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排序方式: 共有2945条查询结果,搜索用时 15 毫秒
1.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
2.
该文对Cd-HEDTA(N-(2-羟基乙基)乙二胺-N',N',N'-三乙酸),Cd-PDTA(1,2丙二胺四乙酸)和Cd-DTPA(二乙三胺五乙酸)的113Cd NMR谱和自旋晶格弛豫时间T1,及NOE因子进行了研究.结果表明,Cd-HEDTA和Cd-PDTA结构与Cd-EDTA类似,Cd-PDTA双线归因于其可能的两种异构体.Cd-DTPA大的化学位移表明其具有七配位的五角双锥结构.在这种结构中DTPA可用三个氮原子参加配位.对113Cd自旋晶格弛豫时间分析表明,Cd-DTPA配合物中质子偶极作用机理的贡献较大,这归因于Cd DTPA有更多的乙酸根亚甲基质子参与偶极作用. 相似文献
3.
微波消解ICP-AES法同时测定花岗石中铜、镉、铬和砷 总被引:9,自引:3,他引:6
本文采用微波消解和ICP-AES法,同时测定花岗石样品的铅、镉、铬、砷4有害元素,检出限分别为0.0008、0.0007、0.0018、0.0012μg.mL^-1,回收率为93.4%-102.5%,RSD为1.3%-3.6%,该法准确、快速、简便,结果令人满意。 相似文献
4.
Effects of Substrate Temperature on Helium Content and Microstructure of Nanocrystalline Titanium Films 下载免费PDF全文
Helium-charged nanocrystalline titanium films have been deposited by HeAr magnetron co-sputtering. The effects of substrate temperature on the helium content and microstructure of the nanocrystalline titanium films have been studied. The results indicate that helium atoms with a high concentration are evenly incorporated in the deposited titanium films. When the substrate temperature increases from 60℃ to 350℃ while the other deposition'parameters are fixed, the helium content decreases gradually from 38.6 at.% to 9.2at.%, which proves that nanocrystalline Ti films have a great helium storage capacity. The 20 angle of the Bragg peak of (002) crystal planes of the He-charged Ti film shifts to a lower angle and that of (100) crystal plane is unchanged as compared with that of the pure Ti film, which indicates that the lattice parameter c increases and a keeps at the primitive value. The grain refining and helium damage result in the diffraction peak broadening. 相似文献
5.
6.
The magnetic properties of annealed Fe-Pt multilayer thin films with a broad composition range were investigated in order to identify the effects of composition and annealing temperature on the achievable coercive field, and to identify its maximum at low processing temperatures. Two types of multilayer systems were deposited as materials libraries to vary the composition from Fe20Pt80 to Fe75Pt25. The first type of multilayer was comprised of alternating opposing wedges, whereas the second type consisted of repeated uniform Fe and Pt layers interspersed periodically with Fe wedge layers. It was found that coercive fields μ0HC > 0.7 T can be achieved at an annealing temperature of about 300 °C (60 min) for both types of multilayers as long as the composition is close to 50:50. Higher annealing temperatures are needed for films, which deviate from this composition. Increasing the annealing temperature up to 700 °C leads to increased coercivity values. Multilayers with additional Fe layers showed increased remanence but reduced coercive fields. 相似文献
7.
C.H Chung S.D KimH.J Kim F.O AdurodijaK.H Yoon J Song 《Solid State Communications》2003,126(4):185-190
The dependence of structural properties and surface morphology of Cu-In alloy layers on the composition and sputtering deposition sequence were investigated by X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. The properties of the co-sputtered alloy layers changed abruptly around the composition boundary when the Cu/In ratio reached 1/2. This can be explained by the effective heat of formation (EHF) model, which has been used to predict the sequence of phase formation for metal diffusion couples. The use of a co-sputtered alloy layer with a high In concentration was not suitable for fabricating solar cells, because the film had a very rough morphology due to large In islands formed on the CuIn2 phase. However, it was possible to minimize this phase by In sputtering followed by co-sputtering with a Cu/In ratio of 1 (Cu-In/In/Glass). This permitted the fabrication of a homogeneous Cu-In alloy layer, which was not possible through the simple co-sputtering. 相似文献
8.
A simple procedure for the synthesis of an important standard, isotopically enriched methylmercury, which is not commercially available, has been established successfully. The isotopically enriched standard synthesized is utilized in conventional isotope dilution mass spectrometry (IDMS), as well as in speciated IDMS (SIDMS), for determination of the true concentration of methylmercury in environmental samples. The CH3201Hg+ standard has been synthesized from commercially available 201HgO and tetramethyltin. The synthesis time required is 1 h at 60°C. The product is highly pure, yielding more than 90% as 201Hg in CH3201Hg+. Hazardous dimethylmercury does not occur during this synthesis procedure. The product synthesized was analyzed using high‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP‐MS) and ICP‐MS alone in order to determine its concentration, isotopic composition and purity. The stability of the product was also evaluated for over 6 months and found to be stable at 4°C in the dark. The isotopically enriched methylmercury synthesized can be used in SIDMS and IDMS analyses as a standard. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
9.
火焰原子吸收光谱法测定磁化杯中铅、镉和铁 总被引:1,自引:0,他引:1
本文研究了火焰原子吸收光谱法测定磁化杯陶瓷内胆中Ph、Cd和Fe含量的方法。样品经粉碎,用硝酸-高氯酸混合液进行消解后测定。本法灵敏度高,干扰少,简单,快速,具有良好的精密度和准确度,其相对标准偏差分别为Pb3.99%,Cd10.7%,Fe0.9%。回收率Pb100.61%,Cd101.18%,Fe102.4%。 相似文献
10.
Noora Virtanen Ville Nevalainen Taru Lehtinen Satu Mikkola 《Journal of Physical Organic Chemistry》2007,20(1):72-82
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献