全文获取类型
收费全文 | 2134篇 |
免费 | 34篇 |
国内免费 | 15篇 |
专业分类
化学 | 1497篇 |
晶体学 | 48篇 |
力学 | 39篇 |
数学 | 146篇 |
物理学 | 453篇 |
出版年
2022年 | 8篇 |
2021年 | 12篇 |
2020年 | 12篇 |
2019年 | 21篇 |
2017年 | 11篇 |
2016年 | 34篇 |
2015年 | 33篇 |
2014年 | 48篇 |
2013年 | 131篇 |
2012年 | 106篇 |
2011年 | 100篇 |
2010年 | 61篇 |
2009年 | 84篇 |
2008年 | 115篇 |
2007年 | 126篇 |
2006年 | 126篇 |
2005年 | 113篇 |
2004年 | 108篇 |
2003年 | 85篇 |
2002年 | 93篇 |
2001年 | 47篇 |
2000年 | 42篇 |
1999年 | 36篇 |
1998年 | 20篇 |
1997年 | 20篇 |
1996年 | 28篇 |
1995年 | 18篇 |
1994年 | 32篇 |
1993年 | 23篇 |
1992年 | 23篇 |
1991年 | 14篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 10篇 |
1987年 | 20篇 |
1986年 | 15篇 |
1985年 | 43篇 |
1984年 | 30篇 |
1983年 | 25篇 |
1982年 | 37篇 |
1981年 | 34篇 |
1980年 | 20篇 |
1979年 | 30篇 |
1978年 | 20篇 |
1977年 | 15篇 |
1976年 | 22篇 |
1975年 | 15篇 |
1974年 | 12篇 |
1973年 | 24篇 |
1967年 | 8篇 |
排序方式: 共有2183条查询结果,搜索用时 15 毫秒
41.
Hideo Kurosawa 《Journal of organometallic chemistry》2004,689(24):4511-4520
This review summarizes the author’s contributions to the field of chemistry of group 10 metal complexes containing unsaturated hydrocarbon ligands, with a brief introduction showing how his research subject has shifted from mononuclear type to multinuclear type complexes. New structure and reactivity trends in the multipalladium complexes with bridging allyl and allenyl/propargyl ligands, as well as bridging conjugated polyene molecules are discussed in terms of some unique bonding features of these complexes. 相似文献
42.
The oxygen ions of the β-VOPO4 catalyst were exchanged with an
tracer by a reduction–oxidation method and by a catalytic oxidation of but-1-ene using
2. The bands at 992 and 900 cm−1 were more shifted to lower frequencies than those at 1076 and 1002 cm−1. Applying the correlation between the Raman bands and stretching vibrations in the literature, the exchanged oxygen species were estimated. The results suggest that the P–O–V vacancies corresponding to 992 and 900 cm−1 were responsible for reoxidation and the V=O oxygen corresponding to the 1002 cm−1 band of β-VOPO4 was not. The (VO)2P2O7 was oxidized to β-VOPO4 by O2 above 823 K. The insertion position of oxygen was determined at the bands at 992 and 900 cm−1 of β-VOPO4 using
2, which is the same as the exchanged position. 相似文献
43.
Okada Y Yokozawa M Akiba M Oishi K O-kawa K Akeboshi T Kawamura Y Inokuma S Nakamura Y Nishimura J 《Organic & biomolecular chemistry》2003,1(14):2506-2511
A variety of aromatic compounds with both activating and deactivating substituents were brominated with sodium monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that are easily protonated, trifluoroacetic acid may be employed as solvent in the reaction with 1, in contrast NBS was ineffective in trifluoroacetic acid. This renders 1 a superior reagent relative to NBS. In addition to aromatics, alkenes, ketones and esters were also brominated with 1. Diethyl malonate was brominated with 1 and then subjected to a Bingel reaction with NaH to afford the desired methanofullerene in reasonable yield. 相似文献
44.
[reaction: see text] A concise and stereoselective synthesis of the chiral building block, dioxanylpiperidene 4 as a precursor for deoxyazasugars, starting from the Garner aldehyde 5 using catalytic ring-closing metathesis (RCM) for the construction of the piperidine ring is described. The asymmetric synthesis of 1-deoxygalactonojirimycin and its congeners 1-3 was carried out via the use of 4 in a highly stereocontrolled mode. 相似文献
45.
A new preparative method of β- and γ-alkoxy (acetoxy) ketones, which are important precursors of vinyl ketones and 1,4-diketones, respectively, is presented. With PdCl2/CuCl/O2 or PdCl2/p-benzoquinone catalyst system, internal olefins bearing allylic alkoxy or acetoxy group underwent regioselective oxidation to form the corresponding β-alkoxy or β-acetoxy ketones. Similarly, γ-acetoxy ketones were obtained from homoallyl acetates having internal olefins with high regioselectivity. 相似文献
46.
Di(triptycyl)carbene: a fairly persistent triplet dialkylcarbene 总被引:1,自引:0,他引:1
Iiba E Hirai K Tomioka H Yoshioka Y 《Journal of the American Chemical Society》2002,124(48):14308-14309
The title carbene was generated and characterized by matrix spectroscopy (ESR and UV/vis) and laser flash photolysis along with theoretical calculations, which revealed interesting effects of triptycyl groups on structure and reactivities of carbenes. 相似文献
47.
Soh N Imato T Kawamura K Maeda M Katayama Y 《Chemical communications (Cambridge, England)》2002,(22):2650-2651
A novel fluorescent probe, which could be the first example of a ratiometric molecular probe for direct monitoring of NO production, has been developed using a 'spin-exchange' mechanism. 相似文献
48.
Results from full fourth-order perturbation theory [SDTQ MBPT(4)], and the coupled-cluster single- and double-excitation model (CCSD). are compared with recent full CI results for BH, HF, NH3, and H2O. For H2O, studies include large symmetric displacements of the OH bonds, which offer a severe test for any single-reference MBPT/CC method. In every case. CCSD plus fourth-order triple-excitation terms provide agreement with the full CI to < 2 kcal/mole. SDTQ MBPT(4) has an error 10 kcal/mole for displaced H2O. 相似文献
49.
Fumio Kiyono Hideo Tajima Keiichi Ogasawara Akihiro Yamasaki 《Fluid Phase Equilibria》2005,230(1-2):90-98
A method for determining quadruple points of a two-component system containing a simple hydrate phase is proposed. This method utilizes the quasi-static change of the system along three-phase equilibrium lines and was proved to be able to determine the quadruple points as accurately as the conventional method. By using this method, even though some preparation is necessary, a quadruple point can be determined in just a single experimental run. The behavior of the system near the quadruple points was also examined experimentally, for both the quasi-static and the irreversible change cases. At the quadruple points, the temperature and pressure of the system were kept constant for a while, as at the triple point of water. In both cases, the representative point of the state of the system passed through the quadruple point on a p–T diagram. 相似文献
50.
Katsuhiko Tomooka Nobuyuki Komine Tomoya Sasaki Hideo Shimizu Takeshi Nakai 《Tetrahedron letters》1998,39(52):2362-9718
Treatment of (E)-6-phenyl-5-hexenyl carbamates with s-BuLi/(−)-sparteine is shown to afford the trans-1,2-disubstituted cyclopentane derivatives in high % ee, along with the bicyclo[3.1.0]hexanes (bicyclization products). 相似文献