全文获取类型
收费全文 | 30863篇 |
免费 | 4722篇 |
国内免费 | 3420篇 |
专业分类
化学 | 22997篇 |
晶体学 | 447篇 |
力学 | 1724篇 |
综合类 | 254篇 |
数学 | 3448篇 |
物理学 | 10135篇 |
出版年
2024年 | 24篇 |
2023年 | 533篇 |
2022年 | 639篇 |
2021年 | 985篇 |
2020年 | 1242篇 |
2019年 | 1142篇 |
2018年 | 956篇 |
2017年 | 884篇 |
2016年 | 1437篇 |
2015年 | 1424篇 |
2014年 | 1608篇 |
2013年 | 2286篇 |
2012年 | 2714篇 |
2011年 | 2809篇 |
2010年 | 1943篇 |
2009年 | 1787篇 |
2008年 | 2080篇 |
2007年 | 1772篇 |
2006年 | 1687篇 |
2005年 | 1594篇 |
2004年 | 1210篇 |
2003年 | 1050篇 |
2002年 | 1107篇 |
2001年 | 794篇 |
2000年 | 714篇 |
1999年 | 674篇 |
1998年 | 478篇 |
1997年 | 404篇 |
1996年 | 418篇 |
1995年 | 390篇 |
1994年 | 322篇 |
1993年 | 292篇 |
1992年 | 254篇 |
1991年 | 222篇 |
1990年 | 206篇 |
1989年 | 164篇 |
1988年 | 146篇 |
1987年 | 104篇 |
1986年 | 100篇 |
1985年 | 104篇 |
1984年 | 70篇 |
1983年 | 44篇 |
1982年 | 36篇 |
1981年 | 38篇 |
1980年 | 20篇 |
1979年 | 15篇 |
1976年 | 10篇 |
1975年 | 12篇 |
1971年 | 9篇 |
1957年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 250 毫秒
991.
Matthieu Baudelet Myriam Boueri Jin Yu Samuel S. Mao Vincent Piscitelli Xianglei Mao Richard E. Russo 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1329-1334
Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample. 相似文献
992.
993.
The paramagnetic complexes formed in Friedel‐Crafts alkylation reaction systems are invistigated by electron spin resonance (ESR) spectroscopy, in room temperature ionic liquids system 1‐butyl‐3‐methyl‐limidazolium chloride‐aluminium chloride ([bmim]Cl‐AlCl3). The results indicate that ESR spectra observed are due to polycyclic aromatic radical cations formed from their parent hydrocarbons. ESR spectrum of spin adduct is obtained in an ionic liquid system composed of [bmim]Cl‐AlCl3. In acidic solution the 14N hyperfine coupling constant of 4‐oxo‐TEMPO, 2.15 mT, is appreciably larger due to an adduct formed with AlCl3. 相似文献
994.
Shengbao Diao Mei Jin Jinfeng Sun Yi Zhou Chao Ye Yong Jin 《Natural product research》2019,33(5):701-707
A new diarylheptanoid, (2S,3S,5S)-2,3,5-trihydroxy-1,7-bis(4-hydroxy- 3-methoxyphenyl)heptane (1), and a new diarylheptanoid glycoside, (2S,3S,5S)-2,3-dihydroxy-5-O-β-d-xylopyranosyl-7-(4-hydroxy-3-methoxyphenyl)-1-(4-hydroxyphenyl)heptane (2), together with three known compounds, rhoiptelol C (3), rhoiptelol B (4) and 3′,4″-epoxy-2-O-β-d-glucopyanosyl-1-(4-hydroxyphenyl)- 7-(3-methoxyphenyl)heptan-3-one (5) were isolated from the roots of Juglans mandshurica (Juglandaceae). The structures of compounds 1 and 2 were identified based on HR-ESI-MS, 1D and 2D NMR spectroscopic methods. Compounds 1–5 were assayed for their inhibitory effects on the production of NO, TNF-α and IL-6 in LPS-stimulated RAW264.7 cells. 相似文献
995.
选用不同的醇改性剂,在自制的直链淀粉-三(3,5-二甲基苯基氨基甲酸酯)(ADMPC)手性固定相上,对2种吲哚环衍生物对映体进行了手性拆分研究,并考察了样品的保留时间和立体选择性. 相似文献
996.
Maria Weber Hai-Hao Han Bo-Han Li Maria
L. Odyniec Charlotte E. F. Jarman Yi Zang Steven D. Bull Amanda B. Mackenzie Adam C. Sedgwick Jia Li Xiao-Peng He Tony D. James 《Chemical science》2020,11(32):8567
Reaction-based fluorescent-probes have proven successful for the visualisation of biological species in various cellular processes. Unfortunately, in order to tailor the design of a fluorescent probe to a specific application (i.e. organelle targeting, material and theranostic applications) often requires extensive synthetic efforts and the synthetic screening of a range of fluorophores to match the required synthetic needs. In this work, we have identified Pinkment-OH as a unique “plug-and-play” synthetic platform that can be used to develop a range of ONOO− responsive fluorescent probes for a variety of applications. These include theranostic-based applications and potential material-based/bioconjugation applications. The as prepared probes displayed an excellent sensitivity and selectivity for ONOO− over other ROS. In vitro studies using HeLa cells and RAW 264.7 macrophages demonstrated their ability to detect exogenously and endogenously produced ONOO−. Evaluation in an LPS-induced inflammation mouse model illustrated the ability to monitor ONOO− production in acute inflammation. Lastly, theranostic-based probes enabled the simultaneous evaluation of indomethacin-based therapeutic effects combined with the visualisation of an inflammation biomarker in RAW 264.7 cells. Pinkment, a resorufin based ONOO− selective and sensitive ‘plug and play’ fluorescence-based platform for in vitro and in vivo use, enables facile functionalisation for various imaging and theranostic applications. 相似文献
997.
[reaction: see text] Highly stereodivergent Woodward-Prevost reaction applied to iodoacetates derived from homochiral alpha-amino acids afforded enantiopure 3,4-cis- and 3,4-trans-pyrrolidinediol derivatives, with control over the protecting group, allowing for differential protection. 相似文献
998.
用EXAFS研究NiO在γ-Al2O3表面上的分散 总被引:1,自引:0,他引:1
本文使用EXAFS方法研究NiO在γ-Al_2O_3的表面上的分散情况。文章讨论了Ni含量为7%、13%、18%、26%、35%的NiO/γ-Al_2O_3体系的径向结构函数图以及Ni含量为13%、26%的NiO/α-Al_2O_3样品的径向结构函数图,认为NiO能在γ-Al_2O_3表面上成单层分散。分散后的Ni-O距离接近NiO晶体的Ni-O距离,表明Ni离子和γ-Al_2O_3表面上的氧有很强的相互作用。 相似文献
999.
Huilan C Deyan H Tian L Hong Y Wenxia T Jian Chen J Peiju Zheng P Chenggang Chen C 《Inorganic chemistry》1996,35(6):1502-1508
Alkylcobalt(III) Schiff base B(12) model complexes with secondary alkyls or a bulky diamine in the equatorial position were synthesized and characterized. Structures have been first determined by X-ray diffraction analysis for i-C(4)H(9)Co(salen)(gamma-pic) (I), n-C(3)H(7)Co(salen)(gamma-pic) (II) and C(2)H(5)Co(SB) (III), where salen = N,N'-ethylenebis(salicylideneamine) dianion; SB = 1,1,2,2-tetramethyl-N,N'-ethylenebis(salicylideneamine) dianion, gamma-pic = gamma-picoline. Crystal data for I (CoC(26)N(3)O(2)H(30)): space group P2(1)/c with a = 6.661(5) ?, b = 18.612(2) ?, c = 19.533(3) ?, beta = 98.93(1) degrees, V = 2392.10 ?(3), D(calcd) = 1.320 g.cm(-3), Z = 4, and R = 0.048 for 4469 measured reflections. Crystal data for II (CoC(25)N(3)O(2)H(28)): space group P2(1)/c, a = 9.609(6) ?, b = 19.169(8) ?, c = 12.995(9) ?, beta = 106.9(7) degrees, V = 2290.4 ?(3), D(calcd) = 1.332 g.cm(-1), Z = 4, and R = 0.048 for 4358 measured reflections. Crystal data for III (CoC(22)N(2)O(2)H(27)): space group P2(1)/c, a = 8.318(3) ?, b = 21.579(2) ?, c = 11.572(2) ?, beta = 93.35(1) degrees, V = 2073.7 ?(3), D(calcd) = 1.314 g.cm(-1), Z = 4, and R = 0.060 for 3954 measured reflections. The crystal structure data reveal that complexes I and II display six-coordinate octahedral geometry; their Co-C, Co-N bond lengths, as well as the Co-C-C angles, are very close to those in 5'-deoxyadenosylcobalamin. Complex III is one of the very few compounds having five-coordinate square pyramidal geometry and observed instability of the Co-C bond. 相似文献
1000.
Nguyen Van Do Tran Duc Thiep Truong Thi An Tran Minh Duc Han Ngoc Cuong 《Journal of Radioanalytical and Nuclear Chemistry》1986,107(1):29-37
Photon activation analysis has been success-fully applied to the fast and non-destructive analysis of tin in cassiterite ores
based on the 159.7 keV gamma line of123mSn produced in the124Sn/γ, n/123mSn reaction. In order to improve the accuracy of analytical results, corrections for self-absorption and pile-up effects were
performed. Under typical conditions /15 μA electron beam current, 15 MeV bremsstrahlung energy, 5 min irradiation time and
10 min measurement/ the sensitivity of the analysis is 10 ppm. The proposed method can be used for routine analysis of tin
in geological samples. 相似文献