Z)-对羟基肉桂酰-28-齐墩果酸(11)、hycandinic acid ester(12)、绿原酸丁酯(13)、4,5-二咖啡酰奎尼酸丁酯(14)、4,5-dihydroxyprenyl caffeate(15)、28-O-β-D-glucopyranosyl rotundioic acid (16)、4-(6-O-caffeoyl-β-D-glucopyranosyloxy)-5-hydroxyprenyl caffeate (aohada-glycoside C, 17)、 4-β-D-glucopyranosyloxy-5-hydroxy-prenyl caffeate (aohada-glycoside A, 18)、β-胡萝卜甙(19)以及3-[O-β-D-(6-O-咖啡酰吡喃葡萄糖)]-甲基-2-烯-γ-内酯 (20)。化合物13、14、15和17有较强的α-葡萄糖甙酶抑制活性。当浓度为1 mg/ml时，它们对α-葡萄糖甙酶的抑制分别为61.5%、95.5%、72.1%、62.6%，活性高于阿卡波糖。 综述了木犀属植物化学成分及1993年以来苯丙素甙类化合物活性研究进展。 Twenty compounds were isolated from the 95% ethanol extract of the aerial parts of Osmanthus yunnanensis Fr. P. S. Green by chromatography for the first time. On the basis of spectral data, they were identified as (E)-ferulic acid eicosyl ester (1), β-sitosterol (2), lupenol (3), oleanolic acid (4), 7-oxo-β-sitosterol (5), acetyloleanolic acid (6), (6′-O-palmitoyl)-sitosterol 3-O-β-D-glucoside (7), rotundioic acid (8), ziyu glycosideⅡ (9), 3β-hydroxy-27-p-(E)-coumaroyloxy-olean-12-en-28-oic acid (10), 3β-hydroxy-27-p-(Z)-coumaroyloxyolean-12-en-28-oic acid (11), hycandinic acid ester (12), chlorogenic acid butyl ester (13), 4,5-di-O-caffeoylquinic acid butyl ester (14), 4,5-dihydroxyprenyl caffeate (15), 28-O-β-D-glucopyranosyl rotundioic acid (16), 4-(6-O-caffeoyl-β-D-glucopyranosyloxy)-5-hydroxyprenyl caffeate (aohada- glycoside C, 17), 4-β-D-glucopyranosyloxy-5-hydroxyprenyl caffeate (aohada- glycoside A, 18), β-daucosterol(19) and 3-[O-β-D-(6-O-caffeoylglucopyranosyl)]- methyl-2-en-γ-lactone (20). Compound 20 is a new one. Compounds 13, 14, 15 and 17 inhibit α-glucosidase with corresponding inhibitory rate of 61.5%, 95.5%, 72.1% and 62.6% at a concentration of 1 mg/ml, higher than acarbose. The chemical studies on Osmanthus genus and bioactivities of phenylpropanoid glycosides were summarized.

钮子瓜和袋花忍冬的化学成分研究

钮子瓜（Zehneria maysorensis Arn.）是一种常用的中草药，其性味苦、凉，主要功效为清热利湿、散风止痛，主治膀胱炎、头痛。体外活性筛选实验表明，袋花忍冬（Lonicera saccata Rehd.）95%乙醇提取物的乙酸乙酯部分对血管紧张素转化酶显示较强的抑制活性。为明确钮子瓜的药用物质基础和袋花忍冬中具有ACE抑制活性的成分，首次对两个植物的成分进行了研究。 1. 从钮子瓜95%乙醇提取物中主要通过色谱方法首次分离了14个化合物，通过波谱方法鉴定为(2S,3S,4R,10E)-2-[(2R)-2-羟基二十四烷酰基氨基]-10-十八烷-1,3,4-三醇（1）、(2S,3S,4R)-2-二十四烷酰基氨基-十八烷-1,3,4-三醇 （2）、胡萝卜苷（3）、swertish （4）、苯甲酸（5）、水杨酸（6）、loliolide （7）、胸腺嘧啶（8）、尿嘧啶（9）、(23Z)-9,19-环阿尔廷-23-烯-3β,25-二醇（10）、(20S,22E,24R)-5α,8α-表二氧-麦角甾-6,22-二烯-3β-醇（11）、十六烷酸 1-甘油酯（12）、大豆脑苷Ⅰ（13）和(22E,24S)-24-甲基-5α-胆甾-7,22-二烯-3β,5α,6β-三醇（14）。其中化合物4为一黄酮碳苷，具有旋转异构现象，有止痛作用；化合物6具有抗炎、镇痛、减热的活性，它们可能是钮子瓜药用物质基础的一部分。 2. 从袋花忍冬95%乙醇提取物中首次分离并鉴定了16个已知化合物：胡萝卜苷（3）、(20S,22E,24R)-5α,8α-表二氧-麦角甾-6,22-二烯-3β-醇（11）、十六烷酸 1-甘油酯（12）、E-p-coumaryl behenate (15)、谷甾醇（16）、2,6-dihydroxyhumula-3(12), 7(13),9(E)-triene (17)、环阿尔廷-25-烯-3β,24ξ-二醇 (18)、二十四烷酸 (19)、2,4-二羟基-3,6-二甲基苯甲酸甲酯 (20)、乌苏酸 (21)、柚皮素 (22)、木犀草素 (23)、柏双黄酮（24）咖啡酸 (25)、洋芹素（26）和木犀草素-7-O-β-D-葡萄糖苷 (27)。其中木犀草素（23）和咖啡酸（25）含量较高，它们为抑制ACE活性的成分。 3．综述了黄酮碳苷的旋转异构现象。 Zehneria maysorensis is a folk medicine for the treatment of cystitis and headache. The ethyl acetate soluble fraction of the 95% ethanol extract of Lonicera saccata showed obvious ACE inhibitory activity in vitro. To reveal their active constitutents, they were subjected to chemically study. From the 95% ethanol extract of the whole plants of Zehneria maysroensis fourteen compounds were isolated for the first time. On the basis of spectral data and/or by comparison with authentic samples, they were characterized to be (2S,3S,4R,10E)-2-[(2R)-2-hydroxytetracosanoylamino]-10-octadecene-1,3,4-triol (1), (2S,3S,4R)-2-tetracosanoylamino-1,3,4-octadecanetriol (2), daucosterol (3), swertish (4), benzoic acid (5), salicylic acid (6), loliolide (7), thymine (8), uracil (9), (23Z)-9,19-cycloart-23-ene-3β,25-diol (10), (20S,22E,24R)-5α,8α-epidioxy-ergosta- 6,22-diene-3β-ol (11), 2,3-dihydroxypropyl hexadecoate (12), soya-cerebroside (13) and (22E,24S)-24-methyl-5α-cholesta-7,22-diene-3β,5α,6β-triol (14). Compound 4, a C-glycosylflavone, showed a very interesting rotational isomerism. Compounds 4 and 6 may be the active constituents of Zehneria maysorensis considering their sedative and anti-inflammation activity, respectively. From the whole plants of Lonicera saccata, sixteen compounds were isolated for the first time. On the basis of spectral data and/or by comparison with authentic samples, they were identified to be daucosterol (3), (20S,22E,24R)-5α,8α-epidioxy- ergosta-6,22-diene-3β-ol (11), 2,3-dihydroxypropyl hexadecoate (12), E-p-coumaryl behenate (15), β-sitosterol (16), 2,6-dihydroxyhumula-3(12),7(13),9(E)-triene (17), cycloart-25-ene-3β,24ξ-diol (18), tetracosanoic acid (19), methyl 2,4-dihydroxy- 3,6-dimethylbenzoate (20), ursolic acid (21), naringenin (22), luteolin (23), cupressuflavone (24), caffeic acid (25), apigenin (26) and luteolin-7-O-β-D- glucopyranoside (27). Luteolin (23) and caffeic acid (25) were the ACE inhibitory active constituents. Rotational isomerism for C-glycosylflavonoid was reviewed.

五枫藤、小驳骨和川西茶藨的化学成分研究

八月瓜属植物五枫藤(Holboellia latifolia Wall.)和驳骨草属植物小驳骨(Gendarussa vulgaris Nees)均为药用植物, 前者化学成分研究不深入, 后者的化学成分未见报道。川西茶藨(Ribes takare D. Don)为茶藨子属植物, 没有化学成分的报道。本论文对三个植物的化学成分和活性成分进行了研究, 主要通过色谱方法分离得到了48 个化合物, 采用波谱分析或与已知标准品对照等手段鉴定了它们的结构, 其中有1 个新的原小檗碱类化合物和3 个新的联苯类化合物,发现了具有细胞毒活性和α-葡萄糖苷酶抑制活性的化合物。1、从五枫藤地上部分的95%乙醇提取物中分离得到了12 个化合物: 五加苷K (1)、hederagenin 3-O- α-L-rhamnopyranosyl-(1→2)- α-L-arabinopyranoside (2)、β-萘乙酸(3) 、3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-α-L-arabinopyranosyl oleanolic acid 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (4) 、3-O- α-L-rhamnopyranosyl-(1→2)-O- β- D-glucopyranosyl-(1→2)- α-L-arabinopyranosyl oleanolic acid (5) 、3-O-( β-D-glucopyranosiduronic acid)-oleanolic acid 28-O- β-D-glucopyranoside (6)、lup-20(29)-en-3-one (7)、lupeol (8)、β-谷甾醇(9)、齐墩果酸(10)、乌苏酸(11)、β-胡萝卜苷(12)。化合物1 对Lu-06、N-04 和Bre-04 癌细胞株的GI50 分别是0.77µg/mL、1.26 µg/mL 和1.55 µg/mL, 化合物2 对N-04 癌细胞株的GI50 为2.44 µg/mL。2、从小驳骨地上部分的95%乙醇提取物中分离得到了1 个原小檗碱类新化合物13-hydroxyl gusanlung A (25), β-谷甾醇(9)、齐敦果酸(10)、β-胡萝卜苷(12)、棕榈酸(1-)甘油酯(13)、棕榈酸(14)、阿苯哒唑(15)、阿苯哒唑砜(16)、阿苯哒唑亚砜(17)、aurantiamide acetate (18)、华良姜素(19)、芫花素(20)、(-)-丁香树酯醇(21)、gusanlung B (22) 、eupteleasaponinsⅤ acetate (23)、gusanlungA (24)、刺五加苷E (26)、岩白菜素(27)、咖啡酸(28)。化合物25 对肝癌细胞株(HepG2) 的GI50 为2.08 µg/mL。3、从川西茶藨地上部分的95%乙醇提取物中分离鉴定了22 个化合物: β-谷甾醇(9) 、β- 胡萝卜苷(12) 、O-acetyloleanolic aldehyde (29),4,7,8-trimethoxy-2,3-methylenedioxydibenzofuran (30) 、3', 5-dimethoxy-3, 4-methylenedioxybiphenyl (31) 、桦木醇(32) 、6,7-dimethoxy-1-methyl-3,4-dihydroquinolin-2-one (33)、3'-hydroxy-5-methoxy-3,4-methylenedioxybiphenyl (34) 、7-hydroxy-4,8-dimethoxy-2,3-methylenedioxydibenzofuran (35)、桦木醛(36)、没食子酸(37) 、6β- 羟基-4- 烯-3- 酮- 豆甾醇(38) 、5α, 8α-epidioxy-(22E,24R)-ergosta-6, 22-dien-3β-ol (39)、verrucofortine (40)、6-methoxycalpogoniumisoflavone A (41)、2-羟基二苯甲酮(42)、桦木酸(43), 3, 5-二甲氧基苯甲酸-4-O-β-D-吡喃葡萄糖苷(44)、洋芹素(45)、刺槐素(46)、水杨酸(47)、洋芹素-5-O- β-D-葡萄糖苷(48), 化合物30、31 和35 为新的联苯化合物。化合物30的α-葡萄糖苷酶抑制率为10.2% (1.00 mg/mL); 化合物35 的抑制率为17.2% (1.00mg/mL)。4、综述了1960 年以来原小檗碱类化合物药理活性研究进展。 Plants Holboellia latifolia Wall and Gendarussa vulgaris Nees, are used as folkmedicine. Ribes takare D. Don belongs to the genus Ribes. The three plants have notbeen chemically studied in detail. Chemical and bioactive study of three plants led tothe isolation of 48 compounds by chromatography. Their structures were elucidatedon the basis of spectroscopic evidence or comparison with authentic samples. Amongthe 48 componds isolated one protoberberine alkaloid and three biphenyls are newones. Cytotoxic and α-glucosidase inhibitory compounds had been found.1. Twelve compounds were isolated from the 95% ethanol extract of the aerial partof H. latifolia Wall. They were characterized as fellow: eleutheroside K (1),hederagenin-3-O- α-L-rhamnopyranosyl-(1→2)- α-L-arabinopyranoside (2),2-naphthyl acetic acid (3),3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-α-L-arabinopyranosyl oleanolic acid 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (4), 3-O- α-L-rhamnopyranosyl-(1→2)-O- β- D-glucopyranosyl-(1→2)- α-L-arabinopyranosyl oleanolic acid (5),3-O-( β-D-glucopyranosiduronic acid)-oleanolic acid-28-O- β-D-glucopyranoside (6),lup-20(29)-en-3-one (7), lupeol (8), β-sitosterol (9), oleanolic acid (10), ursolicacid (11), and β-daucosterol (12). Compound 1 showed moderate cytotoxicity againstLu-06 (GI50, 0.77 µg/mL), N-04 (GI50, 1.26 µg/mL) and Bre0-4 (GI50=1.55 µg/mL)and compound 2 showed moderate cytotoxicity against N-04 (GI50=2.44 µg/mL).2. A new protoberberine alkaloid, 13-hydroxyl gusanlung A (25), was isolated fromthe aerial part of Gendarussa vulgaris Nees, together with β-sitosterol (9), oleanolicacid (10), β-daucosterol (12), glycerol monopalmitate (13), palmific acid (14),albendazole (15), albendazole sulphone (16), albendazole sufloxide (17), aurantiamideacetate (18), kumatakenin (19), genkwanin (20), (-)-syringaresinol (21), gusanlung B(22), eupteleasaponinsⅤ acetate (23), gusanlung A (24), eleutheroside E (26),bergenin (27) and caffeic acid (28). Compound 25 showed cytotoxicity against HepG2 cells (GI50, 2.08 µg/mL).3. Phytochemical study of the Ribes takare D. Don led to the isolation of three newbiphenyls, 4,7,8-trimethoxy-2,3-methylenedioxydibenzofuran (30), 3', 5-dimethoxy-3,4-methylenedioxybiphenyl (31) and 7-hydroxy-4,8-dimethoxy-2,3-methylenedioxydibenzofuran (35), along with nineteenknown compounds, β-sitosterol (9), β-daucosterol (12), O-acetyloleanolic aldehyde(29), betulin (32), 6,7-dimethoxy-1-methyl-3,4-dihydroquinolin-2-one (33),3'-hydroxy-5-methoxy-3, 4-methylenedioxybiphenyl (34), betulinic aldehyde (36),gallic acid (37), stigmast-4-en-6β-ol-3-one (38), 5α, 8α-epidioxy-(22E, 24R)-ergosta-6,22-dien-3β-ol (39), verrucofortine (40), 6-methoxycalpogonium isoflavone A (41),2-hydroxybenzophenone (42), betulinic acid (43), 3,5-dimethoxygallic acid-4-O- β-D-glucopryranoside (44), apigenin (45), acacetin (46), salicylic acid (47) andapigenin-5-O- β-D-glucopryranoside (48). α-Glucosidase inhibitory rates ofcompound 30 and 35 were respectively 10.2% and 17.2% at a concentration of 1.00 mg/mL).4. Pharmacological activities of protoberberines were summarized.

非粮原料燃料乙醇发酵关键技术的研究

生物质燃料乙醇是一种高度清洁的交通液体燃料，是减少温室气体排放，缓解大气污染的最佳技术选择。以非粮原料生产燃料乙醇可以在进行能源生产的同时保证粮食安全，有利于产业的可持续发展。在众多的非粮原料中，甘薯是我国开发潜力最大的生物质能源作物之一。我国占世界甘薯种植总面积和产量的90％。同时，甘薯的单位面积燃料乙醇产量远大于玉米和小麦。其成本是目前酒精中最低廉的，因此利用甘薯生产乙醇是发展生物质燃料乙醇的首要选择。目前采用薯类全原料主要采用分批发酵生产乙醇，其技术水平低，发酵强度低，一般在0.7－2.5g/（L•h），乙醇浓度低，甘薯发酵乙醇为6－8％(v/v)，能耗高，环境负荷大，污染严重。针对上述问题，本文从菌株选育、原料预处理、中试放大、残糖成分分析等方面进行研究。 为了研究乙醇发酵生产规模扩大过程中，大型发酵罐底部高压条件下，CO2对酵母乙醇发酵的影响，我们通过CO2 加压的方法进行模拟试验，研究结果表明，发酵时间随压强的升高而逐渐延长，高压CO2 对乙醇发酵效率影响不大，在0.3 MPa 以下时，发酵效率均可达到90%以上。高压CO2 对发酵的抑制作用是高压和CO2 这两个因素联合作用的结果。高压CO2 条件下，酵母胞外酶和胞内重要酶类的酶活均表现出特征性。0.2 MPa 下，酶活性的变化趋势和0.1 MPa 条件下的较为一致。而0.3 MPa 下的酶活变化趋势与0.4 MPa 下的酶活更为接近。通过全基因表达分析发现在CO2 压力为0.3 MPa 下，乙醇发酵途径中多个基因表达量下调，同时海藻糖合成酶和热激蛋白基因表达量上调。 筛选耐高温的乙醇酵母菌株能够解决糖化温度和发酵温度不协调的矛盾，实现真正意义上的边糖化边发酵。高温发酵还能够降低发酵时的冷却成本，实现乙醇的周年生产。本研究筛选出一株高温发酵菌株Y-H1，进而我们对该菌株的胞外酶和胞内乙醇代谢重要酶类的酶活性进行了分析。结果表明Y-H1 能够在40 ℃条件下正常进行乙醇发酵，发酵33h，最终乙醇浓度达到10.7%（w/w），发酵效率达到90%以上。同时发酵液最终pH 在3.5 左右，显示菌株具有一定的耐酸性能力。同时观察到40 ℃下，菌株的胞外酶和胞内乙醇代谢重要酶类的酶活性发生了变化，乙醇发酵途径中关键酶基因表达下调，而海藻糖合成酶与热激蛋白基因表达量上调，这些结果为进一步研究酵母菌耐热调控机理提供了依据。 糖蜜是一种大规模工业生产乙醇的理想原料，本研究利用选育高浓度乙醇发酵菌株结合配套的发酵稳定剂，研究了糖蜜高浓度乙醇发酵情况。结果表明采用冷酸沉淀预处理糖蜜溶液，采用分批补料的发酵方式，乙醇浓度最高达到了10.26% (w/w)，发酵时间为42 h。同时观察到在糖蜜发酵中，乙醛含量与乙醇浓度存在一定的相关性。 快速乙醇发酵对于缩短乙醇生产周期、降低乙醇生产成本、减少原料腐烂损失具有重要意义。本研究诱变和筛选得到了一株快速乙醇发酵菌株10232B。在优化后的发酵条件下，采用10L 发酵罐进行分批乙醇发酵，经过18h,乙醇的最终浓度达到88.5g/L,发酵效率93.6%，平均乙醇生产速度达到4.92 g/L/h。此菌株在保持较高乙醇生产浓度的同时，拥有快速生产乙醇的能力，适合作为快速乙醇发酵生产菌种。 由于鲜甘薯具有粘度大的特点，传统液化糖化处理很难在短时间内充分糖化原料；高粘度的醪液也难以进行管道输送，容易堵塞管路；同时，也会降低后续的乙醇发酵效率。 本文采用了快速粘度分析法对鲜甘薯糊化粘度特性进行了分析，进而对预处理条件进行了研究，在最佳预处理条件下，糖化2h 后，醪液葡萄糖值最高可达99.3，粘度4.5×104 mPa.s，而采用传统糖化工艺，醪液DE 值仅为85.8，粘度大于1.0×105 mPa.s。 此预处理方法也可用于快速糖化不加水的醪液。后续的乙醇发酵试验表明，通过此预处理方法获得的糖化醪液对乙醇发酵无负面影响。 在前期已实现了实验室水平的鲜甘薯燃料乙醇快速乙醇发酵基础上，进一步将发酵规模扩大到500L，在中试水平上对甘薯乙醇发酵进行了研究。结果表明在500L 中试规模，采用边糖化边发酵（SSF）工艺，在料液比为3∶1，发酵醪液最高粘度为6×104mPa.s 条件下，发酵37h，乙醇浓度达到了12.7%（v/v），发酵效率91%，发酵强度为2.7 g/（L•h）。与目前国内的薯类乙醇发酵生产技术水平具有明显的优越性。 为研究甘薯、木薯乙醇发酵中残糖的组成，采用了高效液相色谱—蒸发光散射检测法，对乙醇发酵残糖进行了分析。结果表明，甘薯、木薯乙醇发酵残糖均为寡聚糖，主要由葡萄糖、木糖、半乳糖、阿拉伯糖和甘露糖构成。随着发酵时间延长，寡聚糖中的葡萄糖、半乳糖、甘露糖可被缓慢的水解释放。提高糖化酶量仅在一定程度上降低残糖，过量的糖化酶反而会导致残糖增加。同时发现3, 5-二硝基水杨酸法不能准确测定甘薯、木薯乙醇发酵中的残总糖含量。进一步筛选了两株残糖降解菌株，对甘薯乙醇发酵残糖的降解利用率均达到了40%以上，而且还能显著降低发酵醪液粘度。经形态学和rRNA ITS 序列分析，确定这两株菌分别属于为木霉属和曲霉属黑曲霉组。 通过对以甘薯原料为代表的非粮原料发酵技术研究开发，以期形成乙醇转化率高，能耗低，生产效率高、季节适应性好，原料适应性广，经济性强，符合清洁生产机制的燃料乙醇高效转化技术，为具有我国特色的燃料乙醇发展模式提供技术支持。 Sweet potato is one of the major feedstock for the fuel ethanol production in China. The planting area and the yield in China take 90% of the world. Sweet potato is an efficient kind of energy crops. The energy outcome per area is higher than corn or wheat. And the manufacture cost of ethanol is the lowest, compared with corn and wheat. So sweet potato is the favorable crop for the bioethanol production in China. However, the low-level fermentation technology restricts the development of ethanol production by sweet potato, including slow ethanol production rate, low ethanol concentration and high energy cost. To solve these problems, we conducted research on the strain breeding, pretreatment, pilot fermentation test and residual saccharides analysis. To study the impact of hyperbaric condition at bottom of the large fermentor on yeast fermentation, high pressure carbon dioxide (CO2) was adopted to simulate the situation. The results showed that the fermentation was prolonged with the increasing pressure. The pressure of CO2 had little impact on the ethanol yield which could reach 90% under the pressure below 0.3 MPa. The inhibition was combined by the high pressure and CO2. Under the high CO2 pressure, the extracellular and important intracellular enzyme activities were different from those under normal state. The changes under 0.1 MPa and 0.2 MPa were similar. The changes under 0.3 MPa were closer to those under 0.4 MPa. The application of thermotolerance yeast could solve the problem of the inconsistent temperature between fermentation and saccharificaton and fulfill the real simultaneous saccharification and fermentation. And it could reduce the cooling cost. A thermotolerance strain Y-H1 was isolated in our research. It gave high ethanol concentration of 10.7%（w/w）at 40 ℃ for 33 h. The ethanol yield efficiency was over 90%. At 40 ℃, the extracellular and important intracellular enzyme activities of Y-H1 showed the difference with normal state, which may indicate its physiological changes at the high temperature. Molasses is another feedstock for industrial ethanol production. By our ethanol-tolerance strain and the regulation reagents, the fermentation with high ethanol concentration was investigated. In fed-batch mode combined with cold acid deposition, the highest ethanol concentration was 10.26% (w/w) for 42h. The aldehyde concentration in fermentation was found to be related to ethanol concentration. The development of a rapid ethanol fermentation strain of Zymomonas mobilis is essential for reducing the cost of ethanol production and for the timely utilization of fresh material that is easily decayed in the Chinese bioethanol industry. A mutant Z. mobilis strain, 10232B, was generated by UV mutagenesis. Under these optimized conditions, fermentation of the mutant Z. mobilis 10232B strain was completed in just 18 h with a high ethanol production rate, at an average of 4.92 gL-1h-1 per batch. The final maximum ethanol concentration was 88.5 gL-1, with an ethanol yield efficiency of 93.6%. This result illustrated the potential use of the mutant Z. mobilis 10232B strain in rapid ethanol fermentation in order to help reduce the cost of industrial ethanol production. As fresh sweet potato syrup shows high viscosity, it is hard to be fully converted to glucose by enzymes in the traditional saccharification process. The high-viscosity syrup is difficult to be transmitted in pipes, which may be easily blocked. Meanwhile it could also reduce the later ethanol fermentation efficiency. To solve these problems, effects of the pretreatment conditions were investigated. The highest dextrose equivalent value of 99.3 and the lowest viscosity of 4.5×104 mPa.s were obtained by the most favorable pretreatment conditions, while those of 85.8 and over 1.0×105 mPa.s was produced by traditional treatment conditions. The pretreatment could also be applied on the material syrup without adding water. The later experiments showed that the pretreated syrup had no negative effect on the ethanol fermentation and exhibited lower viscosity. The fuel ethanol rapid production from fresh sweet potato was enlarged in the 500L pilot scale after its fulfillment on the laboratory level. The optimal ratio of material to water was 3 to 1 in 500L fermentor. With low-temperature-cooking (85 ℃) using SSF, the Saccharomyces cerevisiae was able to produce ethanol 97.44 g/kg for 37h, which reached 92% of theoretical yield. The average ethanol production rate was 4.06 g/kg/h. And the maximum viscosity of syrup reached 6×104mPa.s. The results showed its superiority over current industrial ethanol fermentation. The compositions of the residual saccharides in the ethanol fermentation by sweet potato and cassava were analyzed by high performance liquid chromatography coupled with evaporative light-scattering detector. The results showed that all the residual saccharides were oligosaccharides, mainly composed of glucose, xylose, galactose, arabinose and mannose. The glucose, galactose and mannose could be slowly hydrolyzed from oligosaccharides in syrup during a long period. To increase the glucoamylase dosage could lower the residual saccharides to a certain extent. However, excess glucoamylase dosage led to more residual saccharides. And the method of 3, 5-dinitrosalicylic acid could not accurately quantify the residual total saccharides content. Two residual saccharides degrading strains were isolated, which could utilize 40% of total residual saccharide and lower the syrup viscosity. With the analysis of morphology and internal transcribed spacer sequence, they were finally identified as species of Trichoderma and Aspergillus niger.

Flow-through room temperature phosphorescence optosensing for the determination of lead in sea water

The chelates formed between the heavy metal ion Pb(II) and the reagents 8-hydroxy-5-quinolinesulphonic acid, 8-hydroxy-7-quinolinesulphonic acid and 8-hydroxy-7-iodo-5-quinolinesulphonic acid exhibit strong room temperature phosphorescence (RTP) if retained on the surface of anion exchange resin beads. Based on the on-line formation, in a flow-injection system, of such RTP lead chelates and their transient immobilization on an anion exchange resin, three flow-through optosensing systems are investigated for lead in sea water. Optimum experimental conditions and the analytical performance characteristics of the three optosensors are discussed. Relative standard deviations (RSDs) of the order of 3% are typical at 100 ng ml−1 Pb(II) and the active sensing phases can easily be regenerated by passing 500 μl of 6 M hydrochloric acid. A lead(II) detection limit of 0.1 ng ml−1 (3×background SD, for 2 ml sample injection volumes) was achieved for the optosensor based on 8-hydroxy-7-quinolinesulphonic acid. Possible interferences present in sea water, including cations and anions which could affect the sensor response, are discussed in detail. Finally, the selected RTP flow-through optical sensor has been successfully tested for the determination of lead in sea water at a few ng ml−1.