全文获取类型
收费全文 | 4328篇 |
免费 | 114篇 |
国内免费 | 39篇 |
专业分类
化学 | 2977篇 |
晶体学 | 67篇 |
力学 | 81篇 |
数学 | 729篇 |
物理学 | 627篇 |
出版年
2021年 | 40篇 |
2020年 | 39篇 |
2019年 | 49篇 |
2018年 | 46篇 |
2017年 | 36篇 |
2016年 | 81篇 |
2015年 | 102篇 |
2014年 | 102篇 |
2013年 | 237篇 |
2012年 | 191篇 |
2011年 | 251篇 |
2010年 | 118篇 |
2009年 | 105篇 |
2008年 | 205篇 |
2007年 | 221篇 |
2006年 | 197篇 |
2005年 | 214篇 |
2004年 | 202篇 |
2003年 | 183篇 |
2002年 | 122篇 |
2001年 | 42篇 |
2000年 | 52篇 |
1999年 | 56篇 |
1998年 | 48篇 |
1997年 | 42篇 |
1996年 | 66篇 |
1995年 | 35篇 |
1994年 | 58篇 |
1993年 | 50篇 |
1992年 | 43篇 |
1991年 | 53篇 |
1990年 | 41篇 |
1989年 | 34篇 |
1988年 | 45篇 |
1987年 | 46篇 |
1986年 | 45篇 |
1985年 | 64篇 |
1984年 | 69篇 |
1983年 | 45篇 |
1982年 | 54篇 |
1981年 | 55篇 |
1980年 | 39篇 |
1979年 | 67篇 |
1978年 | 61篇 |
1977年 | 67篇 |
1976年 | 45篇 |
1975年 | 49篇 |
1974年 | 46篇 |
1973年 | 37篇 |
1972年 | 36篇 |
排序方式: 共有4481条查询结果,搜索用时 750 毫秒
61.
Kent Morrill Robert E. Linder Edith M. Bruckmann Günter Barth Edward Bunnenberg Carl Djerassi Lloyd Seamans Albert Moscowitz 《Tetrahedron》1977,33(8):907-911
The magnetic CD spectra of a number of Me substituted trans-2-decalones and bicyelo[2.2.2]octan-2-ones were measured. The results showed a large, and sometimes dominant, contribution to the MCD intensity which could be correlated with the presence of α-substituents lying outside of the plane of the carbonyl chromophore. 相似文献
62.
Spectral Properties of Fluorescein in Solvent-Water Mixtures: Applications as a Probe of Hydrogen Bonding Environments in Biological Systems 总被引:1,自引:0,他引:1
Nectarios Klonis rew H. A. Clayton Edward W. Voss Jr. William H. Sawyer 《Photochemistry and photobiology》1998,67(5):500-510
Although fluorescein is a widely used fluorescent probe in the biosciences, the effect of solvent environment on its spectral properties is poorly understood. In this paper we explore the use of fluorescein as a probe of the state of hydrogen bonding in its local environment. This application is based on the observation, originally made by Martin ( Chem. Phys. Lett . 35, 105–111, 1975), that the absorption maximum of fluorescein undergoes substantial shifts in organic solvents related to the hydrogen bonding power of the solvents. We have extended this work by studying the spectral properties of the dianion form of the probe in solvent–water mixtures. We show that the magnitude of the shift correlates with the α and β parameters of Kamlet and Taft ( J. Am. Chem. Soc . 98, 377–383; 2886–2894, 1976), which provide a scale of the hydrogen bond donor acidities and acceptor basicities, respectively, of the solvents. In solvent–water mixtures, these shifts reflect general effects of the solvents on the hydrogen bonding environment of the fluorescein through water–solvent hydrogen bonding and specific effects due to fluorescein–solvent hydrogen bonding. Indeed, both the absorption and fluorescence properties appear to be dominated by these effects indicating that the spectral shifts of the dianion can be used as an indicator of its hydrogen bonding environment. We discuss the application of fluorescein as a probe of hydrogen bonding in the microenvironment immediately surrounding the fluorophore, and we illustrate the effect with reference to the fluorescein–antifluorescein antibody complex where it appears that antibodies selected during the immune response possess binding sites that are increasingly dehydrated and hydrophobic. 相似文献
63.
The reaction of sodium hydride or potassium t-butoxide with methyl epoxycitronellate (1) in dimethylformamide affords a mixture of cis,cis-puleganolide (2) and cis,trans-puleganolide (3) in high yield. When the cyclization is conducted at 110°, the isomeric 2-isopropenyl-5-methylcyclopentanecarboxylic acids (8a–d) become the major products. It is demonstrated that γ-lactones undergo alkoxide-induced elimination to afford γ,δ-unsaturated acids. 相似文献
64.
Piotr Ziba Agnieszka Skara Emilia Berna Agata Krakowska Katarzyna Sukowska-Ziaja Edward Kunicki Magorzata Suchanek Boena Muszyska 《Molecules (Basel, Switzerland)》2021,26(11)
The use of substrates supplemented with minerals is a promising strategy for increasing the nutraceutical value of Pleurotus spp. The current research was performed to analyze the effect of substrate supplementation with magnesium (Mg) salts on the Mg content, biomass, and chemical composition of pink oyster mushroom (Pleurotus djamor) fruiting bodies. Before inoculation, substrate was supplemented with MgCl2 × 6 H2O and MgSO4, both salts were applied at three concentrations: 210, 420, and 4200 mg of Mg per 2 kg of substrate. The harvest period included three flushes. Substrate supplementation with 4200 mg of Mg caused the most significant decrease in mushroom productivity, of about 28% for both Mg salts. The dry matter content in fruiting bodies was significantly lower in the treatment in which 210 mg of Mg was applied as MgSO4 in comparison to the control. Supplementation effectively increased the Mg content in fruiting bodies of P. djamor by 19–85% depending on the treatment, and significantly affected the level of remaining bioelements and anions. One hundred grams of pink oyster fruiting bodies, supplemented with Mg salts, provides more than 20% of the Mg dietary value recommended by the Food and Drug Administration (FDA); thus, supplementation can be an effective technique for producing mushrooms that are rich in dietary Mg. Although P. djamor grown in supplemented substrate showed lower productivity, this was evident only in the fresh weight because the differences in dry weight were negligible. Mg supplementation increased the antioxidant activity of the fruiting bodies, phenolic compounds, and some amino acids, including L-tryptophan, and vitamins (thiamine and l-ascorbic acid). 相似文献
65.
QI Qu Edward Tucker Sherril D. Christian 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):213-222
A series of sulfoalkyl ether -cyclodextrin derivatives, including sulfoethyl, sulfopropyl and sulfobutyl ethyl -cyclodextrins, have been synthesized and characterized. Each sulfoalkyl ether -cyclodextrin is a mixture of various degrees of substitution and different positional isotherms. Elemental analysis, 1H NMR, MS, and Differential Scanning Calorimetry analysis were used to determine the average degree of substitution for each -cyclodextrin derivative. The average degrees of substitution are 3.4, 1.6 and 2.5 for sulfoethyl, sulfopropyl and sulfobutyl ether -cyclodextrin, respectively. The water solubility of these derivatives is substantially higher than that of -cyclodextrin. 1H NMR indicates thatsulfoethyl ether -cyclodextrin may have major substitution on the secondaryhydroxyl group while the major substitution in sulfopropyl and sulfobutyl ether-cyclodextrin could be on the primary hydroxyl group. MS spectra showthat no more than one substitution occurred on a single glucose unit. 相似文献
66.
Ashok G. Bajaj Sukh Dev Edward Arnold Bruce Tagle Jon Clardy 《Tetrahedron letters》1981,22(46):4623-4626
The steroechemistry of guggulsterol-1, a component of the exudate of , is shown to be 20(R), 22(R)(). 相似文献
67.
68.
Condensation of bis-(2-chloroethyl)phosphoramidic dichloride with 3′-amino-3′-deoxy-N,N-dimethyladenosine afforded the 2′,3′-cyclicphosphorodiamidate (III). By an improved synthesis, methyl 3-amino-3-deoxy-β-D-ribofuranoside was obtained as a model compound for conversion to the analogous 2,3-cyclicphosphorodiamidate (XII). Existence of the latter as two diastereomers due to phosphorus asymmetry was shown by nmr analysis, using comparison with the 5-(O-p-nitrobenzoate) (XIII) as a basis for assignments. 相似文献
69.
Marina S. Fonari Victor Ch. Kravtsov Yurii A. Simonov Edward V. Ganin Vladimir O. Gelmboldt Janusz Lipowski 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(1-2):85-89
The crystalline host–guest type complex [(18-crown-6NH4)2][SiF6]4H2Ohas been obtained as the result of the interaction of SiF42NH3 with 18-crown-6 (18C6) in an aqueous medium. Crystal data: monoclinic, space groupC 2 c, a=26.541(2), b=8.363(2), c=20.469(2) Å, = 122.43(1)°and Z=4. The final R-value is 0.070 for 3253 reflections with I 2(I).The crystals consist of the complex [NH418C6]+ cations, [SiF6]2-anions and water molecules. The ammonium cation is hydrogen bonded by three of its H-atoms to the crown ether oxygen atoms with N(1) O separations2.923(5)–2.940(5) Å and by the fourth H-atom to the fluorine atom of thehexafluorosilicate anion, the N(1)F(4) distance being 2.797(6) Å.The conformation of the macrocycle and the hydrogen-bond geometry in thecomplex cation closely resemble those in related adducts between 18-crown-6and ammonium salts. All crystal components are connected via a system of hydrogen bonds into a ribbon along the b axis in the unit cell. 相似文献
70.
Pt(II) and Pd(II) dichloride complexes with 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) have been synthesized and characterized by infrared and 1H, 13C NMR, 13C CPMAS spectroscopy. The structures of the cis-PtCl2(dbtp)2 · EtOH (1) and cis-PdCl2(dbtp)(dmso) (2) has been determined by signal-crystal X-ray diffraction. In both complexes the X-ray crystal structures shows that heterocycle ligand (dbtp) binds the central atom monodentate via nitrogen atom N(3). In addition, compound (2) is interesting for its structural features, because it is the first report of mixed dichloride Pd(II) complexes with N-donor (triazolopyrimidine) and S-donor (dimethylsulfoxide) ligands. In this structure the Pd–Cl distances are: 2.302(1) and 2.281(1) Å, Pd–N 2.041(3) Å and Pd–S 2.245(1) Å. The 1H, 13C NMR studies show clearly that these structures are retained in solution. 相似文献