全文获取类型
收费全文 | 2172篇 |
免费 | 109篇 |
国内免费 | 66篇 |
专业分类
化学 | 1421篇 |
晶体学 | 23篇 |
力学 | 44篇 |
综合类 | 5篇 |
数学 | 346篇 |
物理学 | 508篇 |
出版年
2023年 | 13篇 |
2022年 | 19篇 |
2021年 | 34篇 |
2020年 | 37篇 |
2019年 | 31篇 |
2018年 | 37篇 |
2017年 | 33篇 |
2016年 | 52篇 |
2015年 | 61篇 |
2014年 | 66篇 |
2013年 | 123篇 |
2012年 | 129篇 |
2011年 | 161篇 |
2010年 | 109篇 |
2009年 | 117篇 |
2008年 | 147篇 |
2007年 | 157篇 |
2006年 | 105篇 |
2005年 | 128篇 |
2004年 | 104篇 |
2003年 | 95篇 |
2002年 | 72篇 |
2001年 | 61篇 |
2000年 | 59篇 |
1999年 | 37篇 |
1998年 | 29篇 |
1997年 | 26篇 |
1996年 | 19篇 |
1995年 | 17篇 |
1994年 | 20篇 |
1993年 | 28篇 |
1992年 | 20篇 |
1991年 | 14篇 |
1990年 | 11篇 |
1989年 | 15篇 |
1988年 | 12篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 24篇 |
1984年 | 11篇 |
1983年 | 13篇 |
1982年 | 11篇 |
1981年 | 10篇 |
1980年 | 16篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1977年 | 9篇 |
1976年 | 4篇 |
1966年 | 3篇 |
1942年 | 3篇 |
排序方式: 共有2347条查询结果,搜索用时 15 毫秒
31.
Aurora Molinari Alfonso Oliva Luc Snchez Arturo San Feliciano 《Journal of heterocyclic chemistry》1997,34(4):1297-1299
1-Phenyl-3,5-dioxopyrazolidine 1 reacts with carbon disufide and alkyl halides in presence of excess of sodium acetate in dimethylformamide to afford the ketene dithioacetals 3a-h . The 13C chemical shift assignments of these compounds were made on the basis of two-dimensional nmr studies performed on the N-methylketene dithioacetal derivative 4. 相似文献
32.
A nonadiabatic quantum dynamic model has been developed to study the process of electron emission from a low-work-function metal surface. The process is initiated by scattering a highly vibrationally excited NO molecule from a surface composed of a Cs layer covering a Ru crystal. The model addresses the increasing quantum yield of the electron emission as a function of the molecular vibrational excitation and incident kinetic energy. The reaction mechanism is identified as a long-range harpooning electron transfer to a molecular ion which is then accelerated toward the surface. Upon impact, the molecular ion emits its excess electron. 相似文献
33.
Single bacterial cells, each expressing a different library variant, were compartmentalized in aqueous droplets of water-in-oil (w/o) emulsions, thus maintaining a linkage between a plasmid-borne gene, the encoded enzyme variant, and the fluorescent product this enzyme may generate. Conversion into a double, water-in-oil-in-water (w/o/w) emulsion enabled the sorting of these compartments by FACS, as well as the isolation of living bacteria cells and their enzyme-coding genes. We demonstrate the directed evolution of new enzyme variants by screening >10(7) serum paraoxonase (PON1) mutants, to yield 100-fold improvements in thiolactonase activity. In vitro compartmentalization (IVC) of single cells, each carrying >10(4) enzyme molecules, in a volume of <10 femtoliter (fl), enabled detection and selection despite the fast, spontaneous hydrolysis of the substrate, the very low initial thiolactonase activity of PON1, and the use of difusable fluorescent products. 相似文献
34.
A. Gil 《Adsorption》1998,4(3-4):197-206
The micropore structure of four microporous materials (two zeolites, ZSM-5 and Y-82; an activated carbon and an alumina pillared clay) and their binary physical mixtures (50-50 wt%) have been examined by nitrogen adsorption at 77 K. Various micropore sizes have been considered from the stages on the micropore filling mechanism in the microporous materials. The application of the Dubinin-Astakhov (DA) equation to characterize and obtain the adsorption potential distributions of the microporous materials is presented. 相似文献
35.
Solid-phase methodology for the preparation of pyrrolo[3,2-d]pyrimidine-6-carboxylates with diversity at the N3 pyrmidine nitrogen has now been elaborated to allow for the generation of pyrrolopyrimidine libraries with members possessing diversity at the N3, N5, and C6 positions. The diversification of the N5 position was achieved by treating the parent resin-bound pyrrolo[3,2-d]pyrimidines 3 with an alkyl halide in the presence of Cs2CO3 in DMF. Modification of the C6 carboxylate of resin-bound pyrrolopyrimidines 3-5 was first achieved by hydrolysis of the benzyl ester using LiOH in a mixture of THF/H2O/MeOH. Further alteration of the C6 position of resin-bound pyrrolo[3,2-d]pyrimidine-6-carboxylic acids 6-8 was then performed by activation with triphosgene and treatment with an amine to furnish resin-bound pyrrolo[3,2-d]pyrimidine-6-amides. Twenty-two pyrrolo[3,2-d]pyrimidines 1a-v with different substituents at the N3, N5, and C6 positions were obtained in yields of 21-83% and purities of 61-98% after cleavage from the solid support. 相似文献
36.
Diverse existing lines for the calculation of excited states are exposed, with an emphasis on those methods that consider
both types of correlation energy: the dynamic and the non-dynamic one. We analyze the possibility of to calculate the dynamic
correlation energy using a correlation energy density functional applied to a multi-determinantal wavefunction, which would
include the non-dynamic correlation energy, versus the use of mono-determinantal wavefunctions, which are not able to include
the long-range correlation energy, and versus the use of variational or perturbative calculations from multi-determinantal
wavefunctions, with their excessive computational cost. The results obtained with several methods are compared.
Contribution to the Serafin Fraga Memorial Issue. 相似文献
37.
We have investigated the electrochemical genosensing properties of gold nanoparticle–carbon nanotube hybrid. Thiolated oligonucleotide probes and mercaptohexanol were self-assembled onto the Au–CNT hybrid. The hybridization events of target oligonucleotides are monitored using electrochemical impedance spectroscopy, cyclic voltammetry and a.c. voltammetry techniques. A redox-active mediator is used to detect the oxidation of guanine residues. The as-fabricated genosensor is able to differentiate between complementary and mismatched hybridizations, relying on the oxidation current of the guanine residues mediated via . 相似文献
38.
The photodegradation of 1,3-dimethyl-1-(2-(3-fluorobenzylthio)-1,3,4-thiadiazol-5-yl)urea as a thin film and in solution is described. The two photoproducts from thin-film photolysis were characterized by spectral and synthetic methods. The X-ray crystal structure of one of the photoproducts is also reported. The rearrangements were shown to involve an S-to-N benzyl migration, followed by a sulfur-oxygen substitution. 相似文献
39.
We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH4)2SiF6 treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm−1 (AlO)(SiO)2SiO1HAl(OSi)3 and more acidic 3625 cm−1 (SiO)3SiO1HAl(OSi)3 groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in 29Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm−1 hydroxyls interacting with extraframework Al species. 相似文献
40.
Spectrafluorimetric method for the rapid screening of toxic heavy metals in water samples 总被引:1,自引:0,他引:1
B. San Vicente de la RivaJ.M. Costa-Fernández R. PereiroA. Sanz-Medel 《Analytica chimica acta》2002,451(2):203-210
A fast and inexpensive sensitive screening test for recognising potential wastewater contamination by the presence of highly toxic heavy metals is described. The test is based on the reaction of the toxic heavy metals Hg(II), Cd(II), Pb(II) and Ag(I) with 6-mercaptopurine (6-MP) to produce highly fluorescent complexes.Optimum experimental conditions include a buffer of pH 7.2 (0.1 M citric acid/0.2 M Na2HPO4), a chelating reagent concentration of 6×10−4 M and the addition of 10−4 M of o-phenanthroline. The fluorescence emitted by the complexes was measured at 380 and 540 nm for excitation and emission wavelengths, respectively.Detection limits of 4, 3, 6 and 3 μg l−1 were achieved for Hg, Cd, Pb and Ag. Relative standard deviation (R.S.D.) were between ±2 and ±6% of the fluorescence signals for five identical samples. Potential interference effects from other heavy metals (Zn, Mn, Co, Fe, Ni and Cu), which could affect the response of the proposed screening test was investigated. Results showed that none of these metals give rise to noticeable fluorescence signals under the above described experimental conditions.Finally, the capability of the proposed heavy metal screening test for the analysis of contaminated water samples is discussed. 相似文献