全文获取类型
收费全文 | 4184篇 |
免费 | 110篇 |
国内免费 | 17篇 |
专业分类
化学 | 2940篇 |
晶体学 | 43篇 |
力学 | 103篇 |
数学 | 191篇 |
物理学 | 1034篇 |
出版年
2022年 | 24篇 |
2021年 | 42篇 |
2020年 | 37篇 |
2019年 | 43篇 |
2018年 | 31篇 |
2017年 | 31篇 |
2016年 | 72篇 |
2015年 | 69篇 |
2014年 | 85篇 |
2013年 | 190篇 |
2012年 | 210篇 |
2011年 | 250篇 |
2010年 | 123篇 |
2009年 | 111篇 |
2008年 | 204篇 |
2007年 | 196篇 |
2006年 | 215篇 |
2005年 | 188篇 |
2004年 | 198篇 |
2003年 | 175篇 |
2002年 | 186篇 |
2001年 | 131篇 |
2000年 | 110篇 |
1999年 | 72篇 |
1998年 | 53篇 |
1997年 | 54篇 |
1996年 | 57篇 |
1995年 | 46篇 |
1994年 | 57篇 |
1993年 | 57篇 |
1992年 | 64篇 |
1991年 | 40篇 |
1990年 | 43篇 |
1989年 | 50篇 |
1988年 | 41篇 |
1987年 | 42篇 |
1986年 | 42篇 |
1985年 | 82篇 |
1984年 | 77篇 |
1983年 | 26篇 |
1982年 | 38篇 |
1981年 | 34篇 |
1980年 | 39篇 |
1979年 | 65篇 |
1978年 | 46篇 |
1977年 | 53篇 |
1976年 | 47篇 |
1975年 | 31篇 |
1974年 | 24篇 |
1973年 | 18篇 |
排序方式: 共有4311条查询结果,搜索用时 15 毫秒
141.
[reaction: see text] Construction and characterization of the C-glycosidic moiety of telomerase inhibitor D8646-2-6 (1) are described. This is the first example of the C-glycosylation using electron-poor aromatics, 4-hydroxypyrone, as a glycosyl acceptor. The glycosylation reaction and base-promoted isomerization affords desired beta-C-glycoside in a 61% overall yield. 相似文献
142.
[structure: see text] Two cytotoxic quaternary Daphniphyllum alkaloids with an unprecedented fused-polycyclic skeleton containing a 1-azoniatetracyclo[5.2.2.0.(1,6)0.(4,9)]undecane ring system, daphniglaucins A (1) and B (2), have been isolated from the leaves of Daphniphyllum glaucescens. Their structures and relative stereochemistry were elucidated on the basis of spectroscopic data. 相似文献
143.
The authors have examined the tumor affinity of various 99mTc-labelled radiopharmaceuticals to Ehrlich's tumor for the purpose of delineating positively human malignant neoplasm. This paper includes biologic distributions of 99mTc-Sn-diphosphonate (99mTc-EHDP), 99mTc-Sn-dimercaptosuccinic acid (99mTc-DMSA) and 99mTc-Sn-diethyl stilbestrol diphosphate (99mTc-DSDP, 99mTc-Honvan) as the second report on the tumor affinity to the Ehrlich-bearing mice. (a) Tumor concentration of 99mTc-EHDP was lowest and the positive delineation of implanted tumor with 99mTc-EHDP was poorest in sequential images, though the active accumulation to some soft tissue maglinant neoplasms, the breast cancer and the thyroid cancer, has been reported. (b) Tumor concentration and tumor to blood ratio of 99mTc-DMSA were not so high on the contrary of our expectation that 197Hg-DMSA may show the high tumor concentration and the high tumor to blood ratio like 197Hg chlormerodrin as same renal scanning radiopharmaceuticals. (c) Tumor concentration of 99mTc-DSDP was highest. Tumor to blood concentration ratio, however, was lower than that of the above mentioned radiopharmaceuticals but tumor to liver ratio and/or tumor to lung ratio was over 1.0 at the earlier time. Biologic distribution of 99mTc-DSDP was similar to that of 32P labeled DSDP and then it is presumed that 99mTc is labeled at phosphate ester of DSDP which is dephospholytated immediately by phospholylase in vivo following the intravenous injection. Therefore, it may be assumed that the accumulation mechanism of 99mTc-DSDP to Ehrlich's tumor is related to the phospholylase activity in neoplasms but is not known precisely. 相似文献
144.
Shingo Kobayashi 《Tetrahedron》2004,60(32):6923-6930
Deoxyfluorination of alcohols was carried out using N,N-diethyl-α,α-difluoro-(m-methylbenzyl)amine (DFMBA). Primary alcohols were effectively converted to fluorides under microwave irradiation or conventional heating. Deoxyfluorination of an anomeric hydroxy group in sugars by DFMBA proceeded at below room temperature and glycosyl fluorides could be obtained in good yields. The deoxyfluorination reaction chemoselectively proceeded and various protecting groups on the sugar can survive under the reaction conditions. 相似文献
145.
Matsuura K Hibino M Ikeda T Yamada Y Kobayashi K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):352-359
We describe herein the relationship between the spatial arrangement of self-organized galactose clusters and lectin recognition. beta-Galactose-modified deoxyuridine phosphoramidite was synthesized and applied to solid-phase synthesis to provide 18-, 20-, and 22-mers of site-specifically galactosylated oligodeoxynucleotides (Gal-ODNs). These Gal-ODNs were self-organized through hybridization with the corresponding 18-, 20-, and 22-mers of half-sliding complementary ODNs (hsc-ODNs) to give periodic galactoside clusters. The self-organization of ODNs was confirmed by size exclusion chromatography and gel electrophoresis. The binding of the Gal-clusters to the FITC-labeled RCA(120) lectin was analyzed by monitoring the change in fluorescence intensity. The assembly of 20-mer Gal-ODN with the 20-mer hsc-ODN was strongly and cooperatively recognized by the lectin. The 18-mer assembly was bound more weakly and less cooperatively, and the 22-mer assembly was minimally bound to the lectin. RCA(120) lectin recognized not only the density of galactoside residues, but also the spatial arrangement. The size of the Gal cluster was estimated from the association constant of Gal-ODN with hsc-ODN. The relationship between lectin-recognition and Gal-cluster size is also discussed. 相似文献
146.
Kaori Suzuki Takayoshi Kobayashi Hiroyuki Ohtani Hiroshi Yesaka Saburo Nagakura Yoshinori Shichida Tôru Yoshizawa 《Photochemistry and photobiology》1980,32(6):809-811
Difference spectra between squid rhodopsin and its bathorhodopsin at room temperature were measured ca. 150 ps and ca. 500 ps after the excitation at 347.2 nm by a double-beam picosecond time-resolved spectrometer. The spectra measured showed a red shift of the isosbestic point between squid rhodopsin and its bathorhodopsin and a lower ΔAmax/ΔAmin value compared with those measured at low temperatures by conventional spectrophotometry. 相似文献
147.
Lewis acid catalysis in supercritical carbon dioxide (CO(2)) was investigated. While solubility of most organic materials is low in scCO(2), poly(ethylene glycol) derivatives or perfluoroalkylbenzenes were found to work as surfactants to dissolve organic materials in scCO(2). In the presence of these molecules, Lewis acid catalyzed organic reactions such as aldol-, Mannich-, and Friedel-Crafts-type reactions proceeded smoothly in scCO(2). Formation of emulsions was observed in these reactions, and the systems were studied in detail. 相似文献
148.
Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) (Eu[2,3-Nc(SC12H25)8]2, 1) and bis(tetra-tert-butyl-2,3- naphthalocyaninato)europium(III) (Eu[2,3-Nc(t-Bu)4]2, 2) have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3.H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV-visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2-->2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = -0.28 V (for 2) and -0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = -0.61, -1.64, -1.97, and -2.42 V, and for 1 they were observed at E1/2 = -0.62, -1.60, -1.86, and -2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared. 相似文献
149.
Two- or three-component aza Diels-Alder reactions of Danishefsky's diene with imines or aldehydes and amines in water took place smoothly under neutral conditions in the presence of a catalytic amount of an alkaline salt such as sodium triflate to afford dihydro-4-pyridones in high yields. 相似文献
150.
S. Tomaru S. Zembutsu M. Kawachi M. Kobayashi 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):885-890
Second harmonic generation (S.H.G.) in inclusion complexes between dimethyl -cyclodextrin (dimethyl -CD) and nitroaniline derivatives occurs. This is due to the destruction of the centrosymmtric crystal structure in nitroaniline derivatives caused by forming inclusion complexes. S.H.G. intensity of dimethyl -CD complex with N-methyl-nitroaniline is 5.5 times as large as that of urea. 相似文献