全文获取类型
收费全文 | 2504篇 |
免费 | 126篇 |
国内免费 | 15篇 |
专业分类
化学 | 1974篇 |
晶体学 | 30篇 |
力学 | 56篇 |
综合类 | 1篇 |
数学 | 208篇 |
物理学 | 376篇 |
出版年
2023年 | 13篇 |
2022年 | 29篇 |
2021年 | 26篇 |
2020年 | 39篇 |
2019年 | 68篇 |
2018年 | 21篇 |
2017年 | 26篇 |
2016年 | 82篇 |
2015年 | 77篇 |
2014年 | 94篇 |
2013年 | 145篇 |
2012年 | 181篇 |
2011年 | 252篇 |
2010年 | 167篇 |
2009年 | 104篇 |
2008年 | 192篇 |
2007年 | 129篇 |
2006年 | 127篇 |
2005年 | 142篇 |
2004年 | 105篇 |
2003年 | 74篇 |
2002年 | 101篇 |
2001年 | 43篇 |
2000年 | 56篇 |
1999年 | 32篇 |
1998年 | 26篇 |
1997年 | 10篇 |
1996年 | 20篇 |
1995年 | 18篇 |
1994年 | 15篇 |
1993年 | 18篇 |
1992年 | 10篇 |
1991年 | 18篇 |
1990年 | 17篇 |
1989年 | 11篇 |
1988年 | 14篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 12篇 |
1979年 | 8篇 |
1978年 | 5篇 |
1977年 | 10篇 |
1976年 | 8篇 |
1974年 | 7篇 |
1973年 | 4篇 |
1914年 | 4篇 |
排序方式: 共有2645条查询结果,搜索用时 15 毫秒
31.
Hwang JY Choi HS Seo JS La HJ Kim DS Jeon HS Jeon MK Lee DH Gong YD 《The Journal of organic chemistry》2005,70(24):10151-10154
[reaction: see text] A library containing 1200 analogues of 2,6-difunctionalized 2-methyl-2H-1-benzopyran was constructed by using a solid-phase synthesis protocol. Polymer-bound 6-amido-, 6-sulfonamido-, and 6-uredo-functionalized 2-hydroxymethyl-2-methylbenzopyrans 10 were prepared as part of a first-generation diversification step by employing reactions of respective acid halides, sulfonyl chlorides, and isocyanates with the amine precursor 7. Transformations of the resin-bound intermediates 10 by reactions with alkyl and acid halides were then used to produce a diverse series of 2,6-difunctionalized 2-methyl-2H-1-benzopyran analogues 12 and 14. 相似文献
32.
Takashi Hayashita Akiyo Yamauchi Ai-Jun Tong Jong Chan Lee Bradley D. Smith Norio Teramae 《Journal of inclusion phenomena and macrocyclic chemistry》2004,50(1-2):87-94
The design and function of novel supramolecular fluoroionophore/cyclodextrin (CyD) complex sensors for ion and molecule recognition in water are reviewed. For the crown ether fluoroionophore/-CyD complex, the dimerization of the fluoroionophore inside the -CyD is found to be selectively promoted by alkali metal ion binding, thereby resulting in metal-ion-selective pyrene dimer emission in water. This supramolecular function is successfully utilized in the design of a podand fluoroionophore/-CyD complex for sensing toxic lead ion in water. The boronic acid fluoroionophore/-CyD complex binds sugars and produces increased fluorescence emission in water. The response mechanism appears to be due to the suppression of the photoinduced electron transfer (PET) from pyrene donor to trigonal phenylboronic acid acceptor. This is a novel emission function provided by the boronic acid fluoroionophore/-CyD complex sensors in water. 相似文献
33.
G. J. De Jong U. A. Th. Brinkman W. Th. Kok 《Journal of Radioanalytical and Nuclear Chemistry》1977,35(2):245-252
An investigation has been made on the system liquid anion-exchanger-Cd(II)-NCS−. The influence of the acidity and thiocyanate concentration of the aqueous phase on the extraction has been studied. Using
various methods of analysis, it has been shown that the complex anion present in the organic extracts is Cd(NCS)
4
2−
. Details are given concerning the removal of traces of Zn(II) from Cd(II)-containing solutions, and the quantitative separation
of Cd(II) from Cr(III). 相似文献
34.
Kang MS Kim JH Kim YJ Won J Park NG Kang YS 《Chemical communications (Cambridge, England)》2005,(7):889-891
The ionic conductivity of polymer electrolytes and their interfacial contact with dye-attached TiO2 particles were enhanced markedly by the addition of amorphous oligomer into polymer electrolytes, resulting in very high overall energy conversion efficiency. 相似文献
35.
Chun Hag Jang Jong Ryul Kim Taikyue Ree 《Journal of polymer science. Part A, Polymer chemistry》1986,24(12):3171-3176
The non-Newtonian intrinsic viscosities [η] of poly(γ-methyl L-glutamate) were measured in the helix–coil transition region under various conditions in this work. The helix content fH, which represents the degree of conformational transition, was obtained by using a polarimeter. Our experimental results show that the non-Newtonian behavior of the polypeptide is markedly affected by its conformation; i.e., the non-Newtonian effect becomes larger as fH increases. The effect of external pressure ΔP on [η] was studied carefully; [η] increases with fH when ΔP < 1.5 psi, but it decreases when ΔP > 1.5 psi and fH > 0.8. The reason for this result is considered in the text. 相似文献
36.
Self-assembling structures of long-chain phenyl glucoside influenced by the introduction of double bonds 总被引:1,自引:0,他引:1
Jung JH John G Yoshida K Shimizu T 《Journal of the American Chemical Society》2002,124(36):10674-10675
Four long-chain phenyl glucoside amphiphiles possessing a saturated or unsaturated long alkyl chain group as the self-assembling unit of a highly organized molecular architecture were synthesized. Their self-assembling properties were investigated by EF-TEM, SEM, CD, FT-IR, and XRD. Compound 2 possessing one double bond in the lipophilic portion showed twisted helical fibers, which formed a bilayered structure with a 3.59 nm period, while compound 3 showed the helical ribbons and left-handed nanotubular structures with 150-200 nm inner diameters and ca. 20 nm of wall. Very interestingly, compound 4 possessing three double bonds showed a nanotubular structure with ca. 70 nm of inner diameter through a helical ribbon, which formed a loose bilayered structure with 4.62 nm. These results indicate that self-assembling properties strongly depend on the number of cis double bonds. 相似文献
37.
A sampling method has been developed for the measurement for polycyclic aromatic hydrocarbons in ambient air by gas chromatography isotope dilution mass spectrometry. The method has been designed to measure the largest possible volatility range of PAHs including the abundant naphthalenes. Sample volumes were approx. 500 m3 in size at a sampling rate of approx. 18 m3/h. The sampler contained three sorption stages for the simultaneous capturing of particle bound and low and high volatile gaseous PAH, respectivley. Recoveries of sampling spikes were on average 90%. The detection limit was approx. 5 pg/m3 for the high boiling range PAH. Results obtained showed a quite steady profile for most PAH in background air in The Netherlands. Comparison of abundance ratios with literature data indicate that traffic exhausts are the major source for the PAH in the area. 相似文献
38.
The capillary electrochromatographic (CEC) analysis of basic compounds on octadecyl-silica stationary phases (Hypersil ODS and Spherisorb ODS I) was studied. A basic drug (fluvoxamine) and one of its possible impurities were used as test compounds. With an eluent of acetonitrile-phosphate buffer (pH 7.0), the compounds could be baseline-separated; however, broad and tailing peaks were obtained. To minimise detrimental interactions with residual silanol groups, the pH of the mobile phase was lowered to 2.5, but the plate numbers were still quite low (<2.6x10(4) plates/m). Addition of a masking agent (hexylamine or triethylamine) to the mobile phase resulted in much better peak efficiencies (ca. 1x10(5) plates/m). Therefore, the influence of the amine concentration and pH of the mobile phase on the CEC performance (peak width, peak tailing, electroosmotic flow, selectivity) was investigated in detail. Highest efficiencies (2.8x10(5) plates/m) could be obtained with the Spherisorb column, while the Hypersil column offered a better selectivity. Furthermore, the results show that the residual silanol groups are (at least partly) responsible for the separation of the basic compounds and that the amount of injected sample has an unusually large effect on the peak efficiency. The usefulness of the system for impurity profiling was demonstrated with a mixture containing fluvoxamine and its stereoisomer (a possible impurity) at the 0.1% level. The general effectiveness of amine additives in CEC was illustrated by the separation of a mixture of five structurally different basic drugs yielding plate numbers in the 1x10(5)-3x10(5) plates/m range. Comparison with capillary electrophoretic analysis revealed a unique selectivity of the CEC system which is based on both electrophoretic mobility and chromatographic partitioning. 相似文献
39.
[reaction: see text] A new recyclable supported catalyst system for orthoalkylation was devised using a self-assembly consisting of the barbiturate and 2,4,6-triaminopyrimidine H-bonding motifs. At high temperature, the system is completely homogeneous so as to give an efficient catalytic activity, while it is heterogenized at room temperature to form an insoluble solid phase for the easy recovery of the catalyst after the reaction. 相似文献
40.
Lee JS Kim DH Liu KH Oh TK Lee CH 《Rapid communications in mass spectrometry : RCM》2005,19(23):3539-3548
Searchable MS/MS spectra libraries, constructed using the results of liquid chromatography coupled with electrospray ionization (ESI) tandem mass spectrometry (LC/MS/MS) with data-dependent acquisition on an ion trap mass spectrometer, are presented with regard to the identification and confirmation of a variety of closely related flavonoids in a set of biological samples. Flavonoids were found to exhibit a maximum amount of structurally specific MS/MS spectra at 45% of normalized collision energy on the instrument used, without wideband activation. These MS/MS spectra were then searched automatically against a 297-substance MS/MS library that contains many previously acquired spectra of standard flavonoids. The possible applications of this powerful technique to biological samples are also discussed. Daidzein and genistein were identified through the MS/MS spectra library while searching through LC/MS/MS data for plant and microbial extracts. Moreover, these compounds proved completely distinguishable from other flavonoids of closely related structures in the MS/MS spectra library, using the NIST MS search program. The applicability of the library-searchable spectra at low concentrations was demonstrated by successful identification of daidzein and genistein at 0.05 and 0.5 microg/mL, respectively. 相似文献