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羟基酮

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Eight hydrazone Schiff bases have been synthesized by the reaction of salicylaldehyde, o–vanillin, 2-hydroxy-1-naphthaldehyde with nicotinic or isonicotinoyl hydrazide in anhydrous ethanol respectively; Three thiosemicarbazone Schiff bases have been synthesized by the reaction of salicylaldehyde, o–vanillin, o–hydroxyacetophenon with thiosemicarbazide in hydrous-ethanol respectively.

主要包括以下五部分的工作: 1、以水杨醛、邻香草醛、邻羟基萘甲醛、邻羟基苯乙酮分别与烟酰肼和异烟酰肼按1:1的比例在无水乙醇中反应,制备了八种酰腙类Schiff碱;以水杨醛、邻香草醛、邻羟基苯乙酮与氨基硫脲在水-乙醇混合溶剂中反应,合成了三种Schiff碱配体,并对Schiff碱配体的结构进行了表征。

By the mechanism of the electrocyclic reaction, three groups of 4-hydroxy-2-cyclobutenones 4 were designed and synthesized to investigate their behaviors underthe thermolysis conditions Meanwhile, a new procedure for preparation of 2(5H)-furanone 5 Was discovered.

根据电环化反应机理,我们设计了三组不同类型的4-羟基-2-环丁烯酮(4)。通过对4-羟基-2-环丁烯酮(4)进行热解,发现了一种制备2(5H)-呋喃酮类化合物(5)的新方法。

To further study the chemical constitutes of lipophilic active parts, we prepared Alc95% and Alc50% according to original literature. 20 compounds were isolated by using macroporous resin, silica gel, polyamide, Sephadex LH-20, Rp-18, preparative TLC and preparative HPLC chromato-graphy. The structures of them were elucidated by means of physical and chemical properties, modern spectroscopic analysis techniques—UV、IR、 EI/MS、ESI/MS、〓H-NMR、〓C-NMR、DEPT、HMQC、HMBC. They are nine anthraquinones: chrysophanol (95-1), physcion (95-2), emodin (95-5), aloemodin (95-7), rhein (50-1), sennoside A or B (50-6),ω-hydroxylemodin (95-10), chrysophanol-8-0-β-D-glucoside (95-12), aloemodin-ω-0-β-D-glucoside (95-13); three phenanthaquinones: tanshinone ⅡA (95-3), cryptotanshinone (95-6), tanshinone Ⅰ(95-4); one isoflavone: 7, 3'-dihydroxyl-5' methoxyisoflavone (95-14) and protocaechuic aldehyde (95-9), protocaechuic acid (95-11), astragaloside Ⅳ(50-4), amygdalin (50-5), 2, 3, 5, 4'-tetrahydroxylstilbene-2-0-β-D-glucoside (50-3),-catechin (50-2), cinnamic acid (95-8). Among them, 3'-dihydroxyl-5' methoxyisoflavone (95-14) is a new compound.

经过溶剂萃取、大孔吸附树脂富集、Sephadex LH-20精制、制备TLC及Semi-pre HPLC等手段从中分离了20个化合物,利用理化性质和波谱技术(UV、IR、EI/MS、ESI/MS、〓H-NMR、〓C-NMR、DEPT、HMQC、HMBC)相结合鉴定了它们的结构,分别为9种蒽醌类化合物:大黄酚,大黄素甲醚,大黄素,芦荟大黄素,大黄酸,番泻苷A或B,ω-羟基大黄素(ω-hydroxylemodin),大黄酚-8-0-β-D-葡萄糖苷(chrysophanol-8-0-β-D-glucoside),芦荟大黄素-ω-0-β-D-葡萄糖苷(aloemodin-ω-0-β-D-glucoside);3种菲醌类化合物:丹参酮ⅡA(tanshinoneⅡA),隐丹参酮,丹参酮Ⅰ(tanshinone Ⅰ);1种异黄酮:7,3'-二羟基-5'-甲氧基异黄酮(7,3'-dihydroxy-5' methoxyisofla-vone)以及原儿茶醛,原儿茶酸,黄芪甲苷(astragaloside Ⅳ),苦杏仁苷,2,3,5,4'-四羟基二苯乙烯-2-0-β-D-葡萄糖苷(2,3,5,4'-tetrahydroxylstilbene-2-O-β-D-g1ucoside),Z—儿茶素,桂皮酸。

Their chemical structures were characterizd on the basis of spectral and chemical evidences to be: Sarracenin (1), 2-methyl-5-hydroxy-7-O-ethyl caffeate chromome (2), Naringenin(3), 2-methyl-5, 7-dihydroxychromome (4), 2-methyl-6-hydroxyl-cinnamic acid methyl ester (5), eriodictyol (6), quercetin (7), Naringenin-7-O-β-D-glucoside( 8 ), eriodictyol-7-O-α-D-glucoside (9), quercetin-3-O-β-D-glucoside(10). In addition, one compound was abtained from the n-butanol frationk, which was finally identified as Morrosiside(11) by spectral and chemical evidences.

以波谱数据及其理化性质鉴定为:Sarracenin(1),2-甲基-5-羟基-7-O-咖啡酸乙酯色原酮(2),柚皮素(3),2-甲基-5,7-二羟基色原酮(4),2-甲基-6-羟基苯丙烯酸甲酯(5),圣草酚(6),槲皮素(7),柚皮素-7-O-β-D-葡萄糖苷(Naringenin-7-O-β-D-glucoside)(8),圣草酚-7-O-α-D-葡萄糖苷(eriodictyol-7-O-α-D-glucoside)(9),槲皮素-3-O-β-D-葡萄糖苷(quercetin--3-O-β-D-glucoside)(10);另外从正丁醇萃取部位分离得到1个化合物,以波谱数据和文献对照鉴定为:Morroniside(11)。

Their structures were identified by physicochemical constant and spectral analysis (IR, UV, EI-MS, 1H-NMR, 13C-NMR, and HMBC). Results The compounds were identified from their ethanol extracts as: 6, 8-dihydroxy-2-[2-(3'-methoxy-4'-hydroxyl phenylethyl)] chromone and 6-methoxy-2-[2-(3'-methoxy-4'-hydroxyl phenylethyl)] chromone.

结果 从沉香乙醇提取物中分得2个色酮类成分,分别鉴定为6,8-二羟基-2-[2-(3'-甲氧基-4'-羟基苯乙基)]色原酮{6,8-dihydroxy-2-[2-(3'-methoxy-4'-hydroxyl phenylethyl)]chromone,Ⅰ}和6-甲氧基-2-[2-(3'-甲氧基-4'-羟基苯乙基)]色原酮{6-methoxy-2-[2-(3'-methoxy-4'-hydroxyl phenylethyl)]-chromone,Ⅱ}。

These compounds were identified as follows:chrysophanol (FP-1),physcion(FP-2),eriosematin(FP-3),scoparone(FP-4),lupeol(FP-5),betulinic acid(FP-6),3\',4\'-Dihydroxy-trans-cinamic acid octacosyl ester(FP-7),β-sitosterol (FP-8),flemiphilippinone A(FP-9),monopalmitin(FP-10),emodin(FP-11),islandicin (FP-12),salicylic acid(FP-13),p-methoxyphenylpropionic acid(FP-14),trideca-1, 3-diene(FP-15),lupinifolin(FP-16),flemichin D(FP-17),flemiphilippinin A(FP-18), auriculasin(FP-19),erythrinin B(FP-20),6-C-prenylluteolin(FP-21), 8-(1,1-dimethylallyl) genistein(FP-22),flemiphilippinin E(FP-23),flemiphilippinin F (FP-24),5,7,3\',4\'-tetrahydroxy-6,8-diprenylisoflavone(FP-25),flemiphilippinin D (FP-26),dorsmaninsⅠ(FP-27),osajin(FP-28),6,8-diprenyleriodictyol(FP-29), lupinalbin A(FP-30),genistein(FP-31),3\'-O-methylorobol(FP-32),orobol(FP-33), 5,7,2\',3\',4\'-pentahrdroxyflavone(FP-34),the mixture of biochanin A and prunetin (FP-35 and 36),genistin(FP-37),sophororicoside(FP-38),3\'-O-methylorobol-7-glucoside(FP-39),the mixture of sissotrin and prunetin 4\'-O-β-D-glucoside(FP-40 and 41),adenosine(FP-42) and luteoloside(FP-43,mixture).

这些化合物分别为大黄酚(FP-1)、大黄素甲醚(FP-2)、eriosematin(FP-3)、滨蒿内酯(FP-4)、羽扇豆醇(FP-5)、白桦酸(FP-6)、咖啡酸二十八烷酯(FP-7)、β-谷甾醇(FP-8)、蔓性千斤拔酮A(FP-9)、单棕榈酸甘油酯(FP-10)、大黄素(FP-11)、islandicin(FP-12)、水杨酸(FP-13)、对甲氧基苯丙酸(FP-14)、十三烷-1,4-二烯烃(FP-15)、lupinifolin(FP-16)、千斤拔素D(FP-17)、蔓性千斤拔素A(FP-18)、auriculasin(FP-19)、erythrinin B(FP-20)、6-C-异戊烯基木犀草素(FP-21)、8-(1,1-二甲烯丙基)-染料木黄酮(FP-22)、蔓性千斤拔素E(FP-23)、蔓性千斤拔素F(FP-24)、5,7,3′,4′-四羟基-6,8-双异戊烯基异黄酮(FP-25)、蔓性千斤拔素D(FP-26)、dorsmaninsⅠ(FP-27)、osajin(FP-28)、6,8-双异戊烯基圣草素(FP-29)、lupinalbin A(FP-30)、染料木黄酮(FP-31)、3\'-O-甲基香豌豆苷元(FP-32)、奥洛醇(FP-33)、5,7,2′,3′,4′-五羟基黄酮(FP-34)、鹰嘴豆素甲和樱黄素的混合物(FP-35和FP-36)、染料木苷(FP-37)、槐属苷(FP-38)、7-葡萄糖基-3\'-O-甲基香豌豆苷(FP-39)、印度黄檀苷和樱黄素4′-O-β-D-葡萄糖苷的混合物(FP-40和FP-41)、腺嘌呤核苷(FP-42)和木犀草苷(FP-43,混合物)。

Green tea contains a number of flavonols with the basic structure Specific flavonols found in tea include myricetin (hydroxyls at carbon 3', 4', and 5'), quercetin (hydroxyls at positions 3' and 4'), and kaempferol (hydroxyl at position 4'), and their glycosides.

绿茶含有一些黄酮醇,其基本化学结构为:茶中特有的黄酮醇有杨梅黄酮(3'、4'、5'碳位上羟基化)、豕草花粉苷(3'和4'碳位上羟基化),莰非醇(4'碳位上羟基化),以及它们的糖苷物。

Twenty-seven compounds were isolated from the methanol extract of the stems of Pinus massoniana by means of chromatographic methods, and their structures were elucidated as 8(14),15-Pimaradien-19-oic acid (1), Pimaric (2), Podocarpic acid (3), 12-Hydroxydehydroabietic acid (4), Dehydroabietic acid (5), 15-Hydroxydehydroabietic (6), 3β-Methoxyserrat-14-en-21-one (7), 3β-Hydroxy- serrat- 14-en-21-one (8), 3β-Methoxyserrat-14-en-21-one-30-al (9),(24R)-Stigmst- 4-ene-3-one (10),β-sitosterol (11),-3-Hydroxy-5-methoxy-stilbene(12), 4-Hydroxy-3- methoxycinnamaldehyde (13),-Ferulic acidtetracosyl ester (14), Alkylferulates (15), Pinocembin (16), Coniferaldehyde (17), Matairesinol (18),-Nortrachelogenin (19), Balanophonin (20), Cedrusin (21),-Pinoresinol (22), Tanegoside (23), 1,2-Bis-(4-hydroxy-3- methoxyphenyl)-propane-1,3-diol (24),(1S*, 2S*)-1-(4- Hydroxyphenyl) glyceri...

同时对马尾松枝条的甲醇提取物利用各种色谱技术进行了分离纯化,并利用现波谱技术鉴定了27个化合物的结构,分别为:8(14),15-Pimaradien-19-oic acid (1)、海松酸(2)、罗汉松酸(3)、12-羟基脱氢松香酸(4)、脱氢松香酸(5)、15-羟基-脱氢松香酯(6)、3β-甲氧基-锯齿石松-14-烯-21-酮(7)、3β-Hydroxyserrat-14-en-21-one (8)、3β-Methoxyserrat-14-en-21– one-30-al (9)、(24R)-豆甾-4-烯-3-酮(10)、-3-羟基-5-甲氧基-二苯乙烯(12)、4-Hydroxy-3-methoxycinnamaldehyde (13)、-Ferulic acidtetracosyl ester (14)、Alkylferulates (15)、Pinocembin (16)、Coniferaldehyde (17)、罗汉松树脂酚(18)、 Balanophonin (20)、tanegoside (23)、1,2-Bis-(4-hydroxy- 3-methoxyphenyl)-propane- 1,3-diol (24)、(1S*,2S*)- 1-(4-hydroxyphenyl)glycerins (25)、(1R*,2R*)-1-(4-hydroxy- phenyl)gly-cerins (26)和赤松素(27)。

In leaf tissue of Arabidopsis, the most abundant hydroxycinnamic acidphenolics are sinapate esters, and the most abundant flavonoids are kaempferol derivatives.

拟南芥药用成分主要有酚类化合物,即羟基苯丙烯酸酚类化合物的芥子酸酯,黄酮类化合物的4,5,7-三羟基黄酮衍生物,芥子酸酯与这种黄酮类化合物具有优良的减少紫外线危害和抗氧化作用。

The activation energy of B ring elementary reaction is between 16~20kJ/mol.

从IRC结果以及对过渡态结构的电子密度拓扑学分析结果可以确定,羟基自由基在反应过程之中抽取了黄酮类化合物A环上未参与分子内氢键结构的酚羟基上的氢原子形成水分子及稳定性更高的半醌式大环自由基,在整个过程之中羟基自由基从反应物一侧进攻并逐渐发生扭转,直至形成一个进平面结构的过渡态结构,这与上一章关于黄酮类化合物B环的研究结果基本一致。

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