禄春安息香种子和攀援孔药花全草的化学成分研究

本文对禄春安息香（Styrax macranthus）种子和攀援孔药花（Porandra scandens）全草的化学成分进行了研究，共获得30个化合物，其中2个为新化合物。 从禄春安息香种子95%乙醇提取物中分离并鉴定了12个化合物，其中2个新化合物鉴定为3-[7-methoxy-2-(3,4-methylenedioxy phenyl) benzofuran-5-yl] propyl 3-[7-methoxy-2-(3,4-methylenedioxyphenyl)benzofuran-5-yl] propanoate (1) 和去甲氧基-egonol-龙胆双糖甙 (2)；已知化合物分别为2-(3,4-二氧亚甲基苯基)-5-甲酰基-7-甲氧基-苯并呋喃 (3)、egonol (4)、去甲氧基-egonol (5)、去甲基-egonol (6)、egonol-葡萄糖甙 (7)、egonol-龙胆双糖甙 (8)、egonol-龙胆三糖甙 (9)、豆甾醇 (10)、二十四烷酸 1-甘油酯 (11) 和胡萝卜甙 (12)。生物活性测试发现，化合物2具有促进雌激素E2合成的作用。 从攀援孔药花全草95%乙醇提取物中分离并鉴定了19个化合物：(2S,3S,4R)-2-[(2R)-2-羟基-二十一烷酰基氨基]-二十一烷-1,3,4-三醇 (13)、(2S,3S,4R)–2–二十四烷酰基氨基-十八烷-1,3,4-三醇 (14)、胡萝卜甙 (12)、β-谷甾醇 (15)、(20S,22E,24R)-5α,8α-表二氧-麦角甾-6,22-二烯-3β-醇 (16)、6β-羟基-豆甾-4-烯-3-酮 (17)、十六烷酸 1-甘油酯 (18)、桦木酸 (19)、大黄素 (20)、二十二烷酸 1-甘油酯 (21)、对羟基苯甲醛 (22)、十七烷酸 1-甘油酯 (23)、金色酰胺醇乙酸酯(24)、十九烷酸 1-甘油酯 (25)、棕榈酸 (26)、(E)-p-香豆酸 (27)、(22E,24S)-24-麦角甾醇-7,22-二烯-3β,5α,6β-三醇 (28)、2-去氧-β-蜕皮激素 (29)和auranamide (30)。 综述了近十年来发现的2－芳基苯并呋喃类新木脂素的结构特征、来源、生物活性和化学全合成。 Phytochemical investigation on the seeds of Styrax macranthus and the whole plants of Porandra scandens led to the isolation of thirty compounds, two of which were new ones. Two new 2-aryl benzofuran derivatives, 3-[7-methoxy-2-(3,4-methylenedioxy phenyl) benzofuran-5-yl]propyl 3-[7-methoxy-2-(3,4-methylenedioxyphenyl)benzo furan-5-yl]propanoate (1) and demethoxy egonol gentiobioside (2), were isolated from the 95% aqueous ethanolic extract of the seeds of Styrax macranthus, together with 7-methoxy-2-(3,4-methylenedioxyphenyl) benzofuran-5-carbaldehyde (3), egonol (4), demethoxy egonol (5), demethyl egonol (6), egonol glucoside (7), egonol gentiobioside (8), egonol gentiotrioside (9), stigmasterol (10), 2,3-dihydroxypropyl tetracosoate (11), and daucosterol (12). In vitro test, compound 2 promote the synthesis of estrogen E2. Nineteen compounds were isolated from the 95% aqueous ethanolic extract of the whole plant of Porandra scandens for the first time. Their structures were identified as (2S,3S,4R)-2-[(2R)-2-hydroxy-heneicosanoylamino]-1,3,4- heneicosanetriol (13), (2S,3S,4R)-2-tetracosanoylamino-1,3,4-octadecanetriol (14), daucosterol (15), β-sitosterol (12), (20S,22E,24R)-5α,8α-epidioxy-ergosta-6,22-diene- 3β-ol (16), 6β-hydroxylstigmast-4-en-3-one (17), 1-glycerol-1-hexadecoate (18), betulinic acid (19), emodin (20), 1-glycerol-1-docosoate (21), p-hydroxybenzaldehyde (22), 1-glycerol-1-heptadecoate (23), aurantiamide acetate (24), 1-glycerol-1- nonadecoate (25), palmatic acid (26), (E)-p-coumaric acid (27), (22E,24S)- 24-metbylcbolesta-7,22-diene-3β,5α,6β-triol (28), 2-deoxycrustecdysone (29), and auranamide (30). The characteristic, natural resource, bioactivity, and the total synthesis of 2-aryl benzofurans were reviewed.

尼泊尔水东哥、水麻、木姜冬青和青荚叶的化学成分研究

活性筛选中发现尼泊尔水东哥 (Saurauia napaulensis DC.) 树皮95%乙醇提取物具有α-淀粉酶抑制活性、水麻(Debregeasia orientalis) 枝叶95%乙醇提取物显示血管紧张素转化酶(ACE)抑制活性、青荚叶(Helwingia japonica (Thunb.) Dieter.) 95%乙醇提取物的中小极性部分显示蛋白酪氨酸磷酸酯酶(PTP)1B抑制活性。为全面了解它们的成分及相关活性成份，主要运用硅胶柱层析方法从这三个植物分离得到39个化合物，通过波谱分析或与已知品对照的方法对其进行了鉴定。对木姜冬青(Ilex litseaefolia Hu et Tang)的成分做了进一步的研究，取得了如下结果。 1. 从尼泊尔水东哥树皮的95%乙醇提取物分离并鉴定12个化合物： auranamide、aurantiamide benzoate、齐墩果酸、β-谷甾醇、β-胡萝卜甙、乌苏酸、2α,3α-二羟基-12-烯-28-乌苏酸、2α,3β,24-三羟基-12-烯-28-乌苏酸、(2S,3S,4R,10E)-2-[(2'R)-2' -hydroxytetracosanoylamino] -10-octadecene -1,3,4-triol、 2α,3α,24-三羟基-12-烯-28-齐墩果酸、2α,3β-二羟基-12-烯-28-乌苏酸和2α,3α,24-三羟基-12-烯-28-乌苏酸。 2. 从水麻枝叶的95%乙醇提取物分离并鉴定了18个化合物：棕榈酸、二十烷酸、二十烷酸甲酯、β-谷甾醇、Monogynol A、桦木酸、Hederagenin、β-胡萝卜甙、18αH-19(29)-烯-3-酮-乌苏烷、3，4-开环-20(30)-烯-乌苏烷-3-酸、Pomolic acid，表儿茶素、儿茶素、槲皮素、槲皮素-3-O-β-D-吡喃葡萄糖苷、紫丁香苷、紫丁香酚苷和山萘酚-3-O-芸香糖。儿茶素、槲皮素和槲皮素-3-O-β-D-吡喃葡萄糖苷为具有ACE抑制活性的成分。 3. 从木姜冬青95%乙醇提取物的乙酸乙酯部分分离并鉴定了5个化合物： 2-O-β-D-吡喃葡萄糖-6,2´-二羟基-4,4´-二香草酰氧甲基-1,1´-二苯醚（冬青苷）和四个已知化合物：七叶内酯、香草酸、3,4-二甲氧基苯乙酸和vanilloylcalleryanin。冬青苷为新化合物。 4. 从青荚叶95%乙醇提取物的中小极性部分分离并鉴定了9个化合物：β-谷甾醇、β-胡萝卜苷、羽扇豆醇、桦木醇、桦木酸、棕榈酸甘油酯、桂皮酸、6αH-4-烯-3-酮-豆甾醇和6βH-4-烯-3-酮-豆甾醇。 5. 对1985-2006年间天然二苯醚类化合物及活性研究进展进行综述. The in vitro test indicated that the 95% ethanolic extract of the barks of Saurauia napaulensis DC showed α-amylase inhibitory activity, the 95% ethanolic extract of the whole plants of Debregeasia. orientalis showed angiotensin converting enzyme (ACE) inhibitory activity and some fractions of the 95% ethanolic extract of the aerial parts of Helwingia japonica showed protein tyrosine phosphatase (PTP)1B inhibitory activity. In order to investigate components and active compounds of the three plants, they were chemically studied mainly using. Thirty-nine compounds were isolated predominantly by column chromatography identified by spectral methods or comparing them with authentic samples. Further investigation of Ilex litseaefolia Hu et Tang was carried out. Major results are as follows: 1. Twelve compounds were isolation from the 95% ethanolic extract of the barks of S. napaulensis DC. They were identified as auranamide, aurantiamide benzoate, oleanolic acid, β-sitosterol, β-daucosterol, ursolic acid, 2α,3α-dihydroxyurs-12-en-28-oic acid, 2α,3β,24-trihydroxyurs-12-en-28-oic acid, (2S,3S,4R,10E)-2-[(2'R)-2'-hydroxytetracosanoyl amino]-10-octadecene-1,3,4-triol, 2α,3α,24 -trihydroxyolean-12-en-28-oic acid, 2α,3β-dihydroxyurs-12-en-28-oic acid, and 2α,3α,24-trihydroxyurs-12-ene-28-oic acid, respectively, by spectral methods or comparing them with authentic samples. 2. Eighteen compounds were isolation from the 95% ethanolic extract of the whole plants of D. orientalis. They were identified as palmitic acid, henicosanoic acid, henicosanoic acid methyl ester, β-sitosterol, monogynol, betulinic acid, hederagenin, β-daucosterol, 18αH-urs-20(30)-en-3-one, 3,4-seco-urs-20(30)-en-3-oic acid, pomolic acid, (-)-epicatechin, (+)-catechin, quercetin, quercetin 3-O-β-D-glucopyranoside, syringin, syringiaresinol digloside and kaempferol-3-O-rutinose. (+)-Catechin, quercetin and quercetin 3-O-β-D-glucopyranoside were the ACE inhibitory active components. 3. Further phytochemical investigation of the ethyl acetate parts of 95% ethanolic extract of the whole plant of I. litseaefolia afforded 2-O-β-D-glucopyranose-4,4´-di-vanilloyloxymethyl-2,6´-dihydroxy-1,1´-diphenyl ether (ilexiside), esculetin, vanillic acid, 3,4-dimethoxybenzylacetic acid and vanilloylcalleryanin. Ilexiside was new compound. 4. Nine compounds were isolation from the 95% ethanolic extract of the whole plant of H. japonica: β-sitosterol, β-daucosterol, lupeol, betulin, betulinic acid, glycerol monopalmitate, cinnamic acid, stignast-4-en-6β-3-one and stignast-4-en-6α-3-one 5.Diphenyl ether compounds from nature between 1985-2006 were summarized.

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.

克拉维酸产生菌的诱变育种与发酵工艺优化研究

以克拉维酸产生菌棒状链霉菌Streptomyces clavuligerus CCRC11518（ATCC 27064）III50为出发菌株, 首先比较各种物理和化学诱变剂处理对其克拉维酸生物合成的影响, 确定了亚硝基胍为棒状链霉菌诱变育种的诱变剂及其处理剂量: 2mg/ml、40min. 经浓度为2mg/ml的亚硝基胍处理40min后, 采用新颖理性化筛选方法, 通过逐步筛选自身代谢产物抗性突变株、克拉维酸抗性突变株和链霉素抗性突变株, 最终得到一株克拉维酸高产菌VI118(效价633μg/ml), 其克拉维酸效价是出发菌株(效价377μg/ml)的167.9%. 该高产突变株在琼脂斜面培养基上连续传接10代, 克拉维酸效价保持稳定. 通过单因子和多因子摇瓶正交试验, 对高产菌株VI118的发酵条件进行了研究, 确定最佳发酵条件: 甘油60g, 水解植物蛋白 60g, KH2PO4 0.5 g, 玉米浆 7.5g, MnSO4•H2O 0.34g, MgSO4•7H2O 0.99g, FeSO4•7H2O 0.56g, 蒸馏1000ml, pH 7.0, 发酵培养基装量20ml/250ml三角瓶, 接种量10％, 培养温度28ºC, 220r/min摇床培养72h后测定效价. 在最佳发酵条件下克拉维酸效价达到651μg/ml, 同时把初始发酵培养基的昂贵成分替换为廉价的工业原料. 通过摇瓶分批补料试验, 得到最佳补料物质和补料方式：在上述最佳发酵条件下, 分别在发酵培养48h、56h、64h、72h时补加4ml无菌水, 80h发酵结束, 克拉维酸效价达到905μg/ml. 在不增加原料成本的情况下通过摇瓶补料方式克拉维酸效价为未补料的139.0％, 总产量为未补料的264％. By a novel rational screening method, mutant Streptomyces clavuligerus CCRC11518（ATCC 27064）III50（titres 377μg/ml）, as the clavulanic acid-producing parent strain, was treated by NTG (2mg/ml) for 40min, and the self-generated metabolites resistant mark, the clavulanic acid resistant mark and the streptomycin resistant mark were added step by step. Finally, the mutant VI118（titres 633μg/ml）with the three marks was obtained. The clavulanic acid productivity of this mutant was increased by 167.9% compared with the parent strain. After reproducing 10 generations on the agar medium slant, the productivity of this mutant was stable. The optimum fermentation conditions were established as followings: glycerol 60g, acid hydrolyzed vegetable protein 60g, KH2PO4 0.5g, corn steep liquor 7.5g, MnSO4•H2O 0.34g, MgSO4•7H2O 0.99g, FeSO4•7H2O 0.56g, distilled water 1 liter, pH 7.0, 20ml in 250ml shake-flask, inoculation 10%(v/v), fermentation temperature 28ºC, rotation speed 220 r/min, time 72h. The clavulanic acid productivity was 651μg/ml, while used the low-priced industrial raw materials. After studying on fed-batch in the shake-flask, the optimum fed-batch manner was obtained: under optimum fermentation conditions, at 48h, 56h, 64h and 72h, adding 4ml distilled water into each flask, fermentation ending at 80h. The clavulanic acid productivity was increased by 139% compared with no fed-batch, meanwhile the total yield was increased by 264%.

Study on conical columns with different conical angles for semi-preparative liquid chromatography

The dynamic flow profiles and separation performances in conically shaped preparative liquid chromatographic columns (inlet i.d. larger than outlet i.d.) with three different angles (7, 10 and 15degrees) were studied and compared with cylindrical column of the same length and internal volume. The shapes of dynamic flow profiles were studied by on-column visualization method. The transparent chromatographic columns made of polymethyl methacrylate (PMMA), packed with C-18 bonded silica, were immerged into a cubic pool filled with glycerol to eliminate the cylindrical and conical lens effect. The flow profiles of colored iodine solution in the columns were observed clearly using cyclohexane as mobile phase since the refractive indices of C-18, column wall and the mobile phase are very close. In the conical column of 15degrees (20-7 mm i.d.) the mobile phase in the central region migrated slower than in wall region as it moved toward the column outlet, while in the conical column of 7degrees (17-11 mm i.d.) the mobile phase in the central region migrated faster than in wall region just like in cylindrical column. We found that a plug-like flow profile was generated in the conical column of 10degrees (18-9 mm i.d.) during the whole migration process. A carmine and brilliant blue mixture was used as a probe to test the separation ability of the columns. The resolutions of the two compounds on the conical column of 7, 10, 15degrees and on the cylindrical column were 0.6, 1.57, 1.29 and 0.8, respectively. (C) 2003 Elsevier B.V. All rights reserved.

A single-strand conformation polymorphism method by capillary electrophoresis with laser-induced fluorescence for detection of the T1151A mutation in hMLH1 gene

Mutation of hMLH1 gene plays an important role in human tumorigenesis. A highly sensitive single-strand conformation polymorphism (SSCP) method for detection of the T1151A mutation in exon 12 of the hMLH1 gene was for the first time developed employing laser-induced fluorescence capillary electrophoresis (LIF-CE). Effects of the concentration of linear polyacrylamide solution, running temperature, running voltage and the addition of glycerol on SSCP analysis were investigated, and the optimum separation conditions were defined. Thirty colorectal cancer patients and eight lung cancer patients were screened and the T1151A mutation was found in four of them. Based on CE-sequencing the mutation was further confirmed. To our knowledge, this is for the first time that the T1151A mutation is found in lung cancer. Our method is simple, rapid, and highly sensitive and is well suited to the analysis of large numbers of clinical samples.

Aliphatic Poly(ester-carbonate)s Bearing Amino Groups and Its RGD Peptide Grafting

This article deals with (1) synthesis of novel cyclic carbonate monomer (2-oxo [1,3]dioxan-5-yl)carbamic acid benzyl ester (CAB) containing protected amino groups; (2) ring-opening copolymerization of the cyclic monomer with L-lactide (LA) to provide novel degradable poly(ester-carbonate)s with functional groups; (3) removal of the protective benzyloxycarbonyl (Cbz) groups by catalytic hydrogenation to afford the corresponding poly(ester-co-carbonate)s with free amino groups; (4) grafting of oligopeptide Gly-Arg-Gly-Asp-Ser-Tyr (GRGDSY, abbreviated as RGD) onto the copolymer pendant amino groups in the presence of 1,1'-carbonyldiimidazole (CDI).

Photoluminescence properties of LaF3: Eu3+ nanoparticles prepared by refluxing method

The europium-doped LaF3 nanoparticles were prepared by refluxing method in glycerol/water mixture and characterized with X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), UV-vis diffuse reflectance spectrum, and photoluminescence spectra. The results of XRD indicated that the obtained LaF3: Eu3+ nanoparticles were well crystallized with a hexagonal structure. ne FE-SEM image illustrated that the LaF3: Eu3+ nanoparticles were spherical with an average size around 30 nm. Under irradiation of UV light, the emission spectrum of LaF3: Eu3+ nanoparticles exhibited the characteristic line emissions arising front the D-5(0)-> F-7(J), (J=1, 2, 3, 4) transitions of the Eu3+ ions, with the dominating emission centered at 590 nm. In addition, the emissions from the 51), level could be clearly observed due to the low phonon energies (-350 cm(-1)) of LaF3 matrix. The optimum doping concentration for LaF3: Eu3+ nanoparticles was determined to be 20mol.%.

Enhanced luminescence of BPO4 by mixing with SiO2 and Al2O3

In this paper, BPO4-xSiO(2) (X: SiO2/BPO4 molar ratio, 0-70%) and BPO4-xAl(2)O(3) (X: Al2O3/BPO4 molar ratio, 0-20%) powder samples were prepared by the Pechini-type sol-gel (PSG) process using glycerol and poly(ethylene glycol) as additives. The structure and optical properties of the resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), diffuse reflection spectra, photoluminescence (PL) excitation and emission spectra, kinetic decay, and X-ray photoelectron spectra (XPS), respectively. It was found that the Pechini-type sol-gel-derived BPO4-xSiO(2) annealed at 1000 degrees C and BPO4-xAl(2)O(3) annealed at 960 degrees C exhibited bright bluish-white emissions centered at 428 and 413 nm, respectively. The luminescence decay curve analysis indicates that each sample has two kinds of lifetimes (more than 0.4 ms and less than 10 ns) and two types of kinetic decay behaviors, which can be fitted into a double-exponential function and a single-exponential function, respectively.

Preparation and Physical Properties of LLDPE Grafted with Novel Nonionic Surfactants

Copolymers of linear low-density polyethylene (LLDPE) grafted with two novel nonionic surfactants, acrylic glycerol monostearate ester (AGMS) and acrylic polyoxyethylenesorbitan monooleate ester (ATW-EEN80), containing hydrophilic and hydrophobic groups and 1-olefin double bond were prepared by using a plasticorder at 190 degrees C. To evaluate the grafting degree, two different approaches based on H-1-NMR data were proposed, and FTIR calibration was showed to validate these methods. The rheological response of the molten polymers, determined under dynamic shear flow at small-amplitude oscillations, indicated that crosslinking formation of the chains could be decreased with increasing the monomer concentration. Their thermal behavior was studied by DSC and polarization microscope (PLM): The crystallization temperature (T-C) of grafted LLDPE shifted to higher temperature compared with neat LLDPE because the grafted chains acted as nucleating agents. Water and glycerol were used to calculate the surface free energy of grafted LLDPE films.

Evaluation of different culture conditions for high-level soluble expression of human cyclin A(2) with pET vector in BL21 (DE3) and spectroscopic characterization of its inclusion body structure

In this paper, we evaluated various parameters of culture condition affecting high-level soluble expression of human cyclin A, in Escherichia coli BL21(DE3), and demonstrated that the highest protein yield was obtained using TB(no glycerol) + 0.5% glucose medium at 25 degrees C. By single immobilized metal ion affinity chromatography, we got highly purified human cyclin A(2) with a yield ranged from 20 to 30 mg/L. By amyloid-diagnostic dye ThT binding and Fourier transform infrared spectroscopy, we observed a significant decrease in alpha-helix content and an increase in beta-sheet structure in cyclin A(2) inclusion body in comparison to its native protein, and confirmed the resemblance of the internal organization of cyclin A(2) inclusion body and amyloid fibrils.

Preparation and properties of a reactive type nonionic surfactant grafted linear low density polyethylene

A reactive type nonionic surfactant, monostearic acid monomaleic acid glycerol diester (MMGD) was synthesized in our laboratory. Grafting-copolymerization of linear low density polyethylene ( LLDPE) with MMGD was carried out by using beta ray irradiation in air in a twin-screw extruder. Evidence of the grafting of MMGD as well as its extent was determined by Fourier-transformed infrared (FT-IR) spectroscopy. The effects of monomer concentration, reaction temperature and screw run speed on degree of grafting were studied systematically. The thermal behavior of LLDPE-g-MMGD was investigated by using differential scanning calorimety ( DSC). Compared with neat LLDPE, the crystallization temperature ( Tc) of LLDPE-g-MMGD increased about 3 degrees C, and the melting enthalpy (Delta H-m) decreased with increase of MMGD content. It showed that the grafted MMGD monomer onto LLDPE acted as a nucleating agent. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE-g-MMGD film. The wettability is expressed by the water contact angle. With an increasing percentage of MMGD, the contact angles of water on film surface of LLDPE- g-MMGD decrease monotonically.

Preparation and properties of a novel nonionic surfactant grafted linear low density polyethylene

A novel nonionic surfactant, glycerol monostearic acid monomaleic acid diester (GMMD) was synthesized in our laboratory. Grafting-copolymerization of linear low density polyethylene (LLDPE) with GMMD was carried out by using P-ray irradiation in a twin-screw extruder. Evidence of the grafting of GMMD, as well as its extent, was determined by FT-IR. The effects of monomer concentration, reaction temperature and screw run speed on degree of grafting were studied systematically. The thermal behavior of LLDPE-g-GMMD was investigated by using differential scanning calorimety (DSC). Compared with neat LLDPE, the crystallization temperature (T,) of LLDPE-g-GMMD increased about 3 degrees C, and the melting enthalpy (Delta H-m) decreased with increase of GMMD content. It showed that the arafted GMMD monomer onto LLDPE acted as a nucleating agent. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE-g-GMMD film. Accelerated dripping property of film samples was investigated. The dripping duration of LLDPE-g-GMMD film and commercial anti-fog dripping film at 60 degrees C were 52 days and 17 days, respectively.

Sol-gel-derived BPO4/Ba2+ as a new efficient and environmentally-friendly bluish-white luminescent material

In this paper, BPO4 and Ba2+-doped BPO4 powder samples were prepared by the sol-gel process using glycerol and poly(ethylene glycol) as additives. The structure and optical properties of the resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), diffuse reflection spectra, photoluminescence (PL) excitation and emission spectra, quantum yield, kinetic decay, and electron paramagnetic resonance (EPR), respectively. It was found that the undoped BPO4 showed a weak purple blue emission (409 nm, lifetime 6.4 ns) due to the carbon impurities involved in the host lattice. Doping Ba2+ into BPO4 resulted in oxygen-related defects as additional emission centers which enhanced the emission intensity greatly (> 10x) and shifted the emission to a longer-wavelength region (lambda(max) = 434 nm; chromaticity coordinates: x = 0.174, y = 0. 187) with a bluish-white color. The highest emission intensity was obtained ;when doping 6 mol % Ba2+ in BPO4, which has a quantum yield as high as 31%. The luminescent mechanisms of BPO4 and Ba2+-doped BPO4 were discussed in detail according to the existing models for silica-based materials.