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CA-CTSs including N,O-carboxymethyl chitosan,N,O-1-carboxyethyl chitosan (N,O-1-CEC),N,O-2-carboxyethyl chltosan(N,O-2-CEC),N-carboxymethyl chitosan and N-1-carboxyethyl chitosan(N-1-CEC) are quaternized using active quaternary salts prepared in laboratory.5 series including 25 kinds amphoteric chitosans characterized with polymeric ampholyte,in which 24 kinds are synthesized firstly,are obtained, 2-Hydroxypropyl dimethylbenzyl ammonium N,O-(1-carboxyethyl) chitosan chloride (GDMBA-N,O-1-CEC) is hydrolyzed into serial low molecular weight GDMBA-N, O-1-CEC with acid as catalyst and microwave as assistant instrumentality innovately.

以合成的活性季铵盐改性了N,O-羧甲基壳聚糖、N,O-1-羧乙基壳聚糖(N,O-1-CEC)、N,O-2-羧乙基壳聚糖(N,O-2-CEC)、N-羧甲基壳聚糖和N-1-羧乙基壳聚糖(N-1-CEC)等羧烷基壳聚糖,得到5个系列25种具有两性高分子电解质特征的新季铵化羧烷基壳聚糖,其中24种为首次合成;创新提出以微波辅助酸催化的方法催化2-羟丙基二甲基苄基-N,O-(1-羧乙基)壳聚糖氯化铵(GDMBA-N,O-1-CEC)水解,得到了低分子量的GDMBA-N,O-1-CEC。

When n/n=0, the product is the mixture of h-WO3 (hexagonal system WO3) and WO3.1/3H2O, and have a morphology of nanorods; when n/n=0.5 or n/n=l, the product is γ-WO3, and have a morphology of rectangular flakes; when n/n=2, the product is β-WO3, with the same morphology of rectangular flakes.

当n/n=0时,产物为h-WO3和WO31/3H2O组成的混合物,形貌为纳米棒;当飞n/n=0.5和n/n=1时,产物为γ-WO3形貌为矩形片;当n/n=2时,产物为β-WO3,形貌同样为矩形片。

This work, concentrated on the asymmetric allylation of aldehydes controlled by different chiral auxiliaries prepared from rotational pure tartaric acid, can be divided into three parts.The first part aims to review the developments of chiral drugs and asymmetric synthesis, from which derived the present research topic backgrounds and works.Synthesis and applications of allylation from aldehydes are the second part of the thesis. By optimizing the reaction conditions, such as solvents, temperature, time and chiral auxiliaries like N,N\'-dibenzyl tartamide, N,N\'-p-dimethylphenyl tartamide, N,N\'-o-dimethylphenyl tartamide, N,N\'-o-dichlorophenyl tartamide, N,N\'-a-dinaphyl tartamide, N,N\'-dicyclohexyl tartamide and N,N\'-diphenyl tartamide, ideal experimenttal conditions are obtained according to HPLC monitoring, as well as the auxiliaries\' recoveries experiments. Starting from benzaldehyde and 3-bromopropaldehyde, N,N\'-dibenzyl tartamide is considered the best auxiliary in this reaction.

本文介绍了醛的不对称烯丙基化反应,以光学纯酒石酸为原料,研究了不同构型手性配体在醛的烯丙基化反应中的立体选择性,全文共分三部分十个章节:第一部分对当前手性药物和手性技术进行了概述,并由此展开了本文的研究背景和任务;第二部分为有机合成部分,对醛的不对称烯丙基化反应进行了深入探讨,以苯甲醛为原料对反应条件进行优化,在优化的反应条件下对制备的七种可回收手性酰胺配体(N-苄基酒石酸二酰胺、N-对甲苯基酒石酸二酰胺、N-邻甲苯基酒石酸二酰胺、N-邻氯苯基酒石酸二酰胺、N-a-萘基酒石酸二酰胺、N-环己基酒石酸二酰胺和N-苯基酒石酸二酰胺)进行筛选,优化配体回收实验条件,最终确定出N-苄基酒石酸二酰胺在苯甲醛的不对称烯丙基化反应中具有较大优越性,结晶回收的手性配体光学纯度保持不变。

And to make the product be easy of purification, the excess of amine was reduced to 50% from 150%. Then the diiodoalkane reacted with dialkylmethylamine into diquaternary ammonium iodide, and obtained three diquaternary compounds whose spacer groups were -(CH2)6-, N,N"-dimethyl- N,N,N",N"-tetraoctyl-1,6-hexane diammonium diiodide, N,N"-dimethyl-N,N,N",N"-tetradecyl-1,6-hexane diammonium diiodide, N,N"-dimethyl-N,N,N",N-tetradodecyl -1,6-hexane diammonium diiodide.

对于更长间隔链的双子型季铵盐,一方面为了加快亲核取代反应速率,先将1,6-二氯己烷、3-氧杂-1,5-二氯戊烷转化成1,6-二碘己烷、3-氧杂-1,5-二碘戊烷,另一方面为了降低产物提纯的难度,将叔胺的过量由150%降到50%,使二碘代烷与双长烷基甲基叔胺在相同的温度下、反应相同的时间,经过相同的后处理,得到3个间隔链为-(CH2)6-的双子型季铵碘化物,(C8H17)2N+(CH3)(CH2)6 (CH3)N+(C8H17)2·2I-、(C10H21)2N+(CH3)(CH2)6(CH3)N+(C10H21)2·2I-和(C12H25)2N+(CH3)(CH2)6(CH3)N+(C12H25)2·2I-。

Dibutyltin maleate,dioctyltin maleate,N-phenyl maleimide, N-(p-chlorophenyl) maleimide,N-(p-nitrophenyl) maleimide with unsaturated groups were synthesized using dibutyltin oxide,dioctyltin oxide,maleic anhydride, aniline,p-chloroaniline,p-nitroaniline as raw materials,respectively.Then dibutyltin male,ate/styrene bipolymer,dibutyltin maleate/styrene/methyl acrylate terpolymer,dibutyltin maleate/styrene/N-phenyl maleimide terpolymer ,dibutyltin maleate/styrene/N-(p-chlorophenyl) maleimide terpolymer ,dibutyltin maleate/styrene/N-(p-nitrophenyl) maleimide terpolymer ,dioctyltin maleate/styrene biopolymer,dioctyltin maleate/styrene/methyl acrylate terpolymer,dioctyltin maleate/styrene/ N-phenyl maleimide terpolymer,dioctyltin maleate/styrene/ N-(p-ehlorophenyl) maleimide terpolymer[P(DOTM/St/NC1PMI)],dioctyltin maleate/styrene/N-(p-nitrophenyl) maleimide terpolymerwere synthesized using DBTO,DOTO,PMI,N-p-ClPMI,N-p-NOPMI,styrene and methyl acrylate as monomers,respectively.

再以DBTO,DOTO,PMI,N-p-ClPMI,N-p-NOPMI,苯乙烯,丙烯酸甲酯等为单体,合成了马来酸二丁基锡/苯乙烯二元共聚物{P},马来酸二丁基锡/苯乙烯/丙烯酸甲酯三元共聚物{P},马来酸二丁基锡/苯乙烯/N-苯基马来酰亚胺三元共聚物{P(DBTM/St/NPMI)},马来酸二丁基锡/苯乙烯/N-对氯苯基马来酰亚胺三元共聚物{P(DBTM/St/NClPMI)},马来酸二丁基锡/苯乙烯/N-对硝基苯基马来酰亚胺三元共聚物{P(DBTM/St/NNOPMI)},马来酸二辛基锡/苯乙烯二元共聚物{P},马来酸二辛基锡/苯乙烯/丙烯酸甲酯三元共聚物{P},马来酸二辛基锡/苯乙烯/N-苯基马来酰亚胺三元共聚物{P(DOTM/St/NPMI)},马来酸二辛基锡/苯乙烯/N-对氯苯基马来酰亚胺三元共聚物{P(DOTM/St/NClPMI)},马来酸二辛基锡/苯乙烯/N-对硝基苯基马来酰亚胺三元共聚物{P(DOTM/St/NNOPMI)}。

Three novel hemicyanine derivatives,-N-(4-sulfopropyl)-4-[2-(4- N, N-diethylaminophenyl)-ethenyl]pyridinium,-N-(4-suMbbutyl)- 4-[2-(4-N, N-diethylaminophenyl)ethenyl]pyridinium (EPS4), and-N-(4- su)fobutyl-4-[2-(4-N, N-diethylaminophenyl)ethenyl]quinolinium (EQS4) with different length of alkyl chains between the adsorbing group (RSO3-) and the chromophore group, were synthesized and their photophysical and photoelectrochemical properties were studied.

设计合成了具有不同空间位阻的吡啶盐类和喹啉盐类半菁染料-N-(4—磺酸根丙基)-4-[2-4(4-N,N-二乙基氨基苯基)乙烯基]吡啶鎓盐,-N-4-磺酸根丁基)-4-[2-(4-N,N-二乙氨基苯基)乙烯基]吡啶鎓盐(EPS4)和-N-(4-磺酸根丁基)-4-2-(4-N,N-二乙基氨基苯基)喹啉鎓盐(EQS4),研究了它们的光物理性质,并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池中。

The increased amount of non--exchangeable NH4^+-N during the incubation indicated as the following tendency, namely, Eum-Orthic Anthrosols 〉 Los - Orthic Entisols 〉 Hap-Ustic Isohumisols 〉 Ust-Sandiic Entisols. Organic material influenced significantly the increased amount of non-exchangeable NH4^+-N (P was 0.0002, 0.0004 and 0.0003 when incubated at 20 d, 50 d and 60 d, respectively). NH4^+-N increased remarkably when Stlpa bungeana and Medicago sativa were added compared with no addition. The contents of non-exchangeable NH4^+-N increased significantly when added (NH4)2SO4 compared without addition at 20 d, 40 d and 60d of incubation and P was 0.0037, 0.0033 and 0.0027, respectively. It was the result that the NH4^+-N from (NH4)2 SO4 was fixed within the soil. The increased amount of non-exchangeable NH4^+-N increased significantly for different soils, on which different vegetation types grew before the collection of soil samples, when incubated at 20 d (P=0.0434), but not significantly at 40 d and 60d (P=0.7378 and 0.5375). The increased amount of non-exchangeable NH4^+-N in the soil, on which crop straw and nitrogen fertilizer had been incorporated for a long-term period, was larger than that of no addition, but it was not significantly different among these two fertilization models. Soil clay, total N and organic matter were positively correlated remarkably with the contents of non-exchangeable NH4^+-N, the increased amount of non-exchangeable NH4^+-N had no correlation with soil clay, whereas it had significantly positive correlation with total N and organic matter.

培养期间非交换性NH4^+-N的增加量均表现为以土垫旱耕人为土最大,其次是黄土正常新成土,简育干润均腐土和干湿砂质新成土较小;添加有机物料极显著影响培养期间的非交换性NH4^+-N增加量(培养20d、40d和60d时P分别为0.0002,0.004和0.0003),表现为紫花苜蓿和长芒草土壤非交换性NH4^+-N的增加量均极显著高于不添加有机物料的对照土壤;在培养20d、40d和60d时,加(NH4)2SO4土样非交换性NH4^+-N的增加量显著大于不加(NH4)2SO4土样(户分别为0.0037,0.0033和0.0027),这是土壤对(NH4)2SO4中NH4^+-N固定的必然结果;不同植被类型土壤培养20d时的非交换性NH4^+-N增加量差异显著(P=0.0434),培养40d和60d时差异不显著(p分别为0.7378和0.5375);长期秸秆和氮肥配施土壤非交换性NH4^+-N增加量大于不施肥对照土壤,但差异不显著土壤黏粒、全氮和有机质与培养0d、20d、40d和60d时土壤的非交换性NH4^+-N含量均呈极显著正相关;而非交换性NH4^+-N的增加量与粘粒无相关性,但与全氛和有机质呈显著正相关。

Four hemicyanine derivatives,-N-(4-sulfobutyl)-4-[2-(4-N,N-dimethylamino-phenyl) etheny1] pyridinium (P1),-N-(4-sulfobutyl)-4-[2-(4-N,N-dimethylaminophenyl)-1,3-buteny1] pyridinium (P2),-N-(4-sulfobutyl)-4-2-(4-N,N-dimethylaminophenyl) ethenyll quinolinium (Q1) and-N-(4-sulfobutyl)-4-

合成了具有不同共轭链长度的吡啶盐类及喹啉盐类半菁染料-N-(4-磺酸丁基)-4-[2-4-N,N-二甲基氨基苯基)乙烯基]吡啶鎓盐(P1、-N-(4-磺酸丁基)-4-[2-4-N,N-二甲基氨基苯基)丁二烯基]吡啶鎓盐(P2、-N-(4-磺酸丁基)-4-[2-(4-N,N-二甲基氨基苯基)乙烯基]哇琳鎓盐(Q1)以及-N-(4-磺酸丁基)-4-[2-4-N,N-二甲基氨基苯基丁二烯基]喹啉鎓盐(Q2)。研究了它们的光物理性质,并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池。

Three cationic surfactants, N -dodecyl- N -(2-hydroxyethyl)- N , N -dimethylammonium bromide, N -tetradecyl- N -(2-hydroxyethyl)- N , N -dimethylammonium bromide and N -cetyl- N -(2-hydroxyethyl)- N , N - dimethylammonium bromide have been synthesized.

合成了 N -十二烷基- N -(2-羟乙基)- N , N -二甲基溴化铵、 N -十四烷基- N -(2-羟乙基)- N , N -二甲基溴化铵和 N -十六烷基- N -(2-羟乙基)- N , N -二甲基溴化铵等3个季铵盐阳离子表面活性剂。

The calculated results show that azido in azides has linear structure , the most optimized CaN6 has linear structure , and the most optimized (CaN6)n (n=2~5) clusters have chain structure of perpendicularity of approximate diamond composed by two azido with two Ca atoms . The middle N atoms of azido show positive, the N atoms at both ends of azido show negative, and the N atoms effected with Ca atoms directly show more negative . There is strong ionic bond between the Ca and N atoms. The IR spectra of the most optimized (CaN6)n (n=1~5) clusters have four vibrational sections , the whole strongest vibrational peak lies in 2195~2280cm-1,and the vibrational mode is anti-symmetric stretching vibration of N-N bonds in azido . Stability analysis show that (CaN6)3 and (CaN6)5 clusters are more stable than other clusters .

结果表明,叠氮化合物中叠氮基以直线型存在,CaN6团簇的最稳定结构为线型结构,(CaN6)n(n=2~5)团簇首先由两个叠氮基与两个Ca原子构成一个近似菱形,再由菱形相互垂直形成链状最稳定结构;叠氮基中间的N原子显示正电性,两端的N原子显示负电性,且与Ca直接作用的N原子负电性更强,金属Ca原子和N原子之间形成很强的离子键;(CaN6)n(n=1~5)团簇最稳定结构的IR光谱分为4个部分,其最强振动峰均位于2195~2280cm-1,振动模式为叠氮基中N-N键的反对称伸缩振动;稳定性分析显示,(CaN6)3和(CaN6)5团簇相对于其他团簇较为稳定。

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Breath, muscle contraction of the buttocks; arch body, as far as possible to hold his head, right leg straight towards the ceiling (peg-leg knee in order to avoid muscle tension).

呼气,收缩臀部肌肉;拱起身体,尽量抬起头来,右腿伸直朝向天花板(膝微屈,以避免肌肉紧张)。

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