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脱醇作用

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Then Doripenem came into the market in the July ,2005. We studied the synthesis of Doripemen.Firstly, we synthesized the chemical 2 from the starting material------o-hydroxylphenylacylamine through Reformastky reaction, alkylation, Diekmann reaction, enolization, esterification and etc. Secondly, we synthesized the chemical 3 from L — hydroxylproline through the protection of carboxyl, amidogen and hydroxyl group, reduction by NaBr, SN_2 substitution and Mitsumobu reaction.

我们以水杨酰胺为起始原料,经Reformatsky反应、烷基化、Diekmann环合、烯醇化、酯化等反应合成双环母核2;再从L-羟基脯氨酸出发,经酯化保护羧基、保护氨基、保护羟基、硼氢化还原酯得醇、Sn2取代和Mitsumobu反应等合成巯基侧链3;最后由化合物3经脱保护、水解得硫醇,和化合物2在二异丙基乙基胺的作用下缩合,最后Pd/C催化脱保护,历经16步反应最终得到产物多尼培南。

Yields from chiral bisoxazolines (5a) with diethyl oxalate using NaOCH〓 as base for the first time. The structures of chiral multioxazolines and their intermediates, multi (β-hydroxylamide) s, were characterized by 〓H NMR, IR, mass spectra and elemental analysis. The catalytic activities and enantioselectivities of chiral multi (β-hydroxylamide) s (4) and chiral multioxazolines (5~8) were investigated by using acetophenone and β-acetonaphthone as former chiral ketone, KBH〓 or NaBH〓 as reductive reagent in chapter three.

在此基础上,对合成方法作了创新,以羧酸或酯为原料,在无催化剂的条件下与手性α-氨基醇反应,通过回流分水或脱醇的方法,一步反应合成了手性多噁唑啉(5~8),产率为89.2%~98.4%;以手性双噁唑啉(5a)为原料,在NaOCH〓的作用下,与草酸二乙酯反应,首次合成了呋喃类双嗯唑啉(6a),产率为72.9%~75.6%。

The object of this study is to evaluate the immunoregulation and anti-tumor activities of Arnebia root polysaccharide in vitro. The ARPS was obtained by hot-water extraction, alcohol precipitation, de-protein, de-color, and dialysis etc. from Arnebia root and was administered on mouse spleen lymphocyte and tumor cell with 24 μgmL^(-1), 121 μgmL^(-1), 364 μgmL^(-1), respectively.

为研究紫草多糖在体外对小鼠脾淋巴细胞的免疫调节活性及对肿瘤细胞的细胞毒作用,本实验采用水提醇沉法,经脱蛋白、脱色、透析等方法提取紫草多糖,MTT法检测紫草多糖对淋巴细胞增殖及对HepG2、SPC-A-1肿瘤细胞的杀伤作用。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area;2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support;3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier;4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling;5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene PolymerizationIn this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that:1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS;2.co-mlling time had no obvious effect on the texture of support after 12 hours;3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现;3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布;4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒;5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明:1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致;2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响;3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area; 2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support; 3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier; 4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling; 5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene Polymerization In this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that: 1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS; 2.co-mlling time had no obvious effect on the texture of support after 12 hours; 3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现; 3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布; 4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒; 5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明: 1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致; 2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响; 3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

Secondly, the silver based catalysts modified by phosphorus, zirconium, zinc, potassium and so on using molecular sieve as carrier, which were produced by ion-exchange method, had also good catalytic performance for 1,2-propane glycol oxidation to methylglyoxal. The conversion of 1,2-propane glycol and the selectivity of methylglyoxal were both high, and the impurity such as formaldehyde and acetaldehyde in the product is little. At the condition of the temperature 300 ℃, the molar ratio of oxygen to 1,2-propane glycol 1.7:1, the space velocity 6000h~(-1), and the concentration of 1,2-propane glycol 70wt%, the conversion of 1,2-propane glycol is 90% and the selectivity of methylglyoxal is 45% on the Ag-P catalyst.

其次对采用离子交换法制备的负载在分子筛上的银系催化剂进行了研究,发现此催化剂在助催化剂磷、锆、锌、钾等的作用下对丙二醇的低温氧化脱氢具有很高的活性,可以得到较好的丙酮醛的收率,并且产物中的甲醛、乙醛副产物的量比较低;经过对Ag-P催化剂上反应条件的考察,发现当温度为300℃、氧醇比1.7:1、空速6000h~(-1)、丙二醇浓度为70wt%时,丙二醇的转化率为90%,丙酮醛的选择性为45%。

Trehalase plays an important role in glycogen accumulation in the formarion of diapaused eggs. At the beginning of diapause, glycogen phosphorylase is the key enzyme to glycogen decomposition and the formation of sorbitol and glycerol, whereas at the stage of diapause termination, NAD-sorbitol dehydrogenase is the key enzyme to sorbitol decomposition and glycogen re-synthesis.

在滞育卵形成过程中,海藻糖酶对糖原的积累起着重要的作用;在滞育开始时,糖原的分解与山梨醇、甘油的形成,糖原磷酸化酶是关键酶;在滞育解除时,山梨醇的分解与糖原的再生成时山梨醇脱氢酶(NAD-sorbito1 dehydrogenase)是关键酶。

Crude enzyme liquid alone had no function in decolorization, while mycelium had great function in decolorization. When added H2O2 and veratryl alcohol into the crude enzyme liquid, the decolorization rate had increased from 0% to more than 30%, so the H2O2 and veratryl alcohol played roles in the decolorization.

在利用粗酶液废水脱色研究时,发现粗酶液单独没有脱色作用,有菌体存在时脱色效果明显:粗酶液中加人过氧化氢和黎芦醇后,脱色率由0%增至30%以上,,因此酶与染料作用过程中也需要过氧化氢和黎芦醇作为中间体。

The ulnas of fetal mice were cultured for 48 hours in BGJb medium treated respectively with estradiol and purearin. After fixing long bones and decalcification, paraffin sections were made, and then performed immunohistochemical staining for determining the level of typeⅠcollagen protein in growth plates. Positive cell locations in the resting zone, proliferative zone and hypertrophic zone of epiphyseal plate were observed under light microscope.

剥离出胎鼠尺骨,置于BGJb培养基中,葛根素和雌二醇作用48 h后,将长骨固定,脱钙后作石蜡切片,进行免疫组织化学染色,光镜下观察骺板静止区、增殖区和肥大区阳性细胞定位,图像分析系统下测定免疫反应阳性细胞面积。

objective to study the effects of berbamine and batiolun on ldh metabolizability in the process of increasing leukocyte.methods enzyme biochemical techniques is used to study the effect of berbamine and batiolˉun in the process of inceasing leukocyte and also to study the effect of ldh metabolizability.results when leukocyte is inhibited by the immune inhibitor cycolophosphamcide,berbamine and batiolun are compared of the effect of ldh activity.conclusionthe study draws the conclusion that both berbamine and batiolun can increase thegranule cell,and they also have some effect of the ldh metabolizability.

目的 研究小檗胺和鲨肝醇升高白细胞作用及对细胞内ldh的代谢的影响。方法采用酶细胞化学方法,对两种药物在治疗由免疫抑制剂环磷酰胺所致的白细胞减少症时,对乳酸脱氢酶活性的影响进行了比较观察。结果小檗胺和鲨肝醇均可升高粒细胞,同时对细胞内ldh的代谢有一定的影响。结论小檗胺和鲨肝醇能使外周血粒细胞增加,可用于治疗多种因素引起的白细胞减少症。

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