全文获取类型
收费全文 | 5363篇 |
免费 | 178篇 |
国内免费 | 41篇 |
专业分类
化学 | 3724篇 |
晶体学 | 30篇 |
力学 | 124篇 |
数学 | 891篇 |
物理学 | 813篇 |
出版年
2023年 | 27篇 |
2022年 | 99篇 |
2021年 | 155篇 |
2020年 | 117篇 |
2019年 | 115篇 |
2018年 | 92篇 |
2017年 | 97篇 |
2016年 | 198篇 |
2015年 | 155篇 |
2014年 | 196篇 |
2013年 | 298篇 |
2012年 | 370篇 |
2011年 | 430篇 |
2010年 | 248篇 |
2009年 | 238篇 |
2008年 | 359篇 |
2007年 | 320篇 |
2006年 | 278篇 |
2005年 | 262篇 |
2004年 | 251篇 |
2003年 | 172篇 |
2002年 | 178篇 |
2001年 | 87篇 |
2000年 | 70篇 |
1999年 | 68篇 |
1998年 | 50篇 |
1997年 | 50篇 |
1996年 | 64篇 |
1995年 | 53篇 |
1994年 | 41篇 |
1993年 | 40篇 |
1992年 | 32篇 |
1991年 | 42篇 |
1990年 | 29篇 |
1989年 | 25篇 |
1988年 | 21篇 |
1987年 | 20篇 |
1986年 | 30篇 |
1985年 | 39篇 |
1984年 | 35篇 |
1983年 | 17篇 |
1982年 | 30篇 |
1981年 | 13篇 |
1980年 | 9篇 |
1979年 | 5篇 |
1978年 | 9篇 |
1977年 | 5篇 |
1976年 | 10篇 |
1974年 | 6篇 |
1973年 | 7篇 |
排序方式: 共有5582条查询结果,搜索用时 0 毫秒
91.
Palacios F Aparicio D Ochoa De Retana AM de los Santos JM Gil JI Alonso JM 《The Journal of organic chemistry》2002,67(21):7283-7288
A simple and efficient asymmetric synthesis of 2H-azirine-2-phosphine oxides 3 is described. The key step is a solid-phase bound achiral or chiral amine-mediated Neber reaction of beta-ketoxime tosylates derived from phosphine oxides 1. Reaction of 2H-azirines 3 and 11 with carboxylic acids 4 gives phosphorylated ketamides 5 and 12. Ring closure of ketamides 5 and 12 with triphenylphosphine and hexachloroethane in the presence of triethylamine leads to the formation of phosphorylated oxazoles 8 and 13. 相似文献
92.
[reaction: see text] Tetrasubstituted pyrazines containing two phosphonate groups 2 in positions 2 and 5 and trisubstituted pyrazines containing a phosphonate 5 or a phosphine oxide group 7 in position 2 are obtained by thermal treatment of 2H-azirine-2-phosphonates 1 and -phosphine oxides 6. These pyrazines can also be prepared from beta-ketoxime tosylates 9 and 10 or from oxime derived from phosphine oxide 11. 相似文献
93.
Alfonso Loaiza Dan Borchardt Francisco Zaera 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1997,53(14):2481-2493
13C NMR at 125.76 MHz with 1H and 2H decoupling, 2H NMR at 76.77 MHz with 1H decoupling, and 1H NMR at 500.14 MHz with 2H decoupling were employed as analytical tools to study the complex mixtures of deuterated ethanes resulting from the catalytic H–D exchange of normal ethane with gas-phase deuterium in the presence of a platinum foil. Reference samples consisting of 1:1 binary mixtures of pure normal ethane and ethane-dn (n=1–6) were used to identify the peak positions in the 13C, 2H, and 1H NMR spectra due to each individual isotopomer, and the effect of isotopic substitution on the chemical shifts was determined in each case. While the NMR of all three nuclei worked well for the identification of the individual components of the 1:1 standard mixtures, both 1H and 2H NMR suffered from inadequate resolution when studying complex reaction mixtures because of the broadening of the lines due to 1H–1H (1H NMR) and 2H–2H (2H NMR) couplings. 13C NMR was therefore determined to be the method of choice for the quantitative analysis of the reaction mixtures. Using the 13C NMR results, a correlation that takes into account the primary and secondary isotope substitution effects on chemical shifts was deduced. This equation was used for the identification of the individual components of the mixtures, and integration of the individual observed resonances was then employed for quantification of their composition. This study shows that 13C NMR with 1H and 2H decoupling is a viable procedure for studying mixtures of deuterated ethanes. Furthermore, the additivity of the isotopic effects on chemical shifts and the transferability of the values obtained with ethane to other molecules makes this approach general for the analysis of other isotopomer mixtures. 相似文献
94.
Combinatorial development of new catalysts with phosphodiesterase and esterase activities requires specific fluorescent probes for rapid visual detection of hydrolytic activity. Such fluorescent probes have been synthesized with special attention to solubility in water and stability towards spontaneous hydrolysis at a given pH. The probes reported here include compound 5 based on a fluorescein fluorophore, compound 12 for FRET-detection of phosphodiester hydrolysis and compound 25 based on a quinolinium fluorophore. 相似文献
95.
Alpha-amino acids are soluble in acetonitrile when treated with phosphazene bases. As a result, the protection/deprotection events that are usually required for peptide coupling reactions can be minimized. This is illustrated in the synthesis of the important angiotensin-converting enzyme (ACE) inhibitor enalapril. [reaction: see text] 相似文献
96.
Monserrat García Gerhard van Vliet Mattijs G. J. ten Cate Francisco Chvez Ben Norder Bart Kooi Werner E. van Zyl Henk Verweij Dave H. A. Blank 《先进技术聚合物》2004,15(4):164-172
Solution impregnations, pulltrusion and film stacking are widely used methods to prepare thermoplastic composite materials. Extruders are used to melt the polymer and to incorporate fibers into the polymer in order to modify physical properties. In this article, the compounding of colloidal silica nanoparticles filled polyamide‐6 (PA‐6) is achieved using a twin‐screw extruder, which has a significant market share due to its low cost and easy maintenance. The experiments were performed at 250 rpm and the bulk throughput was 6 kg h?1 with a pump pressure of 30 bars. The composites were characterized with nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). As determined by WAXD, the PA‐6 showed higher amounts of γ‐phase when compared to other synthesis methods such as in situ polymerization. TEM pictures showed that the silica particles aggregated nevertheless, upon addition of 14% (w/w) silica the E‐modulus increased from 2.7 to 3.9 GPa indicating that an effective mechanical coupling with the polymer was achieved. The behavior, illustrated with dynamic mechanical analysis (DMA) curves, indicated that in general when a filled system is compared to unfilled material, the values of the moduli (E′ and E″) increased and tan δ decreased. Determination of molecular mass distribution of the samples by means of size exclusion chromatography (SEC) coupled to a refractive index (RI), viscosity (DV) and light scattering (LS) detector revealed that the addition of silica did not decrease the average molecular weight of the polymer matrix, which is of importance for composite applications. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
97.
The 4,4′di-tert-butylbiphenyl (DTBB)-catalysed lithiation of dihydrodibenzothiepine (1) at −78 °C for 30 min followed by reaction with a carbonyl compound [tBuCHO, Ph(CH2)2CHO, PhCHO, (n-C5H11)2CO, (CH2)5CO, (CH2)7CO, (−)-menthone] at the same temperature leads, after hydrolysis with 3 M hydrochloric acid, to sulphanyl alcohols 2. If after addition of a carbonyl compound as the first electrophile [Me2CO, (CH2)5CO, (−)-menthone], the resulting dianion of type II is allowed to react at room temperature for 30 min, a second lithiation takes place to give an intermediate of type III, which by reaction with a second electrophile [Me2CO, Et2CO, (CH2)5CO, ClCO2Et], yields, after hydrolysis, difunctionalised byphenyls 4. The cyclisation of the sulphanyl alcohol 2c under acidic conditions yields the eight-membered sulphur containing heterocycle 3. The lithiation of dihydrodinaphthoheteroepines 7 and 10 with 2.2 equiv of lithium naphthalenide in THF at −78 °C followed by reaction with different electrophiles [H2O, D2O, tBuCHO, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO] at the same temperature leads, after hydrolysis, to unsymmetrically 2,2′-disubstituted binaphthyls 9 and 12, respectively. When the lithiation is performed with an excess of lithium in the presence of a catalytic amount of DTBB (10% molar), a double reductive cleavage takes place to give the dianionic intermediate VII, which by reaction with different electrophiles [H2O, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO], followed by hydrolysis with water, yields symmetrically 2,2′-disubstituted binaphthyls 8 and 11. In the case of starting from (R)- or (S)-dihydrodinaphthoheteroepines 7 and 10, these methodologies allow us to prepare enantiomerically pure compounds 8, 11 and 12. 相似文献
98.
Mounir Maafi Belkacem Laassis Jean-Jacques Aaron M. Carmen Mahedero Arsenio Muñoz De La Peña Francisco Salinas 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(3):235-247
The photooxidation of Azure A and fluorescence properties of Azure A and its photoproduct have been investigated in aqueous media and in the presence of-cyclodextrin (-CD). The fluorescence intensity of the complex formed between the photoproduct and -CD was found to be three times higher than that of the uncomplexed Azure A photoproduct. A complex formation constant of 110±40 M–1 was calculated using the Benesi-Hildebrand treatment of the fluorescence emission data. Although the stoichiometry of the Azure A photoproduct: -CD complex was found to be 1: 1, it seems that the Azure A structure is only partially included. Calibration graphs were plotted for the free Azure A photoproduct and the photogenerated product included in -CD. The analytical parameters and quantification limits were determined. 相似文献
99.
Martinez-Diaz MV Rodriguez-Morgade MS Feiters MC van Kan PJ Nolte RJ Stoddart JF Torres T 《Organic letters》2000,2(8):1057-1060
[formula: see text] New unsymmetrically substituted DB24C8-phthalocyanines, which are able to form complexes with suitable dialkylammonium cations, have been prepared. These complexes most probably have a pseudorotaxane geometry. 相似文献
100.
The global optimization basin-hopping (BH) method has been used to locate the global minima (GM) of Mg(n)F(2n) (n=1-30) clusters using a Born-Mayer-type potential. Some of the GM were particularly difficult to find, requiring more than 1.5 x 10(4) BH steps. We have found that both the binding energy per MgF2 unit and the effective volume of the GM isomers increase almost linearly with n, and that cluster symmetry decreases with cluster size. The data derived from the BH runs reveal a growing density of local minima just above the GM as n increases. Despite this, the attraction basin around each GM is relatively large, since after all their atomic coordinates are randomly displaced by values as high as 2.0 bohrs, the perturbed structures, upon reoptimization, relax back to the GM in more than 50% of the cases (except for n=10 and 11). The relative stabilities derived from energy second differences suggest that n=8,10,13,15, and 20 are probably the magic numbers for these systems. Mass spectrum experiments would be very useful to clarify this issue. 相似文献