全文获取类型
收费全文 | 2542篇 |
免费 | 67篇 |
国内免费 | 16篇 |
专业分类
化学 | 1773篇 |
晶体学 | 29篇 |
力学 | 42篇 |
数学 | 420篇 |
物理学 | 252篇 |
无线电 | 109篇 |
出版年
2022年 | 14篇 |
2021年 | 21篇 |
2020年 | 43篇 |
2019年 | 44篇 |
2018年 | 32篇 |
2017年 | 16篇 |
2016年 | 56篇 |
2015年 | 60篇 |
2014年 | 63篇 |
2013年 | 86篇 |
2012年 | 142篇 |
2011年 | 150篇 |
2010年 | 82篇 |
2009年 | 73篇 |
2008年 | 145篇 |
2007年 | 127篇 |
2006年 | 129篇 |
2005年 | 129篇 |
2004年 | 117篇 |
2003年 | 123篇 |
2002年 | 87篇 |
2001年 | 38篇 |
2000年 | 41篇 |
1999年 | 24篇 |
1998年 | 22篇 |
1997年 | 33篇 |
1996年 | 31篇 |
1995年 | 33篇 |
1994年 | 26篇 |
1993年 | 20篇 |
1992年 | 21篇 |
1991年 | 21篇 |
1990年 | 19篇 |
1989年 | 20篇 |
1988年 | 28篇 |
1987年 | 34篇 |
1986年 | 22篇 |
1985年 | 46篇 |
1984年 | 39篇 |
1983年 | 44篇 |
1982年 | 50篇 |
1981年 | 41篇 |
1980年 | 43篇 |
1979年 | 25篇 |
1978年 | 32篇 |
1977年 | 21篇 |
1976年 | 19篇 |
1975年 | 22篇 |
1974年 | 15篇 |
1973年 | 15篇 |
排序方式: 共有2625条查询结果,搜索用时 906 毫秒
61.
Graham Smith Colin H.L. Kennard Thomas C.W. Mak 《Journal of organometallic chemistry》1985,290(1):c7-c10
The crystal structure of trimethyl(thiomethyl)platmum(IV), [Pt(CH3)3(SCH3)]4, has been determined using X-ray diffraction. The compound has three independent but isostructural tetrameric units in the asymmetric unit. The four metal atoms in each tetramer are linked by bridging thiomethyl sulphurs, with three methyl groups completing the octahedral coordination around each platinum. Mean interatomic distances within the tetramer are PtS, 2.48(2), PtC, 2.00(4), PtPt, 3.80(2) Å, with a mean bridge angle SPtS, 79.1(7)°. 相似文献
62.
The syntheses of 3,4- and 4,5-diiodophthalonitriles are described. Coupling of the latter compound with Pd(PPh(3))(2)Cl(2) and 1-octyne, 1-heptyne, 1-hexyne, 1-pentyne, and 3,3-dimethyl-1-butyne gave a series of 4,5-dialkynylphthalonitriles. Hydrogenation of 4,5-bis(1-pentynyl)phthalonitrile and 4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile gave 4,5-dipentylphthalonitrile and 4,5-bis(3,3-dimethylbutyl)phthalonitriles. Condensation of the dialkynylphthalonitriles with lithium 1-pentoxide in 1-pentanol gave 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines, while intervention of the intermediate dilithium phthalocyanines with zinc acetate gave the related zinc(II) phthalocyanines. (1)H NMR spectroscopy of these octaalkynylphthalocyanines exhibited large chemical shifts (1-2 ppm) of the internal and aromatic protons at concentrations ranging from 10(-)(2) to 10(-)(5) M and at temperatures from 27 to 147 degrees C. The effects of aggregation phenomena are discussed. The importance of reporting concentration and temperature values for NMR spectra of phthalocyanines is stressed. 相似文献
63.
Reza Dabestani Robert D. Hall Robert H. Sik Colin F. Chignell 《Photochemistry and photobiology》1990,52(5):961-971
The photochemistry (Type I and II) of anthralin and its photo-oxidation product 1,8-dihydroxyanthraquinone (1,8-DHAQ) has been studied in ethanol, acetonitrile and dimethylsulfoxide using spin-trapping and direct detection of singlet oxygen (1O2) luminescence techniques. In ethanol, where it exists in its neutral form (AN), anthralin does not undergo either Type I or II reactions upon UV-irradiation. In contrast, irradiation of anthralin in acetonitrile, a solvent in which anthralin is partially converted to its corresponding mono-anion (AN-), generates both superoxide and singlet oxygen. Irradiation of anthralin in dimethylsulfoxide, where the AN- form is present in substantial quantity, generates superoxide and solvent derived radicals but no detectable singlet oxygen. UV-irradiation of 1,8-DHAQ in ethanol and acetonitrile produces both superoxide and singlet oxygen in significant yields. In dimethylsulfoxide, on the other hand, only superoxide and solvent derived radicals are observed. The 1O2 quantum yield for AN- and 1,8-DHAQ in acetonitrile were determined to be 0.14 and 0.88 relative to rose bengal in the same solvent. These findings suggest that the AN photosensitization occurs via Type I and II pathways, is solvent dependent and involves AN- as well as its oxidation product 1,8-DHAQ, which is a more potent generator of both singlet oxygen and superoxide. 相似文献
64.
Dr. Colin Thomson 《Theoretical chemistry accounts》1968,11(2):165-166
The zero-field splitting parametersD andE have been calculated for naphthalene using T.B.M. and I. R. M. wave functions, and accurate values of all significant two, three and four centre dipolar interaction integrals. Agreement with experiment is improved in the case ofE, but is less satisfactory forD. 相似文献
65.
Internally consistent assignments of the 31P-{1H} NMR parameters of the complexes [Pt(RCCR′)(PPh3)2] are proposed, based on the premise that the magnitude of 1J(PtP) depends mainly on the nature of the moiety CR trans to P. For a given R, 2J(PP) correlates with 1J(PtP) for thebond trans to CR. The alkynes PhCCSnEt3, PhCCSnPh3, Me3SiCCCl, Me3SiCCBr, Et3SiCCI and MeCCI undergo oxidative addition reactions with [Pt(C2H4)(PPh3)2]; the intermediate alkyne complex was detected for PhCCSnEt3, Me3SiCCCl and Me3CCBr. The triyne Me(CC)3Me forms platinum(0) complexes by coordination with the central or terminal CC bond and appears also to give a platinum(II) complex by oxidative addition. 相似文献
66.
67.
Thermal oxidation of sulfur vulcanized polyisoprene samples was studied by gravimetry and IR mapping of carbonyl groups (to determine the oxidized layer thickness (TOL)) at temperatures ranging from 60 to 150 °C in air. Oxidation appears noticeably lower than that for the starting non-vulcanized polyisoprene, revealing a stabilizing effect of sulfur-containing species. After a short period where mass loss presumably due to water evaporation predominates, the sample mass increases until a plateau corresponding to 6.3% (at 60 °C) to 0.5% (at 140 °C) mass gain. Practically no weight gain (∼0.1%) was observed at 150 °C. The mass uptake is due to oxygen grafting to the chains. TOL varies from about 4.6 mm (70 °C) to about 1 mm (150 °C).A kinetic model, derived from a mechanistic scheme of radical chain oxidation including stabilizing events due to hydroperoxide reduction by sulfur-containing groups and taking into account the diffusion-reaction coupling, was established and numerically resolved. The model predictions for mass changes and TOL values are in good agreement with experimental data. 相似文献
68.
Capon RJ Skene C Liu EH Lacey E Gill JH Heiland K Friedel T 《Natural product research》2004,18(4):305-309
Bioassay directed fractionation of a Raspailia (Raspailia) sp. (Order Poecilosclerida; Family Raspailiidae) collected during scientific trawling operations off the Northern Rottnest Shelf yielded as nematocidal agents the known metabolites, phorboxazoles A (1) and B (2). Further examination revealed the new natural product but known synthetic compound, esmodil (3). The structure for 3 was confirmed by spectroscopic analysis and total synthesis. 相似文献
69.
Dalgarno SJ Hardie MJ Warren JE Raston CL 《Dalton transactions (Cambridge, England : 2003)》2004,(16):2413-2416
Two types of arrays are formed in water involving aza-crown ethers, p-sulfonatocalix[5]arene and europium(III) ions. One is a co-ordination polymer connecting calixarenes, sodium ions and lanthanide ions based on "ferris wheel" moieties incorporating aza-18-crown-6 and sodium ions. The second structure is a host-guest arrangement with di-protonated diaza-18-crown-6 in the cavity of the calixarenes as part of secondary coordination spheres of aquated europium(iii) ions. 相似文献
70.
Thermodynamic and kinetic parameters have been established for the reaction between the carbon acid, 4-nitrophenylnitromethane,
(4-NPNM), and the base N’-n-propyl-N,N-di-n-propylbenzimidamide, (N’PDPBA), in mesitylene and in chlorobenzene. In some cases deuteron transfer from 4-(D2)NPNM to the base has also been studied. In addition, some results for the proton transfer reaction in tetrahydrofuran have
been collected. Spectrophotometric methods have been employed to monitor the ion-pair product, which is solvatochromic. In
general the solvent dependence of the parameters is as expected, but there is some indication of specific solvation. The kinetic
isotope effects of 11 and 8 in mesitylene and chlorobenzene, respectively, are larger than those predicted classically. However,
as is discussed the n-propyl group on the secondary nitrogen of the base may serve to reduce the extent of tunneling compared
to that in an unsubstituted analogue by a steric effect. 相似文献