全文获取类型
收费全文 | 4177篇 |
免费 | 140篇 |
国内免费 | 19篇 |
专业分类
化学 | 3039篇 |
晶体学 | 17篇 |
力学 | 63篇 |
数学 | 534篇 |
物理学 | 683篇 |
出版年
2022年 | 24篇 |
2021年 | 43篇 |
2020年 | 86篇 |
2019年 | 61篇 |
2018年 | 40篇 |
2017年 | 29篇 |
2016年 | 110篇 |
2015年 | 87篇 |
2014年 | 90篇 |
2013年 | 174篇 |
2012年 | 159篇 |
2011年 | 180篇 |
2010年 | 136篇 |
2009年 | 114篇 |
2008年 | 172篇 |
2007年 | 163篇 |
2006年 | 188篇 |
2005年 | 179篇 |
2004年 | 141篇 |
2003年 | 123篇 |
2002年 | 155篇 |
2001年 | 99篇 |
2000年 | 88篇 |
1999年 | 86篇 |
1998年 | 66篇 |
1997年 | 75篇 |
1996年 | 81篇 |
1995年 | 74篇 |
1994年 | 72篇 |
1993年 | 60篇 |
1992年 | 68篇 |
1991年 | 55篇 |
1990年 | 35篇 |
1989年 | 62篇 |
1988年 | 43篇 |
1987年 | 29篇 |
1986年 | 55篇 |
1985年 | 44篇 |
1984年 | 45篇 |
1983年 | 49篇 |
1981年 | 38篇 |
1980年 | 44篇 |
1979年 | 47篇 |
1978年 | 46篇 |
1977年 | 35篇 |
1976年 | 41篇 |
1975年 | 36篇 |
1974年 | 29篇 |
1973年 | 36篇 |
1971年 | 26篇 |
排序方式: 共有4336条查询结果,搜索用时 15 毫秒
31.
32.
A novel linear trinuclear mu-O-bridging 2-phosphinophenolate nickel(II) complex with fac-tris(P(intersection)O- chelates) in the terminal positions and the three oxygen atoms each facing the central nickel(II) cation was synthesized and structurally characterized by X-ray crystallography. To the best of our knowledge, this is the first example of an octahedral Ni(II) tris(P(intersection)O- chelate). 相似文献
33.
Immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex) with a cyclodextrin content of approximately 30 % by weight, previously employed as a versatile chiral stationary phase for the separation of enantiomers by GC, has been used for the separation of enantiomers by capillary supercritical fluid chromatography (SFC). A considerable number of racemates could be resolved, e.g. aromatic alcohols, amino alcohols (TFA derivatives), and underivatized acids. Many pharmaceutical compounds were among those analyzed, including several NSAIDs (e.g. ibuprofen and ketoprofen), a steroidal drug (nor-gestrel), a barbiturate (hexobarbital), and others. Among the racemates resolved were many which cannot be analyzed by GC owing to low volatility or decomposition at elevated temperatures. For two racemates, analysis temperature and mobile phase density were systematically varied to give constant analysis times or capacity factors k. Low temperatures (ca 60 °C) yielded the best separation in term of separation factor, α, or resolution, Rs, even though higher densities had to be used. In comparison with GC, capillary SFC was able to furnish higher separation factors and similar resolution. The applicability of capillary SFC for the analysis of mixtures of cyclodextrin derivatives, e.g. those used in the synthesis of Chirasil-Dex, was, furthermore, demonstrated. 相似文献
34.
The redox properties of the system Fe(tmphen)3(II/III) (tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) have been studied in the solvents nitromethane, acetonitrile, propanediol-1,2-carbonate, dimethylformamide, dimethylacetamide, dimethylsulfoxide and of the systems Fe(phen)3(II/III) (phen=1,10-phenanthroline) and Fe(niphen)3(II/III) (niphen=5-nitro-1,10-phenanthroline) in the solvents nitromethane, acetonitrile, propanediol-1,2-carbonate and acetone. The redox potentials of Fe(tmphen)3(II/III) are nearly independent of the solvent suggesting that the system might be used as a reference redox couple similar to the systems ferrocene/ferricinium or bisbiphenylchromium(0/I). In contrast the redox potentials of Fe(niphen)3(II/III) show a significant decrease with increasing donor number of the solvent which can be explained by nucleophilic attack of solvent molecules at the iron. It is shown that such a mechanism is consistent with the known solvent and salt effects on the kinetics of dissociation of ferroin and ferriin type complexes. 相似文献
35.
36.
37.
Jean-Franois Nierengarten Tilo Habicher Roland Kessinger Francesca Cardullo Franois Diederich Volker Gramlich Jean-Paul Gisselbrecht Corinne Boudon Maurice Gross 《Helvetica chimica acta》1997,80(7):2238-2276
The macrocyclization between buckminsterfullerene, C60, and bis-malonate derivatives in double Bingel reaction provides a versatile and simple method for the preparation of covalent bis-adducts of C60 with high regio- and diastereoselectivity. A combination of spectral analysis, stereochemical considerations, and X-ray crystallography (Fig. 2) revealed that out of the possible in-in, in-out, and out-out stereoisomers, the reaction of bis-malonates linked by o-, m-, or p-xylylene tethers afforded only the out-out ones (Scheme 1). In contrast, the use of larger tethers derived from 1,10-phenanthroline also provided a first example, (±)- 19 (Scheme 2), of an in-out product. Starting from optically pure bis-malonate derivatives, the new bis-functionalization method permitted the diastereoselective preparation of optically active fullerene derivatives (Schemes 4 and 5) and, ultimately, the enantioselective preparation (enantiomeric excess ee > 97%) of optically active cis-3 bis-adducts whose chirality results exclusively from the addition pattern (Fig. 6). The macrocyclic fixation of a bis-malonate with an optically active, 9,9′-spirobi[9H-fluorene]-derived tether to C60 under generation of 24 and ent- 24 with an achiral addition pattern (Scheme 4) was found to induce dramatic changes in the chiroptical properties of the tether chromophore such as strong enhancement and reversal of sign of the Cotton effects in the circular dichroism (CD) spectra (Figs. 4 and 5). By the same method, the functionafized bis-adducts 50 and 51 (Schemes 10 and 11) were prepared as initiator cores for the synthesis of the fullerene dendrimers 62 , 63 , and 66 (Schemes 12 and 13) by convergent growth. Finally, the new methodology was extended, to the regio- and diastereoselective construction of higher cyclopropanated adducts. Starting from mono-adduct 71 , a clipping reaction provided exclusively the all-cis-2 tris-adduct (±)- 72 (Scheme 14), whereas the similar reaction of bis-adduct 76 afforded the all-cis-2 tetrakis-adduct 77 (Scheme 15). Electrochemical investigations by steady-state voltammetry (Table 2) in CH2Cl2 (+0.1M Bu4NPF6) showed that all macroeyciic bis(methano)fullerenes underwent multiple reduction steps, and that regioisomerism was not much influencing the redox potentials, All cis-2 bis-adducts gave an instable dianion which decomposed during the electrochemical reduction. In CH2Cl2, the redox potential of the fullerene core in dendrimers 62, 63 , and 66 is not affected by differences in size and density of the surrounding poly(ether-amide) dendrons. The all-cis-2 tris- and tetrakis(meihano)fullercnes (±) -72 and 77 , respectively, are reduced at more negative potential than previously reported all-e tris- and tetrakis-adducts with methane bridges that are also located along an equatorial belt. This indicates a larger perturbation of the original fullerene π-chromophore and a larger raise in LUMO energy in the former derivatives. 相似文献
38.
Wagner F Gruber O Lackner K Murmann HD Speth E Becker G Bosch HS Brocken H Cattanei G Dorst D Eberhagen A Elsner A Erckmann V Fussmann G Gehre O Gernhardt J Gierke Gv Glock E Grieger G Grigull P Haas G Hacker H Hartfuss HJ Jäckel H Jaenicke R Janeschitz G Junker J Karger F Kasparek W Keilhacker M Kick M Klüber O Kornherr M Kroiss H Kuehner M Lenoci M Lisitano G Maassberg M Mahn C Marlier S Mayer HM McCormick K Meisel D Mertens V Müller ER Müller Müller G Niedermeyer H Ohlendorf W 《Physical review letters》1986,56(20):2187-2190
39.
Volker Staemmler 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,39(2):121-125
Accurate quantum-chemical ab initio calculations have been performed at the SCF and CEPA (coupled electron pair approximation) levels for the van der Waals interaction in the X 2 Σ + ground state of LiHe. An extended basis set has been used and the counterpoise correction for the basis set superposition error (BSSE) has been applied. The calculated potential energy curve has a very shallow minimum at 11.56 a 0 with a well depth of only 1.49 cm?1. This is too small to allow for a bound vibrational level. The analysis of the results shows that the interaction mainly consists of the Pauli repulsion between Li(1s 22s) and He (1s 2), which is decaying exponentially, and the attractive London dispersion energy. Van der Waals coefficients C6, C8, and C10 have been determined by a least squares fit to the long-range part of the calculated potential curve. 相似文献
40.
Five different structures of CH5
+ and one structure of CH5
– are calculated using a gaussian basis both in the SCF approximation and with the inclusion of electron correlation in the independent electron pair approximation (IEPA). While on SCF level the C
sstructure of CH5
+ has to lowest energy, the energy difference between the C
sand C
2vstructures becomes negligible if correlation is included. In contrast to this the approach of a proton to CH4 at large and intermediate distances is most favorable towards a corner of the CH4 tetrahedron which means a structure. The decomposition of CH5
+ into CH3
+ and H2 requires 20kcal/mol on SCF level and 40 kcal/mol if correlation is included. 相似文献