全文获取类型
收费全文 | 90486篇 |
免费 | 16374篇 |
国内免费 | 9190篇 |
专业分类
化学 | 61527篇 |
晶体学 | 915篇 |
力学 | 5747篇 |
综合类 | 512篇 |
数学 | 10093篇 |
物理学 | 37256篇 |
出版年
2024年 | 344篇 |
2023年 | 2043篇 |
2022年 | 3293篇 |
2021年 | 3496篇 |
2020年 | 3927篇 |
2019年 | 3510篇 |
2018年 | 3216篇 |
2017年 | 2866篇 |
2016年 | 4583篇 |
2015年 | 4363篇 |
2014年 | 5320篇 |
2013年 | 6765篇 |
2012年 | 8210篇 |
2011年 | 8398篇 |
2010年 | 5546篇 |
2009年 | 5379篇 |
2008年 | 5779篇 |
2007年 | 5065篇 |
2006年 | 4760篇 |
2005年 | 3818篇 |
2004年 | 2940篇 |
2003年 | 2294篇 |
2002年 | 2108篇 |
2001年 | 1815篇 |
2000年 | 1605篇 |
1999年 | 1839篇 |
1998年 | 1591篇 |
1997年 | 1576篇 |
1996年 | 1563篇 |
1995年 | 1323篇 |
1994年 | 1150篇 |
1993年 | 996篇 |
1992年 | 858篇 |
1991年 | 784篇 |
1990年 | 645篇 |
1989年 | 501篇 |
1988年 | 371篇 |
1987年 | 308篇 |
1986年 | 324篇 |
1985年 | 261篇 |
1984年 | 151篇 |
1983年 | 117篇 |
1982年 | 100篇 |
1981年 | 57篇 |
1980年 | 42篇 |
1979年 | 15篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1957年 | 31篇 |
1922年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
A general and efficient Cu(I)-catalyzed cross-coupling reaction of terminal alkynes and monooxalyl chloride for the synthesis of 2-oxo-3-butynoates and 2-oxo-3-butynoamides was developed. Readily available starting materials, the mild reaction conditions, wide functional group tolerance, and the obviation of stoichiometric organolithium or magnesium reagents combine to highlight this reaction. 相似文献
962.
For the first time, a new method is described for the determination of scandium based on the cathodic adsorptive stripping of the scandium-alizarin red S complex onto a carbon paste electrode. The second-order derivative linear scan voltammograms of the complex are recorded by use of model JP-303 polarographic analyzer from 0.0 to -1.0 V (versus SCE). Optimum conditions are found to be: an acetic acid (0.36 mol l(-1))-potassium biphthalate (0.064 mol l(-1)) buffer solution (pH 4.0) containing 2.0x10(-5) mol l(-1) alizarin red S, a preconcentration potential of 0.0 V, a preconcentration time of 60 s, a rest time of 10 s and a scan rate of 100 mV s(-1). The results show that the complex can be adsorbed on the surface of a carbon paste electrode, yielding one peak at -0.58 V, corresponding to the reduction of alizarin red S in the complex at the electrode. The detection limit is found to be 6.0x10(-10) mol l(-1) for 3 min of preconcentration time. The linear range is 1.0x10(-9) to 4.0x10(-7) mol l(-1). Application of the procedure to the determination of scandium in the ore samples gave good results. 相似文献
963.
964.
JPC – Journal of Planar Chromatography – Modern TLC - A new bonded RP-18 sintered silica gel plate for use in reversed-phase planar electrochromatography has been prepared in our... 相似文献
965.
Wang M Wang BM Shi L Tu YQ Fan CA Wang SH Hu XD Zhang SY 《Chemical communications (Cambridge, England)》2005,(44):5580-5582
A quinine/Selectfluor combination inducing rearrangement reaction of allylic alcohols was discovered, which involved a moderate yield with good enantioselective construction of alpha-quaternary carbon center and beta-fluoro aldehyde under base condition. 相似文献
966.
A rapid tandem mass spectrometric (MS-MS) method for the quantification of gabapentin (GBP) in human plasma using 4-phenyl-4-aminobutanoic acid as an internal standard (IS) has been developed and validated. The drug and the internal standard were analyzed, by flow injection analysis without chromatographic separation, using a mobile phase of acetonitrile-water-formic acid (50:50:0.025, v/v/v) at a flow rate of 0.1 mL min?1. The run-cycle time was <3 min injection-to injection. Quantitation was achieved using multiple reaction monitoring (MRM) scan at MRM transitions m/z 172 > 154 and m/z 180 > 117 for GBP and the IS, respectively. Ion suppression study indicated practically no suppressive effect of plasma constituents on the mass ions detection of GBP and IS, when measured in MRM scanning mode. Calibration curves were linear over the concentration range of 0.1–10 μg mL?1 (r > 0.999) with a limit of quantification of 0.1 μg mL?1 (RSD%; 7.6 and % DEVs; ?3.0 to +17.0%). Validation data showed that the RSD% values were in the range of 1.85 to 13.06%, whereas, the % DEVs values ranged from ?1.4 to +10.0% indicating good precision and accuracy. Analytical recoveries of GBP from spiked human plasma were in the range of 98.9 to 101.3%. On the other hand, recoveries of GBP from stored human plasma samples were in the range of 100.0 to 107.5% indicating that GBP was stable in plasma, with no appreciable degradation, when stored at ?20 °C. The developed method was applied for GBP monitoring in plasma samples of patients treated with GBP. 相似文献
967.
Sodium phosphate tellurite glasses in the system (NaPO(3))(x)(TeO(2))(1-) (x) were prepared and structurally characterized by thermal analysis, vibrational spectroscopy, X-ray photoelectron spectroscopy (XPS) and a variety of complementary solid-state nuclear magnetic resonance (NMR) techniques. Unlike the situation in other mixed-network-former glasses, the interaction between the two network formers tellurium oxide and phosphorus oxide produces no new structural units, and no sharing of the network modifier Na(2)O takes place. The glass structure can be regarded as a network of interlinked metaphosphate-type P(2) tetrahedral and TeO(4/2) antiprismatic units. The combined interpretation of the O 1s XPS data and the (31)P solid-state NMR spectra presents clear quantitative evidence for a nonstatistical connectivity distribution. Rather, the formation of homoatomic P--O--P and Te--O--Te linkages is favored over mixed P--O--Te connectivities. As a consequence of this chemical segregation effect, the spatial sodium distribution is not random, as also indicated by a detailed analysis of (31)P/(23)Na rotational echo double-resonance (REDOR) experiments. 相似文献
968.
Nitropyridines reacted with an excess of vinyl Grignard reagent to produce 4- or 6-azaindoles. Improved yields were obtained when a halogen atom was present at the position alpha to the nitrogen atom in the pyridine ring. 相似文献
969.
Liang SC Wang H Zhang ZM Zhang X Zhang HS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(12):2605-2611
A new thiol weak-fluorescence probe, 5-maleimidyl-2-(m-methylphenyl)benzoxazole (MMPB), gives a highly fluorescence product in the presence of Cys. In this paper, MMPB has been developed for the fluorimetric determination of cysteine (Cys). At lambda(ex)/lambda(em) = 305.6/425.6 nm, the linear range is from 0 to 3.3 x 10(-7) mol l(-1) and the detection limit (sigma = 3) of 6.2 x 10(-10) mol l(-1). The main advantage of this method lies in the relative high selectivity compared with the methods using other N-substituted maleimide type of thiol reagents, in which 0.15-fold (molar ratio) of GSH is allowed and most of other amino acids at 100-fold (molar ratio) level had no obvious effect on the results. The proposed method has been applied to the determination of Cys in real samples. 相似文献
970.
利用辐射方法制备硫酸根离子选择电极活性材料,至今未见报导,我们首次采用辐射接枝方法制备了以疏水性高分子为骨架的带有SO~-活性基团的功能高分子活性材料,研制了硫酸根离子选择电极。结果表明,该电极具有内阻低,响应快,稳定性较好的特点,且其功能曲线的线性范围为10~(-1)~10~(-4)MSO_4~-,适宜的pH范围为4~9。 相似文献