全文获取类型
收费全文 | 2937篇 |
免费 | 62篇 |
国内免费 | 10篇 |
专业分类
化学 | 1784篇 |
晶体学 | 59篇 |
力学 | 98篇 |
数学 | 284篇 |
物理学 | 784篇 |
出版年
2022年 | 23篇 |
2021年 | 18篇 |
2020年 | 24篇 |
2019年 | 37篇 |
2018年 | 28篇 |
2017年 | 30篇 |
2016年 | 67篇 |
2015年 | 42篇 |
2014年 | 67篇 |
2013年 | 161篇 |
2012年 | 134篇 |
2011年 | 225篇 |
2010年 | 143篇 |
2009年 | 139篇 |
2008年 | 159篇 |
2007年 | 207篇 |
2006年 | 156篇 |
2005年 | 126篇 |
2004年 | 104篇 |
2003年 | 104篇 |
2002年 | 69篇 |
2001年 | 31篇 |
2000年 | 35篇 |
1999年 | 39篇 |
1998年 | 33篇 |
1997年 | 30篇 |
1996年 | 30篇 |
1995年 | 28篇 |
1994年 | 27篇 |
1993年 | 26篇 |
1992年 | 30篇 |
1991年 | 26篇 |
1990年 | 33篇 |
1989年 | 20篇 |
1987年 | 32篇 |
1986年 | 33篇 |
1985年 | 31篇 |
1984年 | 28篇 |
1983年 | 21篇 |
1982年 | 32篇 |
1981年 | 36篇 |
1980年 | 22篇 |
1979年 | 33篇 |
1978年 | 27篇 |
1976年 | 24篇 |
1975年 | 21篇 |
1974年 | 19篇 |
1973年 | 21篇 |
1972年 | 18篇 |
1971年 | 22篇 |
排序方式: 共有3009条查询结果,搜索用时 93 毫秒
31.
32.
33.
34.
35.
Monolayers of single-stranded DNA (ssDNA) immobilized on surfaces form the basis of a number of important biotechnology applications, including DNA microarrays and biosensors. The organization of ssDNA as layer on a solid substrate allows one to investigate various properties of the DNA in a controlled manner and to use DNA for analytical applications as well as for exploring futuristic schemes for molecular electronics. It is commonly assumed that the adsorbed DNA layer contains some structural water and the cations. Here we show, based on XPS studies, that when monolayers of ssDNA are formed from sodium phosphate buffer and washed thoroughly, no Na+ signal is detected. A finite concentration of ions is observed when the DNA is made from a solution of Mg2+ ions, but it is still only a fifth of what it would be if all the phosphate ions were fully neutralized by the metal cations. 相似文献
36.
M. F. Jarrold U. Ray Y. Ijiri 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,19(4):337-342
The chemical reactions of size selected silicon cluster ions (containing up to 70 atoms) have been studied with a number of different reagents using injected ion drift tube techniques. Both kinetic and equilibrium measurements have been performed as a function of temperature, and the influence of cluster annealing on chemical reactivity explored. Unlike metal clusters, where bulk behavior appears to be approached with around 30 atoms, large silicon clusters (n up to 70) are much less reactive than bulk silicon surfaces. These results suggest that the clusters in the size range examined here are not small crystals of bulk silicon, but have compact, high coordination number structures with few dangling bonds. 相似文献
37.
A novel Mitsunobu-based protocol has been developed for the synthesis of O,S-dialkyl dithiocarbonates from a variety of primary, secondary and tertiary alcohols using carbon disulfide, in good to excellent yields. This protocol is mild and efficient compared to other reported methods. 相似文献
38.
Non-K-region -quinones of polycyclic aromatic hydrocarbons are prepared in four steps from cyclic ketones via dehydrogenation of tetrahydrodiols with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. 相似文献
39.
Fluoxetine (Prozac) is currently one of the widely prescribed selective serotonin reuptake inhibitors (SSRIs) for the treatment of depression. A high-throughput sample preparation procedure using liquid-liquid extraction (LLE) in a 96-well plate format in conjunction with liquid chromatography/tandem mass spectrometry (LC/MS/MS) was developed and validated for quantification of fluoxetine enantiomers in human plasma. After addition of internal standard and ammonium hydroxide, samples were extracted with ethyl acetate. The organic extract was evaporated to dryness and reconstituted in methanol. Where possible, sample transfer and LLE steps were automated using a Tomtec Quadra 96 workstation. Adequate separation of fluoxetine enantiomeric pairs (resolution of 1.17) was achieved on a vancomycin column eluted with methanol containing 0.075% (by weight) ammonium trifluoroacetate. A triple quadrupole mass spectrometer, operated in the multiple reaction monitoring mode at m/z 310-->44 for fluoxetine enantiomeric pairs and m/z 287-->241 for oxazepam (internal standard), was used. Analysis was performed in the positive ion mode using atmospheric pressure chemical ionization (APCI). The standard curve range was 2.0-1000 ng/mL for each fluoxetine enantiomer. The intra- and inter-day precision and accuracy of the quality control (QC) samples were <12.5% (CV) and <13.6% (CV), respectively, for each fluoxetine enantiomer; the correlation coefficient was >0.990. Method ruggedness was demonstrated by the reproducible performance of the assay during a three-day validation period. 相似文献
40.
Kaldor I Feldman PL Mook RA Ray JA Samano V Sefler AM Thompson JB Travis BR Boros EE 《The Journal of organic chemistry》2001,66(10):3495-3501
The quaternizations of dibenzoquinolizines 9 and 14 with 3-halo-1-propanols are highly cis-selective (94-100% cis), results consistent with the N-methylation of O-methylcapaurine (7b), but in contrast to the proposed trans-stereochemistry of dibenzo[a,h]quinolizine methiodide 10 and the analogous quaternizations of 1-benzyl- and 1-phenylisoquinoline congeners 5b and 5c. In this report, we describe stereoselective preparation of the unique cis-dibenzoquinolizinium propanols 15 and 16and their transformation into bis- and mixed-onium chlorofumarates 19, 20ab, and 26. Dibenzo[a,g]quinolizinium propanol 15 was prepared enantioselectively in three steps from dihydroisoquinoline 11. Asymmetric transfer hydrogenation of 11 in the presence of triethylamine/formic acid and Noyori's chiral ruthenium catalyst 12 produced R-(-)-5',8-dimethoxynorlaudanosine (13) in 98% yield and 87% ee. Pictet-Spengler cyclization of 13 in formalin/formic acid afforded the dibenzo[a,g]quinolizine 14 in 65% yield. Quaternization of 14 with 3-chloro-1-propanol under Finkelstein conditions generated cis-dibenzoquinolizinium propanol 15 in 85% yield with >94% cis-selectivity. The cis-dibenzo[a,h]quinolizinium propanol 16 was obtained as a single stereoisomer by reaction of the known tetramethoxyquinolizine 9 with neat 3-iodo-1-propanol. Bis-onium chlorofumarates 18 and 19 and the mixed-onium derivative 20ab were prepared by a pool synthesis procedure from (1R)-trans-6a, 16, and chlorofumaryl chloride (17). Mixed-onium alpha-chlorofumarate 26 was synthesized from (1S)-trans-6d, 15 and (+/-)-trans-2,3-dichlorosuccinic anhydride (22), employing a recently disclosed chlorofumarate mixed-diester synthesis. The title compounds (19, 20ab, and 26) displayed curare-like effects of ultrashort duration in rhesus monkeys. 相似文献