全文获取类型
收费全文 | 3231篇 |
免费 | 82篇 |
国内免费 | 17篇 |
专业分类
化学 | 2186篇 |
晶体学 | 21篇 |
力学 | 127篇 |
数学 | 545篇 |
物理学 | 451篇 |
出版年
2023年 | 13篇 |
2022年 | 23篇 |
2021年 | 33篇 |
2020年 | 39篇 |
2019年 | 43篇 |
2018年 | 32篇 |
2017年 | 36篇 |
2016年 | 70篇 |
2015年 | 49篇 |
2014年 | 74篇 |
2013年 | 181篇 |
2012年 | 155篇 |
2011年 | 183篇 |
2010年 | 124篇 |
2009年 | 117篇 |
2008年 | 191篇 |
2007年 | 173篇 |
2006年 | 181篇 |
2005年 | 199篇 |
2004年 | 174篇 |
2003年 | 136篇 |
2002年 | 150篇 |
2001年 | 55篇 |
2000年 | 45篇 |
1999年 | 47篇 |
1998年 | 50篇 |
1997年 | 54篇 |
1996年 | 38篇 |
1995年 | 25篇 |
1994年 | 38篇 |
1993年 | 37篇 |
1992年 | 22篇 |
1991年 | 28篇 |
1990年 | 15篇 |
1989年 | 25篇 |
1988年 | 15篇 |
1987年 | 18篇 |
1986年 | 20篇 |
1985年 | 34篇 |
1984年 | 35篇 |
1983年 | 22篇 |
1982年 | 31篇 |
1981年 | 35篇 |
1980年 | 40篇 |
1979年 | 28篇 |
1978年 | 25篇 |
1977年 | 38篇 |
1976年 | 37篇 |
1975年 | 36篇 |
1974年 | 26篇 |
排序方式: 共有3330条查询结果,搜索用时 15 毫秒
21.
Three new porphyrins bearing in the meso positions 4-(pyrazol-1-yl)-2,3,5,6-tetrafluorophenyl substituents have been prepared and characterized by nmr spectroscopy. 相似文献
22.
In the paper we prove two inequalities involving Gelfand numbers of operators with values in a Hilbert space. The first inequality is a Rademacher version of the main result in [Pa-To-1] which relates the Gelfand numbers of an operator from a Banach spaceX intol
2
n
with a certain Rademacher average for the dual operator. The second inequality states that the Gelfand numbers of an operatoru froml
1
N
into a Hilbert space satisfy the inequality
相似文献
23.
Strong, low-energy two-photon absorption in extended amine-terminated cyano-substituted phenylenevinylene oligomers 总被引:8,自引:0,他引:8
Chung SJ Rumi M Alain V Barlow S Perry JW Marder SR 《Journal of the American Chemical Society》2005,127(31):10844-10845
Three quadrupolar oligophenylenevinylenes with five rings in the conjugated backbone, terminal donor groups, and various acceptors and/or donors along the backbone were synthesized and their two-photon spectroscopic properties investigated. These chromophores exhibit large two-photon absorption cross sections over a wide wavelength range and two distinct peaks, the strongest of which (deltamax > 3600 GM) is observed at 960-970 nm, a wavelength close to twice the value of the linear absorption maximum (2lambda(1)max). The findings on these chromophores are compared with those for analogous molecules with shorter conjugation length, for which the main two-photon band is at significantly shorter wavelength than 2lambda(1)max. 相似文献
24.
Tran Quang Minh Léon Christiaens Pierre Grandclaudon Alain Lablache-Combier 《Tetrahedron》1977,33(17):2225-2229
Photoirradiated in presence of acetophenone, benzo[b]selenophene and its 3-methyl derivative add to dimethyl acetylenedicarboxylate. In each ease, the primary reaction product is unstable and has not been isolated. Photoexeited in its triplet state (the energy of which is in the neighbourhood of 69 ) benzo[b]selenophene and its 2- and 3-methyl, 2,3 dimethyl, 3 acetoxy and 2-methyl-3-acetoxy derivatives add to 1,2 dichloroethylene leading to cyclobutanes. Neither cyclo-addition occurs in absence of photosensitiser. Single-crystal X-ray analysis gave the structures of the two adducts of 3-acetoxybenzo[b]selenophene with trans-1,2-dichloroethylene. In both compounds the chlorine atoms are trans. 相似文献
25.
26.
We report a molecular dynamics study of the solvation of UO2(2+), Eu3+ and Eu2+ ions in two "basic" (Lewis acidity) room-temperature ionic liquids (IL) composed of the 1-ethyl-3-methylimidazolium cation (EMI+) and a mixture of AlCl4- and Cl- anions, in which the Cl-/AlCl4- ratio is about 1 and 3, respectively. The study reveals the importance of the [UO2Cl4]2- species, which spontaneously form during most simulations, and that the first solvation shell of europium is filled with Cl- and AlCl4- ions embedded in a cationic EMI+ shell. The stability of the [UO2Cl4]2- and [Eu(III)Cl6]3- complexes is supported by quantum mechanical calculations, according to which the uranyl and europium cations intrinsically prefer Cl- to the AlCl4- ion. In the gas phase, however, [Eu(III)Cl6]3- and [Eu(II)Cl6]4- complexes are predicted to be metastable and to lose two to three Cl- ions. This contrasts with the results of simulations of complexes in ILs, in which the "solvation" of the europium complexes increases with the number of coordinated chlorides, leading to an equilibrium between different chloro species. The behavior of the hydrated [Eu(OH2)8]3+ complex is considered in the basic liquids; the complex exchanges H2O molecules with Cl- ions to form mixed [EuCl3(OH2)4] and [EuCl4(OH2)3]- complexes. The results of the simulations allow us to better understand the microscopic nature and solvation of lanthanide and actinide complexes in "basic" ionic liquids. 相似文献
27.
Simultaneous separation of flavanone glycosides and polymethoxylated flavones in citrus juices using liquid chromatography 总被引:5,自引:0,他引:5
We present a simultaneous liquid chromatographic method for the separation of two flavonoid compound families, flavanone glycosides (FGs) and polymethoxylated flavones (PMFs), which are usually found in citrus fruit species and varieties. This technique permits the quantitation of six FGs (narirutin, naringin, hesperidin, neohesperidin, didymin, poncirin) and six PMFs (sinensetin, hexamethoxyflavone, nobiletin, scutellarein, heptamethoxyflavone and tangeretin). This technique, to be used to characterize a citrus juice by its polyphenolic profile, has been applied to the determination of flavonoid compounds in grapefruit- and orange juice. Differentiation of orange juice varieties and mixtures containing tangor juice using polyphenolic profiles and flavonoid content has been achieved. 相似文献
28.
Jean M. J. Tronchet Bernard Gentile Alain P. Bonenfant Olivier R. Martin 《Helvetica chimica acta》1979,62(3):696-699
Further examples of O-isopropylidenaldehydosugars in the furanose series Formyl-bearing furanose derivatives 1–3 (α-D -xylo or α-D -erythro configurations) and 5–8 (configurations α-D -ribo, α-D -lyxo, β-L -threo and D -arabino) have been prepared by classical synthetic steps and their properties mainly spectroscopic, reported. The coupling constant between the formyl and the vicinal proton is always small. Like other members of the series, these new aldehydosugars constitute very useful and flexible synthetic intermediates. 相似文献
29.
Alain Pellegatti Et Andr Julg 《International journal of quantum chemistry》1976,10(1):113-121
The influence of various correlation functions, multiplying the monoelectronic space function, is studied and applied to the Helium atom and its isoelectronic series. We used Slater-type basis orbitals and the ground and first excited states have been studied, taking into account the virial and cusp conditions. In the ground state, a very good value for the correlation energy is obtained, using a function of the type For the excited states, this type of function overestimates the assumed value of the correlation energy. 相似文献
30.
Kassi S Macko P Naumenko O Campargue A 《Physical chemistry chemical physics : PCCP》2005,7(12):2460-2467
The absorption spectrum of natural water vapour around 750 nm has been recorded with a typical sensitivity of 3 x 10(-10) cm(-1) using a cw cavity ring down spectroscopy set up based on a Ti:sapphire laser. The 13 312.4-13 377.7 cm(-1) spectral interval was chosen as it corresponds to the region where water dimer absorption was recently measured (K. Pfeisticker et al., Science, 2003, 300, 2078-2080). The line parameters (wavenumber and intensity) of a total of 286 lines of water vapor were measured by a one by one fit of the lines to a Voigt profile. For the main water isotopologue, 276 lines were measured with line intensities as weak as 5 x 10(-29) cm molecule(-1)i.e. about 50 times smaller than the weakest H(2)16O line intensities included in the 2004 edition of the HITRAN database. On the basis of the predictions of Schwenke and Partridge, all but 16 lines could be assigned to different isotopologues of water (H(2)16O, H(2)18O, and HD16O) present in natural abundance in the sample. A total of 272 energy levels of H(2)16O were determined and rovibrationally assigned to 18 upper vibrational states. Half of them had not been reported previously. The importance of the additional absorbance resulting from the observation of many new weak lines is discussed in relation to the detection of water dimer absorption and compared to the absorbance predicted by Schwenke and Partridge. The quality of the line parameters of water monomer is shown to be of crucial importance to identify the absorbance of the water dimer in the considered region. 相似文献
|