全文获取类型
收费全文 | 618篇 |
免费 | 23篇 |
国内免费 | 3篇 |
专业分类
化学 | 531篇 |
晶体学 | 6篇 |
力学 | 7篇 |
数学 | 23篇 |
物理学 | 77篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 5篇 |
2020年 | 22篇 |
2019年 | 15篇 |
2018年 | 9篇 |
2017年 | 7篇 |
2016年 | 18篇 |
2015年 | 12篇 |
2014年 | 14篇 |
2013年 | 23篇 |
2012年 | 35篇 |
2011年 | 25篇 |
2010年 | 15篇 |
2009年 | 19篇 |
2008年 | 40篇 |
2007年 | 40篇 |
2006年 | 33篇 |
2005年 | 28篇 |
2004年 | 30篇 |
2003年 | 34篇 |
2002年 | 22篇 |
2001年 | 12篇 |
2000年 | 17篇 |
1999年 | 6篇 |
1997年 | 6篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 5篇 |
1991年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 8篇 |
1983年 | 9篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1980年 | 14篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 6篇 |
1975年 | 8篇 |
1974年 | 4篇 |
1973年 | 12篇 |
1972年 | 4篇 |
1971年 | 2篇 |
1966年 | 1篇 |
1965年 | 1篇 |
排序方式: 共有644条查询结果,搜索用时 15 毫秒
21.
A stepwise reaction of p-tert-butylthiacalix[4]arene (TC4A-(OH)(4)) with [CpTiCl3]-NEt(3) and cis-[Mo(N(2))(2)(PMe(2)Ph)(4)] afforded a new Ti-Mo heterobimetallic complex [TC4A-(O)(4)Ti(micro2-C(5)H(5))MoH(PMe(2)Ph)(2)] which shows an unusual alpha-agostic micro2-eta5:eta2-coordination of a cyclopentadienyl ligand. 相似文献
22.
Izaki M 《Chemical communications (Cambridge, England)》2002,(5):476-477
Highly (0001) oriented zinc oxide (ZnO) films of smooth layer type and hexagonal columns have been prepared on quartz glass substrates at temperature as low as 323 K by UV light assisted chemical deposition from an aqueous solution containing hydrated zinc nitrate and dimethylamine-borane (DMAB). 相似文献
23.
Uchiyama M Miyoshi T Kajihara Y Sakamoto T Otani Y Ohwada T Kondo Y 《Journal of the American Chemical Society》2002,124(29):8514-8515
We have developed new methods for preparing functionalized benzynes through deprotonative zincation as a key reaction using R2Zn(TMP)Li, and we also describes dramatic ligand effects on the benzyne formation. Deprotonative zincation of various meta-substituted bromobenzenes with Me2Zn(TMP)Li proved effective for the one-pot generation of various 3-functionalized benzynes, particularly those electrophilic substituents such as ester, amide, and cyano. On the other hand, zincation with tBu2Zn(TMP)Li, followed by electrophilic trapping (with I2) proved a powerful tool for the preparation of 1,2,3-trisubstituted aromatic compounds.8 The resultant 1,2,3-trisubstituted benzenes are available as precursors for generation of 3-substituted benzynes by halogen-zinc exchange reactions with Me3ZnLi. These methods offer far greater generality than previous methods for the synthesis of functionalized asymmetric benzynes, and should be of value in new syntheses of various natural products and functional materials. In addition, these results underline the utility of spectator ligands on the central metal of ate complexes as a tunable functionality in the development of new ate complex-promoted reactions. 相似文献
24.
The chiral separation ability of unmodified and di- and trimethylated -, β- and γ-cyclodextrins (CDs) as chiral selectors in capillary zone electrophoresis was investigated in the presence of urea derivatives using twelve dansylamino acids as model solutes. The addition of these urea derivatives (unsubstituted, methyl-, ethyl- and 1,3-dimethylureas) produced dramatic enhancement in the enantioselectivity of unmodified β-CD but also reduced the enantioselectivities of the other CDs. 相似文献
25.
Helaleh MI Tanaka K Mori M Xu Q Taoda H Ding MY Hu W Hasebe K Haddad PR 《Journal of chromatography. A》2003,997(1-2):139-144
Determination of aromatic carboxylic acids by conventional ion-exclusion chromatography is relatively difficult and methods generally rely on hydrophobic interaction between the solute and the resin. To overcome the difficulties in determining aromatic carboxylic acids a new approach is presented, termed vacancy ion-exclusion chromatography, which is based on use of the sample as mobile phase and an injection of aqueous 10% methanol onto a weakly acidic cation-exchange column (TSKgel OApak-A). Highly sensitive conductivity detection occurred with sharp and well-shaped peaks, leading to very efficient separations. The effects of sulfuric acid concentration added to the mobile phase, flow-rate, and column temperature on the retention volume of tested aromatic carboxylic acids was investigated. Retention times were found to be affected by the concentration of the analytes in the mobile phase and to some extent also by the addition of an organic modifier such as methanol to the injected water sample. Separation of sulfuric acid (SA), naphthalenetetracarboxylic acid (NTCA), phthalic acid (PA) and benzoic acid (BA) was satisfactory using this new approach. Detection limits were 0.66, 0.67, 0.42 and 0.86 microM and detector responses were linear in the range 1-100, 1-80, 2.5-100 and 10-40 microM, for SA, NTCA, PA and BA, respectively. Precision for retention times was 0.36% and for peak areas was 1.5%. 相似文献
26.
Motoyoshi Hatada Masanobu Nishii 《Journal of polymer science. Part A, Polymer chemistry》1977,15(4):927-935
In continuation of the previous series of studies, polymerization of octadecyl methacrylate (ODMA) induced by electron beams has been investigated in a form of its multilayer or monolayer in an attempt to prepare a stable thin polymer film having a regular layer structure. ODMA multilayers were prepared by the Langmuir-Blodgett technique and irradiated with electron beams from a Van de Graaff accelerator. Multiple reflection infrared spectroscopy and x-ray diffractometry revealed that the ODMA multilayer was polymerized to give a thin polymer film having a regular layered structure when irradiated in nitrogen atmosphere, but no indication of polymerization was observed when irradiated in air. A preliminary study on the ODMA monolayer at a nitrogen–water interface indicated that the monolayer was polymerized. 相似文献
27.
Reactions of the bis(hydrosulfido) complexes [Cp*Rh(SH)(2)(PMe(3))] (1a; Cp* = eta(5)-C(5)Me(5)) with [CpTiCl(3)] (Cp = eta(5)-C(5)H(5)) and [TiCl(4)(thf)(2)] in the presence of triethylamine led to the formation of the sulfido-bridged titanium-rhodium complexes [Cp*Rh(PMe(3))(micro(2)-S)(2)TiClCp] (2a) and [Cp*Rh(PMe(3))(micro2-S)(2)TiCl(2)] (3a), respectively. Complex 3a and its iridium analogue 3b were further converted into the bis(acetylacetonato) complexes [Cp*M(PMe(3))(micro(2)-S)(2)Ti(acac)(2)] (4a, M = Rh; 4b, M = Ir) upon treatment with acetylacetone. The hydrosulfido complexes 1a and [Cp*Ir(SH)(2)(PMe(3))] (1b) also reacted with [VCl(3)(thf)(3)] and [Mo(CO)(4)(nbd)] (nbd = 2,5-norbornadiene) to afford the cationic sulfido-bridged VM2 complexes [(Cp*M(PMe(3))(micro2-S)(2))2V](+) (5a(+), M = Rh; 5b(+), M = Ir) and the hydrosulfido-bridged MoM complexes [Cp*M(PMe(3))(micro2-SH)(2)Mo(CO)(4)] (6a, M = Rh; 6b, M = Ir), respectively. 相似文献
28.
The biomimetic reactions of epoxygermacrene-D () with basic alumina afforded three new interesting compounds (, , and ), two of which ( and ) have the same carbon skeleton as that of periplanone-A (), a sexual stimulant for the American cockroach. The remaining one () is a bicyclo[3.1.0]hexane derivative, from whch an axisonitrile-3 type compound () has been produced. Finally, preisocalamendiol () was also converted into . 相似文献
29.
The oxidative homocouplings of lithium enolates of (4S)-3-(3-arylpropanoyl)-4-isopropyl-2-oxazolidinones and (4R, 5S)-1-(3-arylpropanoyl)-3,4-dimethyl-5-phenyl-2-imidazolidinones gave the corresponding R,R-dimers stereoselectively with TiCl(4), PhI(OAc)(2), or CuCl(2) as an oxidant. The stereoselectivity can be explained by a radical coupling mechanism. Optically active dibenzylbutyrolactone lignans, such as (-)-hinokinin and (-)-dimethylmatairesinol, and dibenzylbutanediol lignans, such as (-)-dihydrocubebin and (-)-dimethylsecoisolariciresinol, were synthesized from the major R,R-dimers. The oxidative coupling of (4R, 5S)-1-(3-arylpropanoyl)-3,4-dimethyl-5-phenyl-2-imidazolidinones with LDA-I(2) gave R,S-dimers mainly, and this result can be explained by an S(N)2 mechanism. 相似文献
30.
Muranaka A Matsumoto Y Uchiyama M Jiang J Bian Y Ceulemans A Kobayashi N 《Inorganic chemistry》2005,44(11):3818-3826
A series of heteroleptic rare-earth sandwich complexes [M(Nc)(OEP)] (M = La, Nd, Eu, Dy, and Lu; Nc = 2,3-naphthalocyaninate; OEP = octaethylporphyrinate) have been investigated by electronic absorption and magnetic circular dichroism (MCD) spectroscopy. The electronic absorption spectra of the neutral forms showed two characteristic transitions (bands I and II) in the near-IR region, both of which were systematically shifted depending on the size of their central metal. In the MCD spectra, a relatively intense Faraday A term and a significantly weak Faraday B term have been observed corresponding to bands II and I, respectively. The spectral features were successfully interpreted using a simple MO model by considering the relevant interactions of Gouterman's four orbitals of the constituent chromophores. The model succeeded in assigning the MCD spectra of the related compounds, the oxidized and reduced forms of the dimer ([M(Nc)(OEP)]+ and [M(Nc)(OEP)]-), and neutral forms of the triple-decker compounds (M2(Nc)(OEP)2, M = Nd, Eu). DFT calculations of the dimers supported the validity of this model. 相似文献