全文获取类型
收费全文 | 1115篇 |
免费 | 23篇 |
国内免费 | 13篇 |
专业分类
化学 | 658篇 |
晶体学 | 5篇 |
力学 | 36篇 |
数学 | 150篇 |
物理学 | 302篇 |
出版年
2021年 | 14篇 |
2020年 | 15篇 |
2019年 | 14篇 |
2018年 | 9篇 |
2017年 | 9篇 |
2016年 | 9篇 |
2015年 | 12篇 |
2014年 | 25篇 |
2013年 | 36篇 |
2012年 | 49篇 |
2011年 | 57篇 |
2010年 | 30篇 |
2009年 | 23篇 |
2008年 | 43篇 |
2007年 | 48篇 |
2006年 | 43篇 |
2005年 | 43篇 |
2004年 | 39篇 |
2003年 | 43篇 |
2002年 | 36篇 |
2001年 | 23篇 |
2000年 | 22篇 |
1999年 | 22篇 |
1998年 | 13篇 |
1997年 | 18篇 |
1996年 | 21篇 |
1995年 | 16篇 |
1994年 | 21篇 |
1993年 | 13篇 |
1992年 | 21篇 |
1991年 | 20篇 |
1990年 | 13篇 |
1989年 | 8篇 |
1988年 | 10篇 |
1986年 | 9篇 |
1985年 | 16篇 |
1984年 | 14篇 |
1983年 | 9篇 |
1982年 | 14篇 |
1981年 | 14篇 |
1980年 | 21篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 13篇 |
1976年 | 16篇 |
1975年 | 9篇 |
1974年 | 13篇 |
1973年 | 20篇 |
1972年 | 10篇 |
1937年 | 8篇 |
排序方式: 共有1151条查询结果,搜索用时 78 毫秒
41.
Secondary car☐amides (R1CONHR2) undergo different reactions when heated in HMPA at about 220°. If R1 or R2 can form stable carbonium ions, fragmentation reactions are observed and the corresponding nitriles R2CN or R1CN, respectively, are formed. Also amidines are produced. N-benzyl-acetamide rearranges when heated in HMPA to give β-phenyl-propionitrile, It is suggested that in all the reactions investigated the first step is the formation of a phosphorodiamidate followed by formation of a nitrilium carbonium ion. The fragmentation reactions can be used as an alternative to the Sandmeyer reaction (nitrile synthesis). 相似文献
42.
Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids 总被引:3,自引:0,他引:3
Stieger M Richtering W Pedersen JS Lindner P 《The Journal of chemical physics》2004,120(13):6197-6206
The structure of temperature-sensitive poly(N-isopropylacrylamide) microgels in dilute suspension was investigated by means of small-angle neutron scattering. A direct modeling expression for the scattering intensity distribution was derived which describes very well the experimental data at all temperatures over an extensive q range. The overall particle form as well as the internal structure of the microgel network is described by the model. The influence of temperature, cross-linking density, and particle size on the structure was revealed by radial density profiles and clearly showed that the segment density in the swollen state is not homogeneous, but gradually decays at the surface. The density profile reveals a box profile only when the particles are collapsed at elevated temperatures. An increase of the cross-linking density resulted in both an increase of the polymer volume fraction in the inner region of the particle and a reduction of the smearing of the surface. The polymer volume fraction inside the colloid decreased with increasing particle size. The structural changes are in good agreement with the kinetics of the emulsion copolymerization used to prepare the microgel colloids. 相似文献
43.
An analytical method for the speciation of selenomethionine, selenocystine, selenite and selenate by high performance liquid chromatography (HPLC) with atomic spectrometric detection is presented. An organic polymeric strong anion exchange column was used as the stationary phase in combination with an aqueous solution of 6 mmol L–1 of salicylate ion at pH 8.5 as the mobile phase which allowed the isocratic separation of the four selenium analytes within 8 minutes. The separated selenium species were detected on-line by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma mass spectrometry (ICP-MS). The signal-to-noise ratio of the FAAS detector was optimized using a hydrogen-argon entrained-air flame and a slotted-tube atom trap (STAT) in the flame. The limit of detection (3 σ) achieved by the HPLC-FAAS system was 1 mg L–1 of selenium (100 μL injections) for each of the four selenium species. More powerful selenium detection was achieved using an ELAN 5000 ICP-MS instrument. Selenium was measured at m/z = 82. The ICP-MS signal intensity was enhanced by a factor of 3–4 after addition of 3% methanol to the chromatographic mobile phase and by using an increased plasma power input of 1300 W. The limit of detection achieved under these conditions was 1 μg L–1 (100 μL injections). The HPLC-ICP-MS system was used for selenium speciation of selenite and selenate in aqueous solutions during a BCR certification exercise and for selenium speciation in the certified reference material, BCR No. 402 White Clover. Extraction experiments revealed that the selenium species in the biological material were extractable only in the presence of water in the extraction medium. The results indicated that selenate and a compound of unknown identity U were present in the plant sample. 相似文献
44.
N-(Pyren-1-ylmethyl)-(3R,4R)-4-(hydroxymethyl)pyrrolidin-3-ol was synthesised from (3R,4R)-4-(hydroxymethyl)pyrrolidin-3-ol and (3R,4S)-4-[(1S)-1,2-dihydroxyethyl] pyrrolidin-3-ol using alkylation with 1-(chloromethyl)pyrene or reductive amination with pyrene-1-carbaldehyde and NaCNBH3. The incorporation of N-(pyren-1-ylmethyl)azasugar moiety into oligodeoxynucleotides (ODN) as a bulge to form an intercalating nucleic acid (INA) induced a slight destabilization of INA-DNA duplex, whereas the INA-RNA duplex was strongly destabilized and 9 degrees C difference per modification in thermal stability between INA-DNA over INA-RNA duplexes was observed. The stabilization of a DNA three way junction (TWJ) was improved when the intercalator moiety was inserted into the junction region as a bulge. 相似文献
45.
M. A. Zahran E. B. Pedersen C. Nielsen 《Monatshefte für Chemie / Chemical Monthly》1995,126(11):1271-1277
Summary 3-Aryl-7-(2-deoxy--D-erythro-pentofuranosyl)-3,7-dihydro-4H-pyrrolo[2,3-d]-pyrimidin-4-imines (4) as well as 4-arylamino-7-(2-deoxy--D-erythro-pentofuranosyl)-2-methyl-5-phenyl-7H-pyrrolo[2,3-d]pyrimidines (7) have been synthesized by glycosylation of the sodium salt of the corresponding nucleobases with 2-deoxy-3,5-di-O-p-toluyl--D-erythro-pentofuranosyl chloride (2) followed by subsequent deprotection with sodium methoxide in methanol. The deprotected nucleoside4 undergoes aDimroth rearrangement on reflux for 24 h in water to furnish the 4-arylamino nucleoside7.
Synthese und Reaktionen von 2-Deoxy--D-ribofuranosylderivaten von 3-Aryl-4H-pyrrolo[2,3-d]pyrimidin-4-iminen
Zusammenfassung 3-Aryl-7-(2-deoxy--D-erythro-pentafuranosyl)-3,7-dihydro-4H-pyrrolo[2,3-d]-pyrimidin-4-imine (4) und 4-Arylamino-7-(2-deoxy--D-erythro-pentofuranosyl)-2-methyl-5-phenyl-7H-pyrrolo[2,3,-d]pyrimidine (7) wurden durch Glycosylierung der Natriumsalze der entsprechenden Nucleosidbasen mit 2-Deoxy-3,5-di-O-p-toluyl--D-erythro-pentofuranosylchlorid (2) und anschließende Entfernung der Schutzgruppe mit Natriummethoxid in Methanol hergestellt. Das entschützte Nucleosid4 ergibt bei 24-stündigem Erhitzen in Wasser unter Rückfluß über eineDimroth-Umlagerung das 4-Aminonucleosid7.相似文献
46.
We study wild embeddings of S
1 in S
n which are tame in a sense introduced by Quinn. We show that if is a finitely presented group with H
1()=H
2()=0, then any finiteness obstruction K
0() can be realized on the complement of such an embedded S
1. We also realize trivially symmetric K
–1() obstructions on the complements of such embeddings. For trivially symmetric , the embeddings constructed are shown to be isotopy homogeneous. 相似文献
47.
48.
W Nerdal A T Pedersen O M Andersen 《Acta chemica Scandinavica (Copenhagen, Denmark : 1989)》1992,46(9):872-876
Pelargonidin-3-glucoside has been isolated from the acidified methanolic extract of strawberries (Fragaria anannassa variety Corona) by successive application of an ion-exchange resin, droplet-counter chromatography and gel filtration. The pigment in acidified methanolic solution was studied by means of the two-dimensional nuclear Overhauser enhancement NMR technique, and the sugar unit was found to be attached to the 3-position on the aglycone. At +20 degrees C the pigment was found to be in the extreme narrowing limit where the NOESY cross-peaks are negative. However, at -20 degrees C this low-mass anthocyanin could be studied in the slow motion regime where the NOESY cross-peaks are positive. With a mixing time of 0.3 s, the glucose H1"-H4" proton pair was measured in the initial cross-relaxation rate and their cross-peak volume corresponded to the H1"-H4" distance found in a 4C1 chair conformation. 相似文献
49.
Gonçalves SA De Pauli SH Tedesco AC Quina FH Okano LT Bonilha JB 《Journal of colloid and interface science》2003,267(2):494-499
The counterion binding at a water/Aerosol-OT (AOT)/heptane microemulsion interface was treated in the context of the pseudo-phase ion exchange formalism. Two approaches were used to determine the selectivity coefficient for copper/sodium counterion binding at the AOT microemulsion interface: measurements of the Cu(II) concentration taken up by the reverse micelle in a Winsor II microemulsion system and steady-state emission quenching measurements of an anionic water-solubilized probe, the tris-(4,4'-dicarboxy-2,2'-bipyridine) ruthenium (II) ion. In addition, the selectivity coefficient for methyl viologen/sodium at the microemulsion surface was determined by the same photophysical technique. The value for copper (II)/sodium exchange (K(Cu/Na)) is 1.1+/-0.3 and that for methyl viologen/sodium (K(MV/Na)) is 0.9+/-0.3. The results show that the pseudo-phase ion exchange model can be used to obtain the selectivity coefficient in a microemulsion system. 相似文献
50.
Kaloustian J. Pauli A. M. Pieroni G. Portugal H. 《Journal of Thermal Analysis and Calorimetry》2002,70(3):959-973
The human urinary calculi are mainly constituted by calcium oxalate, magnesium ammonium phosphate hexahydrate, and uric acid.
The ions or molecules are easily characterized by wet chemical methods. The difficulties appear in the differentiation of
the hydrates of calcium oxalate (monohydrate COM or Whewellite, and dihydrate COD or Weddelite). A high level of COD in the
urinary stones leads, often, inflammation, sharp pain and blood in urine. In the worse cases, they must be extracted by surgical
way. The identification of the main components of urinary calculi, the knowledge of the true number of water molecules bounded
to the calcium oxalate, and the determination of each hydrate in the mixture, are the interests of this memory. The thermal
analysis (simultaneous DTA-TG) was applied on thirty-three urinary calculi. The determination of the calcium oxalate hydrates
was confirmed by calorimetry (DSC).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献