全文获取类型
收费全文 | 40748篇 |
免费 | 5291篇 |
国内免费 | 5346篇 |
专业分类
化学 | 27609篇 |
晶体学 | 620篇 |
力学 | 2500篇 |
综合类 | 402篇 |
数学 | 4114篇 |
物理学 | 16140篇 |
出版年
2025年 | 23篇 |
2024年 | 471篇 |
2023年 | 826篇 |
2022年 | 1451篇 |
2021年 | 1673篇 |
2020年 | 1841篇 |
2019年 | 1895篇 |
2018年 | 1376篇 |
2017年 | 1388篇 |
2016年 | 1860篇 |
2015年 | 2035篇 |
2014年 | 2461篇 |
2013年 | 3059篇 |
2012年 | 3524篇 |
2011年 | 3569篇 |
2010年 | 2642篇 |
2009年 | 2702篇 |
2008年 | 2938篇 |
2007年 | 2441篇 |
2006年 | 2257篇 |
2005年 | 1826篇 |
2004年 | 1383篇 |
2003年 | 1144篇 |
2002年 | 1157篇 |
2001年 | 940篇 |
2000年 | 755篇 |
1999年 | 625篇 |
1998年 | 457篇 |
1997年 | 407篇 |
1996年 | 361篇 |
1995年 | 291篇 |
1994年 | 291篇 |
1993年 | 234篇 |
1992年 | 181篇 |
1991年 | 145篇 |
1990年 | 143篇 |
1989年 | 94篇 |
1988年 | 81篇 |
1987年 | 63篇 |
1986年 | 74篇 |
1985年 | 47篇 |
1984年 | 26篇 |
1983年 | 30篇 |
1982年 | 14篇 |
1981年 | 14篇 |
1980年 | 10篇 |
1979年 | 21篇 |
1977年 | 11篇 |
1957年 | 8篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
Adsorption, desorption and activities of acid phosphatase on various colloidal particles from an Ultisol 总被引:1,自引:0,他引:1
Adsorption, desorption and activity of acid phosphatase on various soil colloidal particles and pure clay minerals were studied. Higher adsorption amounts and low percentage of desorption of acid phosphatase were found on fine soil clays (<0.2 μm). Electrostatic force and ligand exchange are the major driving forces that are involved in the adsorption of enzymes on soil clays. More enzyme molecules were adsorbed on soil clays in the presence of organic components. However, enzymes on organic clays were more easily released. One-third of the enzyme on goethite was adsorbed via ligand exchange process. Some other interactions, such as van der Waals force, hydrophobic force and hydrogen bonding may be more important in the adsorption of enzyme on kaolinite and the enzyme in this system cannot be easily removed. Coarse clays (0.2–2 μm) and inorganic soil clays had higher affinities for enzyme molecules than fine clays and organic clays, respectively. The activity of enzyme bound on soil clays was inhibited and the thermal stability was increased in the presence of organic matter. Data obtained in this study are helpful for a better understanding of the interactions of enzymes with inorganic and organic constituents in soil and associated environments. 相似文献
22.
The bicyclic keto lactone 26 was synthesized for the purpose of developing a viable route to marine diterpenes of the crenulatan type. Following the efficient conversion of (S)-citronellol ( 5 ) to the allylated alcohol 9a (Scheme 2), the αβ-unsaturated lactone 12 was efficiently accessed in preparation for stereocontrolled conjugate addition. The hydroxymethyl equivalent most suited to this task was (i-PrO)Me2SiCH2MgCl, which gave 13 predominantly in the presence of CuI and Me3SiCl. Once the OH group was deprotected (→ 14 ), it proved an easy matter to implement acid-catalyzed isomerization to lactone 15 , oxidation of which gave the pivotal aldehyde 16 . Condensation of 16 with PhSeCH2Li led via 21 to 22 (Scheme 3). Once the OH group was protected (→ 22b ), it proved possible to effect aldolization with crotonaldehyde (→ 23 ). Exposure of 23 to acid gave the sub-target compound 25 . Its subsequent oxidation and thermal activation resulted in sequential selenoxide elimination with Claisen rearrangement (→ 26 ). The structural features of 26 require that a chair-like transition state be adopted during the [3.3]sigmatropic event. With the clarification of these issues, a highly serviceable and more advanced assault on the crenulatans should prove capable of being mounted. 相似文献
23.
本文提出了富烯碳原子簇的石墨层间闭合形成机理,由该机理推出的许多结果与实验事实符合很好。我们认为碳原子簇自由基的快速淬灭及其淬灭速度是富烯碳原子簇形成及其丰度的决定因素。由此得出富烯碳原子簇在给定实验条件下产生的必然性,并预言不同大小的富烯碳原子簇可以通过优化实验条件选择性地合成。 相似文献
24.
A solution-phase synthesis of bicyclic prolines containing four points of diversity has been developed by a two-step synthesis involving 1,3-dipolar cycloaddition of perfluoroalkylsulfonyl-protected hydroxybenzaldehydes followed by Pd-catalyzed Suzuki coupling reaction of fluorous sulfonates with boronic acids. Both reactions are conducted under microwave irradiation and reaction mixtures are purified by solid-phase extractions without performing chromatography. 相似文献
25.
K. Daum W. Rhode P. Bareyre R. Barloutaud G. Chardin B. Degrange J. Ernwein B. Kuznik H. Meyer L. Mosca L. Moscoso O. Perdereau M. Schubnell S. Tisserant Y. Wei 《Zeitschrift fur Physik C Particles and Fields》1995,66(3):417-428
The combined analysis of the final event set of data on neutrino interactions inside the detector, upward going stopping muons and horizontal muons recorded in the Fréjus experiment is presented. The absolute atmospheric neutrino spectra in the energy range
for electron neutrinos and
for muon neutrinos are determined. Based on the parameterization of Volkova for thev
µ
a spectral index of =2.66±0.05 is obtained from the ratio of horizontal muons over upward going stopping muons and from the measurement of the energy loss of horizontal muons inside the detector. The neutrino spectra are compared with various flux calculations. They do not show any evidence for neutrino oscillations in agreement with earlier analyses of the Fréjus data.Now atUniversity of Michigan, Ann Arbor, USA 相似文献
26.
Summary In this paper it is proved that, for any positive integern 2, 3 (mod 4),n 7, there exists an incomplete idempotent Schröder quasigroup with one hole of size two IISQ(n, 2) except forn = 10. It is also proved that for any positive integern 0, 1 (mod 4), there exists an idempotent Schröder quasigroup ISQ(n) except forn = 5 and 9. These results completely determine the spectrum of ISQ(n) and provide an application to the packing of a class of edge-coloured block designs.Research supported by NSERC grant A-5320.Research supported by NSFC grant 19231060-2. 相似文献
27.
The cis and trans isomers of [Cd(dmbpy)2](NO3)2] (dmbpy = 4,4′-dimethyl-2,2′-bipyridine) have been synthesized simultaneously via a one-pot reaction of Cd(NO3)2 · 4H2O with the dmbpy ligand in a MeOH/H2O mixture; they can be obtained individually by means of the mechanical separation due to their different growing habit of
the single-crystals. Different π-stacking interactions are observed in the cis and trans isomers forming different one-dimensional networks. The outcome of the DFT calculations agrees well with the experimental
results. 相似文献
28.
Ai‐Hua Zhao Yan Zhang Zhao‐Hui Xu Jian‐Wen Liu Wei Jia 《Helvetica chimica acta》2004,87(12):3160-3166
Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3). 相似文献
29.
Alexandra Alimova A. Katz Rakhi Podder Glenn Minko Hul Wei R. R. Alfano Paul Gottlieb 《Photochemistry and photobiology》2004,80(1):41-46
Native fluorescence spectroscopy was used for in situ investigations of two lipid‐containing bacteriophages from the cystovirus family as well as their Pseudomonad host cells. Both the viruses φ6 and φ12 and their bacterial host proteins contain the amino acid tryptophan (trp), which is the predominant fluorophore in UV. Within proteins, trp's structural environment differs, and the differences are reflected in their spectroscopic signatures. It was observed that the peak of the trp emission from both viruses was at 330 nm, a significantly shorter wavelength than trp in either the Pseudomonad host cells or the amino acid's chemical form. This allowed us to monitor the viral attachment process and subsequent lytic release of progeny virus particles by measurement of the trp emission spectra during the infection process. This work demonstrates that fluorescence may offer a novel tool to detect viruses and monitor viral infection of cells and may be part of a biodefense application. 相似文献
30.
The spin states of iron (II) in FeL2(NCS)2 produced from the thermal decomposition of FeL8(NCS)2 (L=2-py-CR1=NR2, R1 or R2=H, Me(CH3), Ph) under nitrogen atmosphere are investigated by means of Mössbauer spectroscopy and magnetic measurements. It was found that the spin states of iron (II) in substitutited bis (2-pyridylimine) iron (II) thiocyanate are included: intermediate-spin (3T1, S=1), mixed-spin of 5T2(S=2)+3T1 and spin incomplete transition of 5T2?3T1. 相似文献