全文获取类型
收费全文 | 119篇 |
免费 | 8篇 |
国内免费 | 31篇 |
专业分类
化学 | 146篇 |
综合类 | 1篇 |
物理学 | 11篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 2篇 |
2019年 | 2篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 5篇 |
2015年 | 4篇 |
2014年 | 2篇 |
2013年 | 18篇 |
2012年 | 5篇 |
2011年 | 2篇 |
2010年 | 4篇 |
2009年 | 2篇 |
2008年 | 6篇 |
2007年 | 6篇 |
2006年 | 10篇 |
2005年 | 6篇 |
2004年 | 12篇 |
2003年 | 8篇 |
2002年 | 5篇 |
2001年 | 7篇 |
2000年 | 16篇 |
1999年 | 10篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1984年 | 1篇 |
排序方式: 共有158条查询结果,搜索用时 234 毫秒
1.
Tertiary N-ethylamines were converted into amide derivatives by reactions with sulfur monochloride and DABCO at 0 °C. Depending on the
nature of the substituents in the amine, the reaction can be accompanied by unexpected transformations.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1135–1140, June, 2007. 相似文献
2.
Hoang The Ban Kei Nishii Yasuo Tsunogae Takeshi Shiono 《Journal of polymer science. Part A, Polymer chemistry》2007,45(13):2765-2773
This article reports a synthetic method for a norbornene–ethylene–styrene (N‐E‐S) terpolymer, which has not been well investigated so far, via incorporation of styrene (S) into vinyl‐type norbornene–ethylene (N‐E) copolymers catalyzed by a substituted ansa‐fluorenylamidodimethyltitanium [Me2Si(3,6‐tBu2Flu)(tBuN)]TiMe2 catalyst ( I ) activated with a [Ph3C][B(C6F5)4]/Al(iBu)3 cocatalyst at room temperature in toluene. The resulting terpolymerization product contained the targeted N‐E‐S terpolymer and the contaminated homopolymers, which were then able to be completely removed by solvent fractionation techniques. While homopolystyrene was easily extracted by fractionation with methylethylketone as a soluble part, homopolyethylene and a trace amount of homopolynorbornene could be perfectly separated by fractionation with chloroform as insoluble parts. The detail characterizations of a chloroform‐soluble polymer with gel permeation chromatography, nuclear magnetic resonance, and differential scanning calorimetry analyses proved that it contained a true N‐E‐S terpolymer with long N‐E sequences incorporated with isolated or short styrene sequences. The homogeneity of the morphology together with a single glass transition temperature that proportionally decreased with the increase of the styrene contents indicated that the N‐E‐S terpolymer obtained in this work is a random polymer with an amorphous structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2765–2773, 2007 相似文献
3.
4.
Magdalena?SkompskaEmail author Mikhail?A.?Vorotyntsev 《Journal of Solid State Electrochemistry》2004,8(6):360-368
We report electrochemical studies on the influence of a small concentration of chloride ions on the electroactivity of the polymer matrix of polypyrrole (PPy), poly(N-methylpyrrole) [p(N-MePy)] and a poly(titanocene-propyl-pyrrole) derivative, p(Tc3Py) [Tc(CH2)3NC4H4; Tc=CpCpTiCl2; Cp=C5H5; Cp=C5H4] in acetonitrile (AN), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). The polymer films were obtained on Pt disc electrodes from AN solutions of the monomers containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte and then transferred to the corresponding monomer-free solution. Studies in Cl–-containing solutions have shown that the p(Tc3Py) matrix is very sensitive to the presence of Cl– ions in all the above solvents, namely that it was subjected to electrochemical degradation at potentials above 0.1 V vs. a Ag/0.01 M Ag+ in AN reference electrode. Degradation of the p(Tc3Py) matrix was also observed in chloride-free DMF+TBAPF6 solutions. Addition of chloride ions to the AN solution containing pyrrole, N-methylpyrrole or Tc3Py inhibits the deposition of the polymer films. On the other hand, we have found that PPy and p(N-MePy) matrices after their deposition in chloride-free AN solutions show much more stable redox responses in contact with chloride and/or DMF solutions. Possible mechanisms of these effects are discussed.Abbreviations AN
acetonitrile
- Cp
cyclopentadienyl
- DMF
N,N-dimethylformamide
- N-MePy
N-methylpyrrole
- p(N-MePy)
poly(N-methylpyrrole)
- PPy
polypyrrole
- p(Tc3Py)
poly[Tc(CH2)3NC4H4]
- Py
pyrrole
- Tc
titanocene=bis(cyclopentadienyl)titanium dichloride, Cp2TiCl2, or its radical CpCpTiCl2 (Cp=C5H4)
- Tc3Py
titanocene-propyl-pyrrole, Tc(CH2)3NC4H4
- THF
tetrahydrofuran
Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003) 相似文献
5.
Dale F Shellhamer David C Gleason Andrew J Ryan Victor L Heasley 《Journal of fluorine chemistry》2003,123(2):171-176
Ionic and photochemical reaction of chlorine (Cl2), bromine (Br2) and iodine monochloride (ICl) to hexafluoro-1,3-butadiene (1) and 1,3-butadiene (2) were carried out under conditions that would provide product distributions under controlled ionic or free-radical conditions. Product distributions for ionic reaction of Cl2 and Br2 with 1 are similar and suggest a weakly-bridged halonium ion species. Theoretical calculations support weakly-bridged chloronium and bromonium ions for both dienes 1 and 2. There are more of the 1,4-dihalo-2-butene products from ionic halogenation of 1 than 2 which correlates with the greater charge density on carbon-4 of halonium ions from 1. Ionic and free-radical reactions of ICl with 1 give 8 and 2% of 3-chloro-4-iodohexafluoro-1-butene and 4-chloro-3-iodohexafluoro-1-butene, respectively. The minor cis-1,4-dihalo-2-butene products from 1 and 2 are reported when formed. 相似文献
6.
Ling-Tian Tang Yu Wei Yi Wang Shao-Wen Hu Xin-Qi Liu Tai-Wei Chu Xiang-Yun Wang 《Journal of Molecular Structure》2004,686(1-3):25-30
The formation of charge-transfer (CT) complexes between N-methyl-6,7-methylenedioxy-tetrahydro-4-isoquinolone (MMDTIQ, the model molecule of alkaloids) and iodine monochloride has been studied with the density functional B3LYP method. The competition for ICl between n-donor(s) and π-donor in the same molecule has been compared for the first time. The results indicate that the electron-donating ability of various donor sites decreases in the following order: amino nitrogen>carbonyl oxygen>etheric oxygen≈aromatic ring. Complexes with a stoichiometry of 1:1 to 1:5 (MMDTIQ–ICl) might form. Among complexes with a given stoichiometry, the one in which the phenyl ring is involved in the binding is always the least stable. According to these results, in order to ensure an alkaloid iodinated, the amount of ICl should be far beyond that of alkaloids and a low polar solvent should be used, which is quite in agreement with our recent experimental results. 相似文献
7.
七十年代末,德国的H.Koepf和P.Koepf-Maier首次证明二氯二茂钛具有抗艾氏腹水癌(EAT)活性后,现在人们又发现了二茂钛衍生物,尤其是二茂钛卤化物对多种肿瘤都具有显著的抑制作用。可以说,二茂钛配合物是继顺铂后又一类型有效的有机金属抗癌剂。现有的研究表明,处量后的二茂钛晶胞中,胞内金属的分布和报导的铂配合物相 相似文献
8.
CrystalandMolecularStructureofaNewMono-substitutedTitanoceneComplex,{(η~5-Cp)[η~5-(1-(4-OCH_3)C_6H_4)C_6H_(10)Cp](TiCl_2)}·0.3(n-... 相似文献
9.
Processes of direct and electrocatalytic (in the presence of electrochemically reduced Cp2TiCl2) reduction of three α-bromoketones containing the C(sp3)-Br or C(sp2)-Br bond, viz., 2-bromo-and 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-ones and α-bromo-acetophenone, were studied by cyclic voltammetry
and preparative electrolysis. In all cases, the dissociative electron transfer proceeds via the concerted mechanism. Preparative electrolysis of these α-bromoketones in the presence of Cp2TiCl2 affords the reductive debromination products in 40–80% yield at low cathodic potentials (−0.85 V vs. Ag/AgCl/KCl). In the case of 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-one in the potentiostatic regime, only one bromine
atom can be eliminated selectively.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 977–983, May, 2007. 相似文献
10.
The crystal and molecular structure of Bis(η5-cyclopentadienyl)titanium(IV) dibromide, Ti(η5?C5H5)2Br2, has been investigated by an X-ray structure determination. Crystal data: triclinic, a = 7.872(5), b = 11.807(5), c = 12.310(3) Å, α = 107.62(3), β = 100.83(4), γ = 90.69(4)°, V = 1 068(14) Å3, T = 293, space group P1 , Z = 4 (there are two crystallographically independent molecules in the asymmetric unit cell and their conformations are similar). Final R and Rw values are 0.068 and 0.073, respectively. The structural results are compared to those for similar type molecules. 相似文献