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We have studied the transition metal complexes catalyzed sequential cross coupling reactions of these new difunctional group reagents with electrophiles and nucleophiles, respectively; developed some convenient and practical new methods for the stereoselective synthesis of disubstituted alkenes, trisubstituted alkenes, conjugated dienes containing heteroatom, conjugated enyne containing heteroatom etc., enriching methodologies for organic synthesis.

继而研究了这些新型双官能试剂在过渡金属配合物催化下分别与亲电试剂、亲核试剂的顺序交叉偶联反应,为双取代烯烃、三取代烯烃、杂原子取代的共轭二烯烃、杂原子取代的共轭烯炔烃等的立体选择合成提供了方便实用的新方法,丰富了烯烃立体选择合成的方法学。

Chromatography peaks were obtained by GC-MS and 56 compounds were identified. The main components were linalyl butyrate (30.212%),(1α, 3α, 4β, 6α)-4,7,7-trimethyl-bicycloheptan-3-ol (10.940%),-4-carene (1.826%), 4-methylene-1-(1-methylethyl)-bicyclo [3.1.0] hexane (1.109%),β-myrcene (1.170%), limonene (5.784%), 3, 7-dimethyl-1, 6-octadien-3-ol (5.742%), n-hexadecanoic acid (0.914%) and-9, 12-octadecadienoic acid (2.952%), etc.

用GC-MS分离出69个峰,鉴定出56种物质,主要成分为:芳樟丁酸酯(30.212%)、(1α, 3α, 4β, 6α)-4,7,7-三甲基-双环[4.1.0]庚烷-3-醇(10.940%)、-4-蒈烯(1.826%)、4-亚甲基-1-(1-甲基乙基)-双环[3.1.0]环己烷(1.109%)、β-月桂烯(1.170%)、柠檬烯(5.784%)、3,7-二甲基-1,6-辛二烯-3-醇(5.742%)、n-棕榈酸(0.914%)、-9,12-十八碳烯酸(2.952%)等。

The double bond in norbornene ring of TCPD was easily saturated at a low temperature, and an intermediate 12,13-dihydrotricyclopentadiene (12,13-DHTCPD) was formed. Higher temperature and hydrogen pressure were required for the saturation of remaining double bond in cyclopentene ring to generate a completely hydrogenated compound tetrahydrotricyclopentadiene.That is to say, the reaction occurred via the TCPD→12,13-DHTCPD→THTCPD route.

采用气质联用、红外光谱和核磁共振对加氢产物进行表征,发现在加氢反应中TCPD的降冰片烯双键首先被饱和,生成中间产物12,13-二氢三环戊二烯(12,13-DHTCPD),残留的环戊烯双键需要在更高的温度和氢压下反应生成四氢三环戊二烯,即反应按照TCPD→12,13-DHTCPD→THTCPD的途径进行。

From comparative research of synchronous and asynchronous reaction of dehydrogenation and cracking of dipentene,it is shown that farraginous extent of by-products from synchronous reaction is relatively high.

双戊烯脱氢裂解的同步反应和异步反应对比研究显示,双戊烯脱氢裂解的同步反应产物比较混杂,反应产物中甲苯的相对含量仅为24.03%,双戊烯相对于甲苯的料耗比为5.34,甲苯的得率为30.79%,中间产物对伞花烃的得率为2.49%;双戊烯脱氢裂解的异步反应产物混杂程度相对较低,反应产物中甲苯的相对含量为40.74%,对伞花烃的相对含量为18.31%,双戊烯相对于甲苯的料耗比为3.33,甲苯的得率为49.26%,中间产物对伞花烃的得率为16.92%。

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)。

Synthesis of organic sulfuric compounds in aqueous media is carried out by: using thio-olefin compounds with carbonyl compounds, acetal/keltone, hydrazone, oxime, osazone and enamine to synthesize mercaptal/keltone compounds in aqueous media; using thio-olefin compounds with alpha-hydroxyaldehyde/keltone or alpha-halogenated aldehyde/keltone to synthesize thia-olefin derivatives in a queous media; using thio-olefin compounds with alpha, beta-unsaturated hydroxy compounds, C-C treble bond, C-N treble bond, C-C double bond, N-N double bond, C-N double bond, C-S double bond, epoxy and its derivatives, aziridine and its derivatives, cyclopropane and its derivatives and halogenated carboxy to synthesize sulfoether compounds in a queous media.

含水介质中有机硫化合物的合成方法,本发明属于有机合成方法,用硫缩烯酮类化合物与羰基化合物、缩醛/酮、腙、肟、脎、烯胺在含水介质中合成缩硫醛/酮化合物,与α-羟基醛/酮或α-卤代醛/酮在含水介质中合成噻烯类衍生物,与α,β-不饱和羰基化合物、碳碳叁键、碳氮叁键、碳碳双键、氮氮双键、碳氮双键、碳硫双键、环氧乙烷及其衍生物、氮杂环丙烷及其衍生物、环丙烷及其衍生物、卤代烃等在含水介质,中合成硫醚化合物。

The EAG results showed that no significant difference between female and male S.bifasciatus.The EAG responses of S.bifasciatus to 3-Carene,Limonene,Terpinene and Thujopsene were increased with the concentration respecitively within the range of 1/1000-1/10.The results of "Y" tube olfactory bioassay showed the pests can be attracted by 1/100 Limonene,3-Carene and Thujopsene.Original and 1/10 Terpinene was the best. In addition,the extracts of A2 and D1 also caused positive attraction to S.bifasciatus,while the extracts by SE and SDE were non-attractive.

触角电位测定结果表明,双条杉天牛雌雄成虫对样品的EAG反应无显著差异。1/10浓度的3-蒈烯、柠檬烯、萜品烯和罗汉柏烯的EAG值最大。Y型嗅觉行为生测结果表明,1/100浓度的柠檬烯、3-蒈烯和罗汉柏烯对天牛有明显引诱效果,萜品烯则是原液和1/10浓度的引诱效果最好;α-蒎烯和β-蒎烯无明显引诱效果。4种提取方法中,改装简易蒸馏法样品(A2)和超临界CO_2萃取样品(D1)对天牛具有明显引诱作用;索氏提取物和并时蒸馏萃取物无引诱效果。

In this study, LDL was oxidized by copper ion, 2, 2'-azobis(2-amidio-propane)dihydrochloride or macrophages in the absence or presence of apoH to delineate the correlation between apoH and LDL peroxidation,. It was shown that the formation of thiobarbituric acid reactive substances and conjugated dienes was decreased and the electrophoretic mobility of LDL was reduced in the presence of apoH. It suggests that apoH exerts an antioxidative effect.

为了进一步了解脂蛋白元 H 的表现与低密度脂蛋白氧化之间的关连性,分别以铜离子、 2, 2'-azobis(2-amidio-propane)dihydrochloride (一种可生成自由基的化合物)或巨噬细胞等来氧化低密度脂蛋白,发现在有脂蛋白元 H 的存在下,不论是 thiobarbituric acid reactive substances、共轭双烯的生成以及低密度脂蛋白电泳移动速率,都受到明显抑制。

Tocopherol, at the same working concentration, Copper-induced LDL oxidation was suppressed by the tamarillo phenolics in EA layer more effectively or compatible to DL--tocopherol, as measured by decreased formation of thiobarbituric acid-reactive substances assay, conjugated diene and electrophoretic mobility.

tocopherol 相类似的活性及氧化抑制效果,其相关的实验有:利用Cu2+离子诱导低密度脂蛋白氧化,并以硫代巴比妥酸反应物质(Thiobarbituric acid reactive substances , TBARS)分析、延缓共轭双烯形成能力及电泳位移分析等试验进行评估。

Series of crosslinked polymers containing POSS were synthesized in this thesis. The main contents include three parts as follows:(1) The preparation of different POSS molecules containing multiple functionalgroups and the development of crosslinked polymers containing POSS were reviewed in detail.

2合成了一种多功能团的POSS分子(T_8H_8)及四种不同长度的双烯功能团有机小分子,这些有机小分子可以通过硅氢化反应与POSS形成交联聚合物,在聚合物中作为连接链将POSS分子连接起来。

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