全文获取类型
收费全文 | 6857篇 |
免费 | 275篇 |
国内免费 | 31篇 |
专业分类
化学 | 4716篇 |
晶体学 | 62篇 |
力学 | 186篇 |
数学 | 668篇 |
物理学 | 1531篇 |
出版年
2023年 | 25篇 |
2022年 | 68篇 |
2021年 | 137篇 |
2020年 | 128篇 |
2019年 | 122篇 |
2018年 | 139篇 |
2017年 | 120篇 |
2016年 | 255篇 |
2015年 | 196篇 |
2014年 | 270篇 |
2013年 | 422篇 |
2012年 | 525篇 |
2011年 | 601篇 |
2010年 | 359篇 |
2009年 | 328篇 |
2008年 | 490篇 |
2007年 | 455篇 |
2006年 | 392篇 |
2005年 | 371篇 |
2004年 | 291篇 |
2003年 | 250篇 |
2002年 | 243篇 |
2001年 | 127篇 |
2000年 | 146篇 |
1999年 | 104篇 |
1998年 | 87篇 |
1997年 | 53篇 |
1996年 | 54篇 |
1995年 | 53篇 |
1994年 | 54篇 |
1993年 | 50篇 |
1992年 | 35篇 |
1991年 | 22篇 |
1990年 | 34篇 |
1989年 | 25篇 |
1988年 | 8篇 |
1987年 | 10篇 |
1986年 | 13篇 |
1985年 | 13篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1977年 | 5篇 |
1976年 | 6篇 |
1975年 | 5篇 |
1974年 | 9篇 |
1973年 | 5篇 |
排序方式: 共有7163条查询结果,搜索用时 305 毫秒
81.
A series of calixcrown ethers for which the cavity size of the crown ring is varied from crown-6 to crown-7 to crown-8 were examined for the transport abilities toward alkali metal ions. These ligands were incorporated into supported liquid membranes (SLMs) and into polymer inclusion membranes (PIMs) composed of cellulose triacetate (CTA) as a support and 2-nitrophenyl octyl ether (NPOE) and tris(2-butoxyethyl) phosphate (TBEP) as a plasticizer. In both membrane systems, calixcrown-6 showed the best selectivity toward a cesium ion over other alkali metal ions. The polymeric CTA membrane showed more rapid transport rate as well as higher durability than did the SLMs. 相似文献
82.
Hong J Kim YH Gil JH Cho K Jung JH Han SY 《Rapid communications in mass spectrometry : RCM》2002,16(22):2089-2093
The structural determination of sn-1 and sn-2 hexadecanoic lysophosphatidylcholine (LPC) regioisomers was carried out using fast atom bombardment tandem mass spectrometry (FAB-MS/MS). The collision-induced dissociation (CID) of protonated and sodiated molecules produced diverse product ions due mainly to charge remote fragmentations. Based on the information obtained from the CID spectra of protonated and sodiated molecules, sn-1 and sn-2 hexadecanoic LPC isomers could be discriminated. Especially, the abundance ratio of the diagnostic ion pair [m/z 224/226] in the CID spectra of [M + H](+) ions was shown to be greatly different. Moreover, the CID-MS/MS spectra of sodium-adducted molecules for hexadecanoic LPC isomers showed characteristic product ions such as [M + Na - 103](+), [M + Na - 85](+), and [M + Na - 59](+), by which their regio-specificity can be differentiated. 相似文献
83.
Abstract— Irradiation of thin films consisting of 4,5',8-trimethylpsoralen (TMP), adenosine and small amounts of alcohols led to TMP-alcohol photoadducts in addition to TMP-adenosine photoadducts. Four TMP-ethanol and two TMP-methanol adducts have been separated and characterized. Covalent bonds were formed between the 4-carbon of TMP and the α-carbon to the hydroxy group in the alcohols. The TMP-alcohol photoadducts were formed only in the TMP film containing small amounts of alcohol and adenosine. Furthermore, no photoadduct of TMP and ribose was detected upon photolysis of a TMP-ribose film, suggesting that the adenine moiety plays a specific role in the reaction. The interaction of adenosine with psoralens in a dry film may be related to the DNA sequence selectivity observed for the photoreaction of psoralens with DNA. 相似文献
84.
85.
I. V. Il’ina K. P. Volcho D. V. Korchagina N. F. Salakhutdinov V. A. Barkhash 《Russian Journal of Organic Chemistry》2004,40(10):1432-1436
Transformations of epoxide derived from nopol in the presence of natural askanite-bentonite clay were studied. The major products of the isomerization in the cold are diols possessing a p-menthane skeleton, which are readily converted into bicyclic ethers when the reaction is carried out at room temperature.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1483–1487.Original Russian Text Copyright © 2004 by Ilina, Volcho, Korchagina, Salakhutdinov, Barkhash. 相似文献
86.
Young-ah WooChang-hee Cho Hyo-jin Kim Jong-soo YangKi-yong Seong 《Microchemical Journal》2002,73(3):299-306
A rapid and nondestructive near infrared (NIR) method using soft independent modeling of class analogy (SIMCA) for the classification of cultivation area (Korea and China) was evaluated and confirmed. Raw, first, and second derivative NIR spectra were compared to develop a robust classification rule. The chemical properties of ginseng samples were also investigated to find out the differences between Korean samples and Chinese samples. These differences make NIR spectroscopic method viable. The average value of each Korean and Chinese ginseng sample for crude fiber, crude protein, starch, and 10 inorganic constituents were measured and compared with F-test and t-test. The inorganic constituents were also measured by induced coupled plasma-atomic emission spectroscopy (ICP-AES). It could be found that the amount of starch and ten inorganic elements for example Na, Mg, P, K, Ca, Mn, Fe, Ni, Cu and Zn in ginseng samples are considerably different based on cultivation area. SIMCA has been applied to the inorganic data to investigate the possibility of ICP-AES as classification tool. However, it was observed that the result was not equal to than NIR spectra data. The overall results showed the availability of NIR method using SIMCA would be adequate for classification of cultivation of ginseng, since NIR spectra includes useful and various information on chemical properties in spite of broad and overlapped bands. 相似文献
87.
V. I. Lozinsky I. A. Simenel M. G. Semenova L. E. Belyakova M. M. Il’in V. Ya. Grinberg A. S. Dubovik A. R. Khokhlov 《Polymer Science Series A》2006,48(4):435-443
The free-radical copolymerization of N-vinylcaprolactam and N-vinylimidazole (at an initial comonomer ratio of 85: 15, mol/mol) initiated by a persulfate-tertiary amine redox system in 10% aqueous DMSO at 25 and 65°C (at temperatures below and above the temperature of phase separation in the reaction system, respectively) yielded macromolecular products that were subsequently separated into thermally precipitating and nonprecipitating fractions. Investigations of these fractions by capillary viscometry, static and dynamic laser light scattering, and high-sensitivity DSC showed that macromolecules of both types of copolymers are strongly associated in aqueous solutions. Upon heating of solutions of thermally nonprecipitating fractions, additional aggregation takes place and this phenomenon is accompanied by a decrease in the size of particles without loss in their solubility until at least 70°C is reached. As for the set of properties exhibited in aqueous solutions, the thermally nonprecipitating fraction of the copolymer synthesized at 65°C may be assigned to protein-like macromolecules. 相似文献
88.
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
89.
The preparation of an 1,3-alternate calix[4]arene phosphorus ligand, 25,27-bis(2-(diphenylphosphino)ethoxy)-26,28-bis(1-propyloxy)calix[4]arene (3), is presented. Ligand 3 is obtained in three steps in 64% overall yield. Reaction of 3 with [Rh(cot)2]BF4 produced the encapsulated rhodium complex [Rh[(P,P)-diphen-calix[4]arene]]BF4 (4). As revealed by a single-crystal X-ray diffraction study, the rhodium center has a bent coordination environment with a P-Rh-P angle of 135.66(3) degrees. Palladation of 3 employing [Pd(MeCN)4](BF4)2 yielded the chelate palladium complex 7 in which the palladium center has a slightly bent configuration. Treatment of the ligand with Pd(cod)Cl2 and [Pd(eta3-C4H7)(THF)2]BF4 leads to the isolation of the monometallic complex. Full characterization includes X-ray structural studies of compounds 3, 4, and 6. 相似文献
90.
L. N. Raevskaya N. I. Il’chenko Yu. I. Pyatnitskii N. V. Pavlenko 《Theoretical and Experimental Chemistry》1997,33(2):78-81
The catalytic transformation of methane into higher hydrocarbons was studied under unsteady conditions on oxides of various
metals (Pb, Fe, Nb, Ti, Cd, Mo, Mg, Zn, Zr, Bi, Mn), and also on Sr-, La-, Y-, and Mn-containing oxides of perovskite structure.
It is shown that the effectiveness of the catalysts not only depends on their chemical composition, but also is determined
to a considerable degree by the specific surface of the oxides.
L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of Ukraine, 252039 Kiev, Prosp. Nauki, 31, Ukraine.
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 2, pp. 91–95, March–April, 1997. 相似文献