全文获取类型
收费全文 | 1753篇 |
免费 | 72篇 |
国内免费 | 16篇 |
专业分类
化学 | 1113篇 |
晶体学 | 32篇 |
力学 | 73篇 |
数学 | 251篇 |
物理学 | 372篇 |
出版年
2023年 | 11篇 |
2022年 | 30篇 |
2021年 | 46篇 |
2020年 | 55篇 |
2019年 | 58篇 |
2018年 | 64篇 |
2017年 | 60篇 |
2016年 | 78篇 |
2015年 | 66篇 |
2014年 | 76篇 |
2013年 | 184篇 |
2012年 | 107篇 |
2011年 | 150篇 |
2010年 | 92篇 |
2009年 | 92篇 |
2008年 | 110篇 |
2007年 | 109篇 |
2006年 | 72篇 |
2005年 | 67篇 |
2004年 | 57篇 |
2003年 | 47篇 |
2002年 | 37篇 |
2001年 | 14篇 |
2000年 | 14篇 |
1999年 | 7篇 |
1998年 | 10篇 |
1997年 | 8篇 |
1996年 | 17篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 11篇 |
1992年 | 11篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1977年 | 2篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1970年 | 1篇 |
1967年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有1841条查询结果,搜索用时 296 毫秒
31.
32.
Jalal A.?Zahra Bassam Abu?Thaher Mustafa M.?El-Abadelah Hans-Hartwig?OttoEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(4):567-570
Summary. Nitrilimines prepared from N-arylhydrazono chlorides reacted with 2-mercaptonicotinic acid yielding the corresponding addition products, 2-[(2-oxo-1-arylhydrazonopropan-1-yl)mercapto] nicotinic acids, which were treated with 1,1-carbonyldiimidazole in THF affording by cyclocondensation the corresponding hitherto unknown 2-arylhydrazono-3-oxothieno[2,3-b]pyridines. 相似文献
33.
34.
Serkan Erdemir Mustafa Tabakci Mustafa Yilmaz 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(3-4):197-202
Herein the synthesis and extraction abilities of new d-/l-phenylalaninol substituted p-tert-butylcalix[4]arene triamide derivatives (3 and 4) towards amino acids are reported. These compounds (3 and 4) have been easily synthesized via aminolysis of p-tert-butylcalix[4]arene trimethylester (2) with d-/l-phenylalaninol in methanol-toluen solvent system at one step. The extraction properties of the prepared chiral calix[4]arene
triamide derivatives (3 and 4) towards some selected amino acid methylesters are studied by liquid–liquid extraction. Results show that these chiral calix[4]arene
triamide derivatives (3 and 4) exhibited a good affinity towards all amino acid species without any remarkably discrimination. 相似文献
35.
Serdar Karabcek Ismail Degirmencioglu Nevin Karabcek Mustafa Er Kerim Serbest 《Journal of heterocyclic chemistry》2003,40(4):639-643
The synthesis and structural properties of three novel imidates, 11,13‐bis‐(2‐amino‐ethylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane ( 2 ), 11,13‐bis‐(3‐aminopropylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane, ( 3 ) and 2,11‐dioxa‐5,8‐dithia‐13,16,19,22‐tetraazabicyclo[10.10.1]tricosa‐1(22),12‐diene, ( 4 ) have been described. These compounds were synthesized by treating 1,10‐dioxa‐4,7‐dithiacyclotridecane‐11,13‐diester ( 1 ) with the appropriate diamine under N2 and their structures have been characterised by elemental analyses, 1H‐ and 13C‐nmr, ir, and mass spectral studies. Elemental analyses and spectroscopic data support the proposed imidate structures. In addition, total energy and heat of formation (Figure 2) calculated for imidates 2a‐4a and 2b‐4b by the semiempirical AM1 calculations have shown that imidates 2b‐4b having intramolecular hydrogen bonds are more stable (5‐10 kcal/mol) than compounds 2a‐4a . 相似文献
36.
The Claisen rearrangement of the N‐protected, silylated allyl glycinates 11 and 12 led to the formation of allyl/silyl‐functionalized amino acids 13 and 14 in yields up to 80%. The diastereoisomer ratio varied from 2 : 1 to 29 : 1 for 11mb , and from 2 : 1 to 46 : 1 (syn/anti) for 12mb , depending on reaction conditions, as shown by X‐ray crystallographic analysis of 14mb . The relationship between the size of the alkyl groups on the chlorosilane reagent (Me2R″SiCl, R″=Cl, Me, t‐Bu, Ph) used as an enolate trap and the observed stereoselectivity was investigated in the case of the Ireland–Claisen variant. Me3SiCl gave the best results. However, the size of the alkyl groups on the silylated ester (Me2R″Si, R=Me, t‐Bu, Ph, i‐Pr) did not exert a significant effect on the diastereoselectivity or yield of the rearrangement. 相似文献
37.
A total of seven pesticides and eight alkylphenols were monitored using this method for the determination of their trace levels in human cord blood. The pesticides are lindane, diazinon, α-endosulfan, β-endosulfan, endosulfan sulfate, chlorpyrifos and endrin; while the alkylphenols are 4-n-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-t-octylphenol, 4-n-heptylphenol, nonylphenol, 4-n-octylphenol and bisphenol A. The pesticides and alkylphenols in the cord blood samples were extracted with solid phase extraction IST C18 cartridges and analyzed by selected ion monitoring mode using quadrapole detector in Shimadzu QP-5000 gas chromatograph-mass spectrometer. Trace levels of pesticide and alkylphenols in the range of non-detectable to 15.17 ng ml−1, were detected in the human cord blood samples. This technique of monitoring the levels of endocrine-disruptors in blood samples is consistent, reliable and cost effective while reducing wastage of time and solvents. 相似文献
38.
The synthesis of 11‐methyl‐6H‐pyrido[4,3‐b]carbazole‐1(2H)‐one (5), which can be important for the synthesis of other pyridocarbazole alkaloids and especially 1‐substituted ellipticines, is described. Construction of the tetracyclic structure was achieved by a new route and two important precursor compounds (4a and 4b) for the synthesis of pyridocarbazole alkaloids and also many new tetrahydrocar‐bazole derivatives (7, 8, 9, 10, 11, 12, 13) were synthesized. 相似文献
39.
3-Alkyl(Aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) reacted with 2-furoyl chloride and thiophene-2-carbonyl chloride to afford the corresponding 3- alkyl(aryl)-4-(2-furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3) and 3-alkyl(aryl)- 4-(2-thienylcarbonylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (4), respectively. The new compounds synthesized were characterized by using IR, 1H-NMR, 13C-NMR and UV spectral data together with elemental analysis. In addition, to investigate the effects of solvents and molecular structure upon acidity, compounds 3 and 4 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents (isopropyl alcohol, tert-butyl alcohol, N,N-dimethylformamide and acetonitrile). The half-neutralization potential values and the corresponding pKa values were determined for all cases. 相似文献
40.
Concanavalin A (Con A) immobilized poly(2-hydroxyethyl methacrylate) (PHEMA) beads were investigated for specific adsorption of yeast invertase from aqueous solutions. PHEMA beads were prepared by a suspension polymerization technique with an average size of 150-200 microm, and activated by epichlorohydrin. Con A was then immobilized by covalent binding onto these beads. The maximum Con A immobilization was found to be 10 mg/g. The invertase-loading capability of the PHEMA/Con A beads was 107 mg/g. The maximum invertase adsorption capacity on the PHEMA/Con A adsorbents was observed at pH 5.0. The values of the Michaelis constant K(m) of invertase were significantly larger upon adsorption, indicating decreased affinity by the enzyme for its substrate, whereas V(max) was smaller for the adsorbed invertase. Adsorption improved the pH stability of the enzyme as well as its temperature stability. Thermal stability was found to increase with adsorption. The adsorbed enzyme activity was found to be quite stable in repeated experiments. Storage stability of adsorbed invertase. 相似文献