全文获取类型
收费全文 | 27061篇 |
免费 | 987篇 |
国内免费 | 157篇 |
专业分类
化学 | 18212篇 |
晶体学 | 255篇 |
力学 | 928篇 |
综合类 | 1篇 |
数学 | 2347篇 |
物理学 | 6462篇 |
出版年
2023年 | 154篇 |
2022年 | 410篇 |
2021年 | 489篇 |
2020年 | 432篇 |
2019年 | 448篇 |
2018年 | 333篇 |
2017年 | 317篇 |
2016年 | 727篇 |
2015年 | 632篇 |
2014年 | 793篇 |
2013年 | 1489篇 |
2012年 | 1947篇 |
2011年 | 2135篇 |
2010年 | 1295篇 |
2009年 | 1143篇 |
2008年 | 1742篇 |
2007年 | 1641篇 |
2006年 | 1532篇 |
2005年 | 1428篇 |
2004年 | 1262篇 |
2003年 | 982篇 |
2002年 | 967篇 |
2001年 | 672篇 |
2000年 | 576篇 |
1999年 | 338篇 |
1998年 | 252篇 |
1997年 | 294篇 |
1996年 | 334篇 |
1995年 | 257篇 |
1994年 | 274篇 |
1993年 | 276篇 |
1992年 | 264篇 |
1991年 | 204篇 |
1990年 | 154篇 |
1989年 | 139篇 |
1988年 | 140篇 |
1987年 | 120篇 |
1986年 | 96篇 |
1985年 | 168篇 |
1984年 | 112篇 |
1983年 | 98篇 |
1982年 | 122篇 |
1981年 | 88篇 |
1980年 | 79篇 |
1978年 | 80篇 |
1977年 | 85篇 |
1976年 | 94篇 |
1975年 | 101篇 |
1974年 | 79篇 |
1973年 | 102篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
221.
Lee JC Chang SW Liao CC Chi FC Chen CS Wen YS Wang CC Kulkarni SS Puranik R Liu YH Hung SC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):399-415
A novel and convenient route for the synthesis of biologically potent and rare L-hexose derivatives from D-glucose is described. Conversion of diacetone-alpha-D-glucose (14) into 1,2:3,5-di-O-isopropylidene-beta-L-idofuranose (19) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6-di-O-isopropylidene-beta-L-idofuranose (27), which underwent regioselective epimerization at the C3 position to give the L-talo- and 3-functionalized L-idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6-anhydro-beta-L-idopyranose (35) in excellent yield, which was successfully transformed into the corresponding L-allo, L-altro, L-gulo, and L-ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6-anhydro-beta-L-hexopyranoses as valuable building blocks to the syntheses of 4-methylcoumarin-7-yl-alpha-L-iduronic acid and the disaccharide moieties of bleomycin A(2) as well as heparan sulfate are highlighted. 相似文献
222.
W. H. Daly Chien-Da S. Lee C. G. Overberger 《Journal of polymer science. Part A, Polymer chemistry》1971,9(6):1723-1739
Poly-S-vinyl-O-tert-butylthiocarbonate is an excellent precursor to poly(vinyl mercaptan) because the tert-butyloxycarbonyl blocking group can be removed by either acid hydrolysis or thermolysis under conditions which minimize the oxidation of the liberated mercaptan to disulfide. Dilatometric studies of the homopolymerization of S-vinyl-O-tert-butylthiocarbonate demonstrated that the polymerization rate was directly proportional to the concentration of free-radical initiator; no thermal initiation was observed. The molecular weight of the homopolymers and copolymers ranged from 30,000 to 50,000 (GPC). Copolymerization of S-vinyl-O-tert-butylthiocarbonate (M2) with styrene, (r1 = 3.0, r2 = 0.2), methyl methacrylate (r1 = 1.40, r2 = 0.17) and vinyl acetate (r1 = 0.04, r2 = 11.0) indicated that a sulfur atom adjacent to the vinyl group increases the resonance stability (Q2 = 0.5) and the electron density (e2 = ?1.4) of the double bond and the corresponding radical. Water-soluble copolymers could be prépared by incorporating either N-vinylpyrrolidone (r1 = 0.12, r2 = 3.94) or N-isopropylacrylamide (r1 = 1.17, r2 = 0.3) with M2. The water solubility of the copolymers decreased markedly when the tert-butyloxycarbonyl group was removed. Copolymers of M2 with N-vinyl-O-tert-butylcarbamate (r1 = 0.13, r2 = 5.10) were utilized to prepare crosslinked poly(vinyl amine–vinyl mercaptan); the crosslinking resulted from urea linkages formed during thermolysis of the copolymer. 相似文献
223.
A tandem free radical cyclization-rearrangement sequence was designed and executed to produce tricyclo[4.3.2.0(1,5)]undecane 7 from cyclopentene 6A in a single operation. The total synthesis of suberosenone was accomplished from 7. 相似文献
224.
[reaction: see text]. Unified and highly convergent total syntheses of (+)-macrosphelides A and B are described. Key features of the syntheses include (1) concise synthesis of the optically active delta-hydroxy-gamma-keto alpha,beta-unsaturated acid fragment via the direct addition of a trans-vinylogous ester anion equivalent to the readily available Weinreb amide and (2) facile construction of the 16-membered macrolide core of the macrosphelide series via an intramolecular nitrile-oxide cycloaddition (INOC). 相似文献
225.
J. Jung H. S. Jeong H. H. Chung M. J. Lee J. H. Jin K. B. Park 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):543-546
The radioactive concentrations of radionuclides were measured in the soil and groundwater below the 12 GeV proton beam-line tunnel at KEK. Various long-lived radionuclides, (7Be, 22Na, 46Sc, 54Mn, 60Co, 134Cs, 152Eu and 154Eu) were observed in the soil samples by -ray spectra measurements, and 3H was also detected by liquid scintillation counting. On the other hand, 3H, 22Na and 54Mn, which were leached from the soil were measured in the groundwater below the EP2 beam line. 3H and 22Na were also found in slight amounts in groundwater collected in a well dug beside the East Counter Hall. From a comparison with the radioactive concentration in soil and groundwater, the order of the leaching percentages were 3H>22Na>54Mn. This tendency was in agreement with an experimental result of the RI laboratory. 相似文献
226.
Phytochemical investigation of the methanol extract of Euchresta formosana resulted in the isolation of thirty-four compounds. Compounds 1, 3-12, 15, 27, 29 and 32-24 were isolated from this species for the first time. These compounds were identified by spectral analyses and tested for antiplatelet aggregation and anti-HIV activities. Among these compounds, tectorigenin (1), 3',4',5-trihydroxyisoflavone (3), and euchretin F (19) were the most effective antiplatelet aggregation compounds; they inhibited both AA- (arachidonic acid) and collagen-induced platelet aggregation. Meanwhile, flemiphyllin (B), quercetin (13), euchretin M (23), and formosanatin C (26) inhibited HIV replication in H9 lymphocyte cells. 相似文献
227.
Photoactivation of pheophorbide a induces a mitochondrial-mediated apoptosis in Jurkat leukaemia cells 总被引:5,自引:0,他引:5
Lee WY Lim DS Ko SH Park YJ Ryu KS Ahn MY Kim YR Lee DW Cho CW 《Journal of photochemistry and photobiology. B, Biology》2004,75(3):119-126
The mechanism of cell death by pheophorbide a (Pba) which has been established to be a potential photosensitizer was examined in experimental photodynamic therapy (PDT) on Jurkat cells, a human lymphoid tumor cell line. In 30-60 min after irradiation, Pba treated cells exhibited apoptotic features including membrane blebbing and DNA fragmentation. Pba/PDT caused a rapid release of cytochrome c from mitochondria into the cytosol. Sequentially, activation of caspase-3 and the cleavage of poly ADP-ribose polymerase (PARP) were followed. Meanwhile, no evidence of activation of caspase-8 was indicated in the cells. In experiments with caspase inhibitors, it was found that caspase-3 alone was sufficient initiator for the Pba-induced apoptosis of the cells. Pba specific emission spectra were confirmed in the mitochondrial fraction and the light irradiation caused a rapid change in its membrane potential. Thus, mitochondria were entailed as the crucial targets for Pba as well as a responsible component for the cytochrome c release to initiate apoptotic pathways. Taken together, it was concluded that the mode of Jurkat cell death by Pba/PDT is an apoptosis, which is initiated by mitochondrial cytochrome c release and caspase-3-pathways. 相似文献
228.
The influence of aryl substituents in dibenzylidene acetone (dba) ligands, for Pd(0) complexes, has been evaluated for Suzuki-Miyaura cross-coupling reactions. Electron-withdrawing substituents such as NO(2) or CF(3) deactivate the catalyst species whereas strongly donating substituents such as OMe increase catalytic activity over that of unsubstituted dba ligands. [reaction: see text] 相似文献
229.
As a new type of foldamers, oligoindoles containing 4, 6, and 8 indole rings were synthesized, and their folding properties were characterized by a combination of 1H NMR techniques and UV/visible titration experiments. When chloride was added, the NH signals of the oligoindoles were downfield shifted as a result of hydrogen-bond formation, and the aromatic signals were upfield shifted by stacking between two indoles. Moreover, the ROESY experiment provided definitive NOE evidence for the helical stacking in the presence of chloride. Finally, the UV/visible titration experiments demonstrated that the oligoindoles formed 1:1 complexes with chloride, and the association constants greatly increased with increasing the number of the indole NHs. These observations are all consistent with the fact that oligoindoles adopt a helical conformation when complexed with chloride by hydrogen-bonding interactions. 相似文献
230.
We have recorded extremely weak absorption in the overtone band 5-0 of 12C16O X 1sigma+ near 0.96 microm with cavity ringdown spectroscopy; the light source was a Raman-shifted dye laser pumped with a frequency-doubled Nd:YAG laser. This band shows lines in branch P to be much more intense than corresponding lines in branch R, in contrast to all lower overtone bands v-0 (v = 1-4). This reversal in relative intensity is explained quantitatively in terms of a radial function for the electric dipolar moment of CO. We have estimated absorption line strengths for P3-P18 in band 5-0 of 12C16O; these strengths are consistent with a pure vibrational matrix element <5/p(x)/0> = (3.6 +/- 0.3) x 10(-36) C m of the electric dipolar moment p(x), a Herman-Wallis coefficient C0(5) of about -0.1, and a band strength of (5.1 +/- 1.3) x 10(-29) m at 293 K. 相似文献