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为了研究自然杂化轨道计算结果与核自旋偶合常数的相关性,本文进行了从头算级别的自然杂化轨道计算。采用STO-3G基组,利用Lowdin正交化原子轨道基组下的密度矩阵,得到了分子中各原子的杂化轨道、净电荷与^13C-H、^13C-^13C键自旋偶合常数^1Jcn和^1Jcc之间关系式。利用这些式子计算得到的结果与实验数据非常一致。 相似文献
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从玉柏石松中分得三个新的△^1^4-serratene型的五环三萜酯(1-3), 根据其理化性质和波谱数据, 运用二维核磁共振新技术异核远程相关谱(HMBC), 证明1为16-oxo-lyclanitin-30-yl-p-coumarate, 2为16-oxo-diepilycocryptol-30-yl-p-coumarate, 3为diepilycocryptol-30-yl-p-coumarate, 并指定了1中所有碳和氢、2和3中所有碳和部分氢的NMR信号的归属。 相似文献
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本文报道了标题类化合物中十个化合物的^1H和^3^1PNMR的研究结果。其中分别运用了2DJ分解谱以及异核COSY谱等多种技术,解析了它们的^1H和^3^1P图谱,从而证实了合成反应的区域选择性和立体选择性。文章中,讨论了手性中心或其它因素而表现出的不等性;讨论了影响δ~P和J~p~H数值的各种因素:还报道了比较少见的^3^1P-^3^1P之间的远程偶合。其中,顺式产物的^4J~P~P数值(约9Hz)大于反式产物的^4J~P~P(约7Hz)。 相似文献
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用^1H,^13C NMR和多种二维磁共振谱表征了本系列化合物的结构,完成了^1H和^13C NMR谱带的归属,测定了氟原子对各质子和碳原子的偶合常数,探讨了影响偶合常数大小的因素。 相似文献
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Wetting of a sessile droplet on structured or patterned surface can be found in a broad range of applications. The researchers have been promoted to keep working on the topic. The review is on the basis of the recent experimental advances on the sessile droplet wetting on the hydrophobic, hydrophilic, or combined hydrophobic and hydrophilic surfaces under isothermal conditions, and on heating or cooling substrates having nonisothermal conditions. More attention has been paid on the wetting configuration between the sessile droplet and the structured substrate; the research gap has been discussed on identifying the three-phase line shape. Further, the three-dimensional measurement for the sessile droplets on the patterned surfaces with focusing more on the contact line of sessile droplets might reveal new physical insights. This review targets at building a holistic overview on the sessile droplet wetting behaviors on the structured substrate in the past 2 years. 相似文献
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环取代基对金属化聚苯胺衍生物膜修饰电极性能的影响 总被引:1,自引:0,他引:1
通过比较聚2,5-二甲氧基苯胺(PDMAn)、聚邻甲基苯胺(POT)和聚间氯苯胺(PmClAn)膜修饰电极的氧化还原电位、沉积在这3种聚合物上的铂微粒的表面形态与晶面取向以及异丙醇在分散Pt微粒的聚苯胺膜修饰电极上的氧化行为,从电子效应和立体效应探讨了聚合物电化学性质与环取代基的关系以及不同聚合基质对Pt沉积机理和有催化性能的影响,结果表明,在硫酸溶液中PDMAn膜修饰电极的氧化还原电位最负、POT次之、PmClAn最正,Pt在PDMAn和POT膜上的电沉积机理与在PmClAn膜上的不同,聚合物膜上沉积的Pt微粒呈现(200)晶面择优取向,其中POT膜上择优取向度最大,PDMAn次之,Pm-ClAn最小,异丙醇在金属化聚合物膜电极上的氧化电位取决于聚苯胺的本质,在POT膜修饰电极上异丙醇的电氧化主要发生在POT的活性电位区,而在PDMAn与PmClAn膜上的电氧化则主要发生在Pt上的氧化电位区,说明聚合物膜不仅作为Pt微粒的分散介质,而且本身有产生催化作用。 相似文献
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CHENTao AnneNeville YUANMing-dong 《高等学校化学研究》2004,20(4):381-385
Magnesium ions, which exist in formation water and injection water under downhole conditions in the oil and gas production industry, are a key determinant in the CaCO3 scale formation. Many studies have focused their attention on the effect of magnesium on the kinetics, the morphology and the content of Mg in the Ca-CO3 scale. Little attention has been paid to the effect of Mg^2 on the initial stages of CaCO3 formation on a metal surface. In this study, an electrochemical technique was used to study the influence of Mg^2 on the ini-tial stages of CaCO3 scale formed on a metal surface. With this electrochemical technique, the reduction of the dissolved oxygen in an analysis solution is considered on the surface of a rotating disk electrode (RDE) un-der potentiostatic control. The rate of oxygen reduction on the surface of the RDE enables the extent of sur-face coverage of scale to be assessed. With this electrochemical technique, a new insight into the effect of Mg^2 on CaCO3 scale formed on a metal surface is given. 相似文献
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Alicia L. Gui Guozhen Liu Muthukumar Chockalingam Guillaume Le Saux Erwann Luais Jason B. Harper J. Justin Gooding 《Electroanalysis》2010,22(16):1824-1830
4‐Nitrophenyl layers were grafted on gold and glassy carbon surfaces by electrochemical reductive adsorption of the corresponding diazonium salt. Electrochemical conversion efficiencies of 4‐nitrophenyl moieties to 4‐aminophenyl moieties on gold versus on glassy carbon in a protic medium were investigated using X‐ray photoelectron spectroscopy (XPS). In total contrast to all previous comparative studies showing greater electrochemical reactivity of aryl diazonium salt‐derived layers on gold than on glassy carbon, a much lower rate of conversion to 4‐aminophenyl was observed on gold than on glassy carbon by both cyclic voltammetry (CV) and chronoamperometry (CA) methods. The lower electron transfer rate during conversion observed on gold versus glassy carbon was proposed to be due to a mechanism related to the molecular structure rearrangement of 4‐nitrophenyl during the process on glassy carbon. However, whilst complete conversion of 4‐nitrophenyl to 4‐aminophenyl on gold by chronoamperometry was achieved, on glassy carbon complete reduction could not be achieved under the same conditions. 相似文献
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Yiu‐Ting R. Lau Lu‐Tao Weng Kai‐Mo Ng Chi‐Ming Chan 《Surface and interface analysis : SIA》2010,42(9):1469-1475
The effect of film thickness on the structural conformation of the surfaces of the amorphous state, edge‐on lamellae and flat‐on lamellae of a semiflexible polymer, poly(bisphenol‐A‐etheroctane), was investigated by time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) with the aid of principal component analysis (PCA). PCA results empirically indicate that a structurally regular polymer surface was obtained with the formation of the flat‐on lamellae from the amorphous state at a low degree of supercooling. A higher concentration of end group and cilium ion fragments, which are indicative of free chain ends, was observed on the edge‐on lamellar surfaces than on the amorphous and the flat‐on lamellar surfaces. This finding was attributed to the fact that the lateral surface of the edge‐on lamellae contains many growth fronts, leaving behind a large number of uncrystallized chain remnants on the surfaces. Structural disorder was facilitated on both edge‐on and flat‐on lamellar surfaces as the film thickness decreased. Hence, this PCA study offers new insights into the nonequilibrium nature of polymer crystals and the mechanism of polymer crystallization in thin and ultrathin films. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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含铈Cu-Fe-O催化剂的氧化还原性研究 总被引:5,自引:1,他引:4
用TPR等方法研究了Cu-Fe-Ce-O/γ-Al2O3(Ⅰ)催化剂的氧化还原性能。结果表明,在(Ⅰ)中铜的存在有利于Fe2O3的还原,铈作为助催化剂能增强Cu-Fe-O/γ-Al2O3(Ⅱ)的氧化还原性能,配合CO、NO和CO+NO气对试样进行预处理后发现,铜吸附CO的能力比铁强,铁吸附NO的能力比铜强,铈的存在可增强(Ⅱ)在NO+CO反应气氛中对CO的吸附能力,并对NO在催化剂表面吸附形成硝酸盐物种产生影响。 相似文献
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Satoshi Kubota Hiromasa Nishikiori Nobuaki Tanaka Morinobu Endo Tsuneo Fujii 《Journal of photochemistry and photobiology. A, Chemistry》2009,206(2-3):148-154
Pyrene crystals were grown on carbon nanofibers (CNFs) by dispersing pyrene polycrystals and CNFs in water during ultrasonic irradiation, and they were characterized by scanning electron microscopy, X-ray diffractometry (XRD) and spectroscopy. The XRD measurements indicated that the orientation and size of the pyrene crystals on the CNF aggregates were different from that of the added pyrene polycrystals. Based on the spectroscopic properties of the pyrene crystals on the CNFs, the pyrene crystals on the CNF aggregates and on the individual CNFs were determined to be polycrystals and single crystals, respectively. These results indicate that pyrene crystals are produced on the CNFs by recrystallization of the added pyrene polycrystals and their crystal states depend on the aggregation state of the CNFs. 相似文献
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本文主要综述有机化学在建立核酸的顺序测定法和自动顺序仪,在破译遗传密码,在建立核酸片段的化学合成方法,固相合成法及DNA合成仪的设计,在合成许多有生物活力的核酸分子,在发展并完善遗传工程以及新近发现酶RNA(Ribozyme)等方面的卓越贡献。最后简要地展望有机化学将对生物学发展作出进一步贡献的几个方面。 相似文献
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本文研究了5-位不同取代基的噻碳菁和吲哚碳菁染料对其在立方型颗粒和T-颗粒溴化银微晶上吸附能力的影响,并采用ACFEM(Analytical Color Fluore scence Electron Microscopy)研究了上述结构染料对其吸附在溴化银微晶所形成的J-聚集体尺寸分布的影响。实验结果表明,对吲哚碳菁染料来说,立方体溴化银微晶表面的吸附能力较T-颗粒溴化银微晶表面的吸附能力强;但对噻碳菁染料来说则相反,它们在T-颗粒溴化银微晶表面的吸附能力较立方体溴化银微晶表面的吸附能力强。另外,对5-位不同取代基的噻碳菁染料而言,无论是在立方型颗粒或T-颗粒溴化银微晶上的吸附能力来说,含取代基(无论4-取代基是吸电子型还是推电子型)的噻碳菁染料较未取代的噻碳菁染料强;而5-位取代基是吸电子型的噻碳菁染料更有利于其吸附在T-颗粒溴化银微晶表面。此外,本文还进一步证明了溴化银微晶表面上染料J-聚集体的生长过程是符合奥斯瓦尔特成熟过程的。吲哚碳菁染料在T-颗粒溴化银微晶上形成的J-聚集体的平均尺寸明显大于在立方体溴化银微晶上形成的J-聚集体的平均尺寸。吸附在立方体溴化银微晶上的5-不同取代基的噻碳菁染料对其形成J-聚集体尺寸分布的影响的研究结果表明,含取代基(-CH3,-Ph,-Cl)的噻碳菁染料形成的J-聚集体的尺寸分布几乎相同,但与未取代的噻碳菁染料形成的J-聚集体的尺寸分布明显不同;5-位含取代基的噻碳菁染料形成的J-聚集体平均尺寸大于未取代的噻碳菁染料的。 相似文献