全文获取类型
收费全文 | 5805篇 |
免费 | 251篇 |
国内免费 | 39篇 |
专业分类
化学 | 4100篇 |
晶体学 | 35篇 |
力学 | 186篇 |
数学 | 854篇 |
物理学 | 920篇 |
出版年
2023年 | 50篇 |
2022年 | 93篇 |
2021年 | 147篇 |
2020年 | 164篇 |
2019年 | 167篇 |
2018年 | 109篇 |
2017年 | 101篇 |
2016年 | 216篇 |
2015年 | 173篇 |
2014年 | 224篇 |
2013年 | 322篇 |
2012年 | 414篇 |
2011年 | 476篇 |
2010年 | 216篇 |
2009年 | 181篇 |
2008年 | 381篇 |
2007年 | 374篇 |
2006年 | 354篇 |
2005年 | 303篇 |
2004年 | 262篇 |
2003年 | 221篇 |
2002年 | 195篇 |
2001年 | 56篇 |
2000年 | 58篇 |
1999年 | 50篇 |
1998年 | 53篇 |
1997年 | 48篇 |
1996年 | 71篇 |
1995年 | 37篇 |
1994年 | 38篇 |
1993年 | 37篇 |
1992年 | 33篇 |
1991年 | 33篇 |
1990年 | 35篇 |
1989年 | 22篇 |
1988年 | 23篇 |
1987年 | 24篇 |
1986年 | 15篇 |
1985年 | 32篇 |
1984年 | 43篇 |
1983年 | 13篇 |
1982年 | 36篇 |
1981年 | 29篇 |
1980年 | 32篇 |
1979年 | 27篇 |
1978年 | 21篇 |
1977年 | 21篇 |
1976年 | 22篇 |
1975年 | 14篇 |
1974年 | 14篇 |
排序方式: 共有6095条查询结果,搜索用时 546 毫秒
41.
1,4-Diamino-2-butyne was prepared from 1,4-dichloro-2-butyne via 1,4-diazido-2-butyne. Bis(amino acid) derivatives of 1,4-diamino-2-butyne having the general structure (Boc-Xxx-NHCH2C[triple bond])2 (Xxx = Ala, Phe and Met) were prepared and examined by 1H NMR spectroscopy. Using chemical shift, coupling constant and DMSO titration data it is found that these compounds adopt a C2-symmetric turn conformation featuring two intramolecular hydrogen bonds. 相似文献
42.
Application of stir bar sorptive extraction for wine analysis 总被引:4,自引:0,他引:4
Yoji?Hayasaka Kevin?MacNamara Gayle?A.?Baldock Randell?L.?Taylor Alan?P.?PollnitzEmail author 《Analytical and bioanalytical chemistry》2003,375(7):948-955
Stir bar sorptive extraction (SBSE) coupled with gas chromatography/mass spectrometry (GC/MS) was used to analyse wine samples for three applications: flavour and compositional analysis; 2,4,6-trichloroanisole (TCA), a common off-aroma in wine; and agrochemicals. SBSE was found to be orders of magnitude more sensitive than modern conventional methodology, allowing for lower detection and quantitation levels, and improved confirmation of identity; SBSE often gave better signal to noise in scan mode than other methods in selective ion monitoring (SIM) mode. With the help of their characteristic mass spectra all agrochemicals could be identified unambiguously at concentrations of 10 microg L(-1) in wine and a further 100 constituents were detected in a Cabernet Sauvignon sample. Thus it is now possible to analyse complex samples such as wine by scan mode, with better confirmation of identity, and without sacrificing sensitivity, where previously SIM methodology had to be used. 相似文献
43.
Tobacco protein separation by aqueous two-phase extraction 总被引:13,自引:0,他引:13
Tobacco has long been considered as a host to produce large quantity of high-valued recombinant proteins. However, dealing with large quantities of biomass is a challenge for downstream processing. Aqueous two-phase extraction (ATPE) has been widely used in purifying proteins from various sources. It is a protein-friendly process and can be scaled up easily. In this paper, ATPE was studied for its applicability to recombinant protein purification from tobacco with egg white lysozyme as the model protein. Separate experiments with poly(ethylene glycol) (PEG)-salt-tobacco extract and PEG-salt-lysozyme were carried out to determine the partition behavior of tobacco protein and lysozyme, respectively. Two-level fractional factorial designs were used to study the effects of factors such as, PEG molecular mass, PEG concentration, the concentration of phase forming salt, sodium chloride concentration and pH, on protein partitioning. The results showed that, among the studied systems, PEG-sodium sulfate system was most suitable for lysozyme purification. Detailed experiments were conducted by spiking lysozyme into the tobacco extract. The conditions with highest selectivity of lysozyme over native tobacco protein were determined using a response surface design. The purification factor was further improved by decreasing the phase ratio along the tie line corresponding to the phase compositions with the highest selectivity. Under selected conditions the lysozyme yield was predicted to be 87% with a purification factor of 4 and concentration factor of 14. From this study, ATPE was shown to be suitable for initial protein recovery and partial purification from transgenic tobacco. 相似文献
44.
Observation of a quadrupole plasmon mode for a colloidal solution of gold nanoprisms 总被引:3,自引:0,他引:3
Millstone JE Park S Shuford KL Qin L Schatz GC Mirkin CA 《Journal of the American Chemical Society》2005,127(15):5312-5313
The synthesis and optical properties of single crystalline gold nanoprisms have been investigated. A three-step mediated seed growth process in an aqueous solution generated gold nanoprisms with a relatively homogeneous size distribution. The purity of these nanostructures has allowed us to observe a weak quadrupole resonance in addition to a strong dipole resonance associated with these novel structures. The experimental optical spectra agree with discrete dipole approximation calculations that have been modeled from the dimensions of gold nanoprisms produced in this synthesis. 相似文献
45.
The use of novel water-in-oil microemulsions in microemulsion electrokinetic chromatography 总被引:3,自引:0,他引:3
We describe the novel use of water-in-oil (W/O) microemulsions to achieve unique separations in microemulsion electrokinetic chromatography (MEEKC). The choice and concentration of the buffer type, surfactant and co-surfactant were all examined and optimized. Separations of a range of neutral and acidic analytes was shown to be markedly different to that obtained by (oil-in-water) O/W MEEKC. Neutral solutes are separated by virtue of their solubility (log P) values in O/W MEEKC with the more water-insoluble solutes migrating last. This separation process does not occur in W/O, as neutral solutes are not separated in order of log P. 相似文献
46.
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
47.
Li YS Xiao Y Wright PB Tran T 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(7):1675-1681
3-(Triethoxysilyl)propionitrile (TESPN) sol-gel has been prepared under different conditions. It was employed for coating the surfaces of quartz and aluminum. Infrared (IR) and Raman spectra of TESPN and TESPN sol-gels have been recorded in the study of the sol-gel process. Transmission and reflection absorption IR (RAIR) spectra of TESPN sol-gel coated quartz and aluminum have also been collected for better understanding the film formation on the substrate surfaces. Spectra collected at different temperatures indicated that the silane film on quartz decomposes at 700 degrees C. Results from thermal gravimetric analysis (TGA) supported this result. Based on the group frequencies and the spectral behavior in different states, some vibrational modes were assigned to the observed bands. The anticorrosion behavior of the sol-gel coated aluminum in comparison with the uncoated metal was evaluated by measuring the potentiodynamic polarization and electrochemical impedance spectra (EIS). 相似文献
48.
David Kessel Kevin M. Smith R. K. Pandey F.-Y. Shiau Barbara Henderson 《Photochemistry and photobiology》1993,58(2):200-203
Abstract— Biophysical and photobiological properties of a group of bacteriochlorins were compared with efficacy of these products for photodynamic therapy of murine tumors. Predictive factors for selective photosensitization in vivo include affinity binding to lipoproteins greater than albumin, extinction coefficient at the wavelength of irradiation and tumor/skin distribution. Efficacy was correlated with circulating plasma levels of the different sensitizers but not with the photodynamic therapy response in cell culture. 相似文献
49.
An automatic method for the absolute determination of total sulfur, which overcomes the tendency of previous methods to give low sulfur recoveries on samples with high oxygen demand, is described. The technique combusts the sample in oxygen and sweeps the combustion gases through a hydrogen peroxide trap to remove the sulfur oxides from the gas stream. The trap contents are volatilized and swept with nitrogen through reduced copper heated to 890 °C. Sulfur oxides are quantitatively converted to sulfur dioxide and titrated coulometrically with iodine. Halogens are held by the copper and do not interfere with the sulfur determination. Analysis time is 12 min and automation of the method allows unattended operation. Sample size is 0.5 to 20 mg. Sulfur levels of 0.05 to 100% can be determined. 相似文献
50.