全文获取类型
收费全文 | 1318篇 |
免费 | 41篇 |
国内免费 | 3篇 |
专业分类
化学 | 1170篇 |
晶体学 | 5篇 |
力学 | 9篇 |
数学 | 94篇 |
物理学 | 84篇 |
出版年
2023年 | 6篇 |
2022年 | 22篇 |
2021年 | 22篇 |
2020年 | 6篇 |
2019年 | 19篇 |
2018年 | 8篇 |
2017年 | 5篇 |
2016年 | 38篇 |
2015年 | 31篇 |
2014年 | 23篇 |
2013年 | 75篇 |
2012年 | 86篇 |
2011年 | 106篇 |
2010年 | 60篇 |
2009年 | 45篇 |
2008年 | 95篇 |
2007年 | 109篇 |
2006年 | 91篇 |
2005年 | 103篇 |
2004年 | 54篇 |
2003年 | 46篇 |
2002年 | 53篇 |
2001年 | 23篇 |
2000年 | 16篇 |
1999年 | 20篇 |
1998年 | 15篇 |
1997年 | 11篇 |
1996年 | 31篇 |
1995年 | 9篇 |
1994年 | 12篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 15篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1931年 | 1篇 |
1914年 | 1篇 |
1908年 | 2篇 |
排序方式: 共有1362条查询结果,搜索用时 0 毫秒
21.
Harmon BA Laird CE Fishman GJ Parnell TA Camp DC Frederick CE Hurley DL Lindstrom DJ Moss CE Reedy RC Reeves JH Smith AR Winn WG Benton EV 《Radiation measurements》1996,26(6):863-880
We present an overview of the Long Duration Exposure Facility (LDEF) induced activation measurements. The LDEF, which was gravity-gradient stabilized, was exposed to the low Earth orbit (LEO) radiation environment over a 5.8 year period. Retrieved activation samples and structural components from the spacecraft were analyzed with low and ultra-low background HPGe gamma spectrometry at several national facilities. This allowed a very sensitive measurement of long-lived radionuclides produced by proton- and neutron-induced reactions in the time-dependent, non-isotropic LEO environment. A summary of major findings from this study is given that consists of directionally dependent activation, depth profiles, thermal neutron activation, and surface beryllium-7 deposition from the upper atmosphere. We also describe a database of these measurements that has been prepared for use in testing radiation environmental models and spacecraft design. 相似文献
22.
García-Granados A López PE Melguizo E Moliz JN Parra A Simeó Y Dobado JA 《The Journal of organic chemistry》2003,68(12):4833-4844
Several triterpenic derivatives, with the A-ring functionalized, were semisynthesized from oleanolic and maslinic acids. The reactivities of sulfites, sulfate, and epoxides in these triterpene compounds were investigated under different reaction conditions. Moreover, contracted A-ring triterpenes (five-membered rings) were obtained, by different treatments of the sulfate 7. From the epoxide 8, deoxygenated and halohydrin derivatives were semisynthesized with several nucleophiles. Ozonolysis and Beckmann reactions were used to yield 4-aza compounds, from five-membered ring olanediene triterpenes. The X-ray structure of sulfate 7 is given and compared with density functional theory geometries. Theoretical (13)C and (1)H chemical shifts (gauge-invariant atomic orbital method at the B3LYP/6-31G*//B3LYP/6-31G* level) and (3)J(H,H) coupling constants were calculated for compounds 5-9 and 34-36, identifying the (R)- or (S)-sulfur and alpha- or beta-epoxide configurations together with 4-aza or 3-aza structures. 相似文献
23.
Verdejo B Aguilar J Doménech A Miranda C Navarro P Jiménez HR Soriano C García-España E 《Chemical communications (Cambridge, England)》2005,(24):3086-3088
L-glutamate and L-aspartate selectivity is achieved by the action of two Cu2+ metal ions rightly disposed in a cyclophane-type macrocyclic framework; electrochemical sensing of glutamate has been achieved by adsorption of the copper complexes on graphite electrodes. 相似文献
24.
Estimation of diuretic drugs in biological fluids by HPLC 总被引:1,自引:0,他引:1
Summary This critical review of different methods proposed for the determination and screening of diuretics is directed mainly, because of its potential application, towards highperformance liquid chromatography. 相似文献
25.
Ruiz-Medina A Ortega-Barrales P Fernández-de Córdova ML Molina-Díaz A 《Journal of AOAC International》2002,85(2):369-374
A simple, rapid, inexpensive, and automated flow-through solid-phase spectroscopic sensing device is proposed for the sequential determination of 2 vitamins: thiamine and ascorbic acid. The vitamins are concentrated on ion-exchange gels, thiamine on Sephadex SP C-25, and ascorbic acid on Sephadex QAE A-25; both solid supports are packed in 2 different flow cells. The absorbance is monitored directly on the solid phase with a double-beam spectrophotometer at 250 nm, without derivatization or additional elution. With the use of 2 carrier/self-eluting solutions (0.1 5M sodium acetate/acetic acid and 0.18M citric acid/K2HPO4) and a sample volume of 1000 microL, the sensor responds linearly in the range of 0.5-15 and 3-50 microg/mL with detection limits of 0.14 and 0.36 microg/mL for thiamine and ascorbic acid, respectively. When the method was applied to synthetic samples and pharmaceutical preparations, precise and accurate values were obtained. 相似文献
26.
A solution of a Zn-complex of recombinant mouse MT-1 isoform (Zn(7)-MT-1) was prepared and titrated with Cd(2+) ions. A method based on the coupling of capillary zone electrophoresis (CZE) with electrospray MS detection was developed for the analysis of the stoichiometry of the species formed during the titration. The method offered the possibility of the on-line removal of up to 100 mM Tris or phosphate buffer solutions that would otherwise suppress the electrospray signal. By allowing the determination of the metal stoichiometry of the complex species present in solution the method was shown to be complementary to circular dichroism and UV-VIS spectrophotometry conventionally used for similar studies. The titration of the Zn(7)-MT complex with Cd(II) showed the sequential displacement of the Zn by Cd. The unusually high stability of the Cd(6)Zn(1)-MT species was observed which suggests a structural role of the remaining Zn(II) ion. 相似文献
27.
Pilar De Miguel Nazario Martín Miguel F. Braa 《Journal of heterocyclic chemistry》1994,31(5):1235-1239
Novel tetrahydroimidazo[1,5-b]-β-carbolines derivatives 6 bearing complex basic chains as substituents on the imidic nitrogen have been prepared in a one-pot reaction. This simple experimental procedure overcomes the direct handle of isocyanates which can be favorably generated “in situ” from carbonyldiimidazole (CDI) and different amines. The stereochemistry of the novel compounds was determined by nmr experiments. 相似文献
28.
29.
New cis-clerodane diterpenoids from Croton schiedeanus 总被引:1,自引:0,他引:1
Puebla P Correa SX Guerrero M Carron R San Feliciano A 《Chemical & pharmaceutical bulletin》2005,53(3):328-329
The acid fraction of extracts from the aerial part of Croton schiedeanus afforded six cis-clerodane type diterpenoids. Two of them (1 and 4) are new natural compounds. Structural elucidation was achieved on the basis of their spectral data. 相似文献
30.
In contrast to lower phosphorylation states (e.g. the tryptic monophosphopeptide FQpSEEQQQTEDELQDK from bovine beta-casein), the specific detection of multi-phosphorylated peptides (e.g. the tetraphosphopeptide RELEELNVPGEIVEpSLpSpSpSEESITR from tryptic digestion of bovine beta-casein) has often been problematic for liquid chromatographic mass spectrometric (LC/MS) analysis owing to their high affinity for adsorption to exposed surfaces. We observed an enhancement in the overall detection of phosphopeptides on addition of phosphoric acid (0.1-1.0%) to the sample solution; a 10-fold increase in sensitivity was determined for the detection of two tryptic phosphopeptides and also a significant improvement in the detection of the tetraphosphopeptide. Using capillary LC with ion trap tandem MS for detection and identification, the achievable detection limits were 50 fmol and 50 pmol for the monophosphopeptide and the tetraphosphopeptide, respectively. Phosphoric acid is believed to act as a blocking agent to available silanol groups on both the silica capillary surface and the C(18)-bonded stationary phase silica surface. 相似文献