全文获取类型
收费全文 | 2010篇 |
免费 | 44篇 |
国内免费 | 3篇 |
专业分类
化学 | 1049篇 |
晶体学 | 8篇 |
力学 | 40篇 |
数学 | 199篇 |
物理学 | 761篇 |
出版年
2022年 | 24篇 |
2021年 | 27篇 |
2020年 | 30篇 |
2019年 | 18篇 |
2018年 | 14篇 |
2017年 | 24篇 |
2016年 | 40篇 |
2015年 | 41篇 |
2014年 | 32篇 |
2013年 | 69篇 |
2012年 | 90篇 |
2011年 | 94篇 |
2010年 | 65篇 |
2009年 | 61篇 |
2008年 | 86篇 |
2007年 | 82篇 |
2006年 | 80篇 |
2005年 | 82篇 |
2004年 | 77篇 |
2003年 | 54篇 |
2002年 | 69篇 |
2001年 | 35篇 |
2000年 | 53篇 |
1999年 | 15篇 |
1998年 | 16篇 |
1997年 | 18篇 |
1996年 | 37篇 |
1995年 | 32篇 |
1994年 | 46篇 |
1993年 | 49篇 |
1992年 | 43篇 |
1991年 | 27篇 |
1990年 | 34篇 |
1989年 | 28篇 |
1988年 | 25篇 |
1987年 | 34篇 |
1986年 | 23篇 |
1985年 | 47篇 |
1984年 | 31篇 |
1983年 | 21篇 |
1982年 | 25篇 |
1981年 | 15篇 |
1980年 | 18篇 |
1979年 | 33篇 |
1978年 | 24篇 |
1977年 | 19篇 |
1976年 | 17篇 |
1975年 | 17篇 |
1974年 | 27篇 |
1973年 | 16篇 |
排序方式: 共有2057条查询结果,搜索用时 31 毫秒
21.
Klein SR Himel TM Abrams G Amidei D Baden AR Barklow T Boyarski AM Boyer J Burchat PR Burke DL Butler F Dorfan JM Feldman GJ Gidal G Gladney L Gold MS Goldhaber G Golding L Haggerty J Hanson G Hayes K Herrup D Hollebeek RJ Innes WR Jaros JA Juricic I Kadyk JA Karlen D Lankford AJ Larsen RR LeClaire BW Levi M Lockyer NS Lüth V Matteuzzi C Nelson ME Ong RA Perl ML Petersen A Richter B Riles K Rowson PC Schaad T Schellman H Schmidke WB Sheldon PD Trilling GH de la Vaissiere C Wood DR Yelton JM 《Physical review letters》1987,58(7):644-647
22.
23.
Gidal G Boyer J Butler F Cords D Abrams GS Amidei D Baden AR Barklow T Boyarski AM Burchat P Burke DL Dorfan JM Feldman GJ Gladney L Gold MS Goldhaber G Golding LJ Haggerty J Hanson G Hayes K Herrup D Hollebeek RJ Innes WR Jaros JA Juricic I Kadyk JA Karlen D Klein SR Lankford AJ Larsen RR LeClaire BW Levi ME Lockyer NS Lüth V Matteuzzi C Nelson ME Ong RA Perl ML Richter B Riles K Rowson PC Schaad T Schellman H Schmidke WB Sheldon PD Trilling GH de la Vaissière C Wood DR Yelton JM Zaiser C 《Physical review letters》1987,59(18):2016-2019
24.
25.
Li W Nelson DP Jensen MS Hoerrner RS Javadi GJ Cai D Larsen RD 《Organic letters》2003,5(25):4835-4837
Imidazo[1,2-a]pyrimidine can be arylated at the 3-position with aryl bromides in the presence of base and a catalytic amount of palladium. This provides an efficient one-step synthesis of 3-arylimidazo[1,2-a]pyrimidines from the unsubstituted heterocycle. [reaction: see text] 相似文献
26.
Maria do Carmo B. Pimentel Eduardo Henrique M. Melo José Luiz Lima Filho William M. Ledingham Nelson Durán 《Applied biochemistry and biotechnology》1997,66(2):185-195
This work is a study of lipase production by a Brazilian strain ofPenicillium citrinum using an inexpensive and simple medium without organic nitrogen sources and of some important industrial properties, including
thermostability in relation to ionic strength. The maximal lipase activity (1585 U/L) was obtained whenPenicillium citrinum was cultured on 0.75% ammonium sulfate complemented with minerals salts instead of yeast extract. Although this activity
was about 55% lower than that produced in medium with yeast extract (2850 U/L), the specific activity (7.8 U/mg proteins)
was higher than that obtained with the yeast extract (4.9 U/mg proteins). The morphology of fungus changed totally, with yeast
extract there are smooth, solid, and spherical pellets whereas on ammonium sulfate there are small “hairy” pellets uniformly
suspended in the medium. The effect of ferrous (Fe++) ions was carried out using medium MA with and without Fe++ ions. Lipase production byPenicillium citrinum in medium MA requires Fe++ ions, the absence of which caused a decreased of about 50% in the specific activity (3.5 U/mg proteins). The utilization
of commercial, locally available oils as carbon sources, such as soybean oil (236 U/L) and corn oil (74 U/L) resulted in lower
activity compared to olive oil, showing that lipase production byPenicillium citrinum is specifically induced by olive oil. Potassium concentration in the medium can effects the production of lipase (1 mM (1585
U/L), 10 mM (1290 U/L), and 30 mM (1238 U/L), 50 mM (195 U/L), and 100 mM (2 U/L). The crude culture filtered was susceptable
to thermal deactivation. It was stable at pH 6.0, but was not stable at the optimum pH (8.0-8.5) at 50 mM. At the low ionic
concentration (1-25 mM) this lipase was stable at low pH (3.5-4.0). The activation energy was 22.4 ±2.2 Kcal. mol 1. 相似文献
27.
The development of analytical methods for routine simultaneous identification and quantification of carboxylic fatty acids (CFAs) are required in different fields, such as, pharmaceutical cosmetics, food products and formulations of water–microemulsion–oil systems. Determination of CFAs has been developed mainly by gas chromatography (GC). As an alternative to GC, liquid chromatography (LC) has better sensitivity and selectivity. However, most CFAs show no useful absorption in ultraviolet–violet (UV–Vis) region, one of the more used detection technique in high-performance liquid chromatography (HPLC). In order to allow the use of UV–Vis detection, the use of pre-column derivatization has been reported to increase sensitivity and selectivity. Therefore, establishment of a simpler and faster on-line method with complete separation is needed for the screening of large numbers of samples. 2,4-Dinitrophenylhydrazine (2,4-DNPH.), benzoil chloride (BC), and phenylhydrazine (PH) were used for derivatization of different FAs by microwaves radiation (MW). After the on-line derivatization, products were separated and quantified by HPLC. Reactor coil was placed inside of microwaves oven at 450 W. Parameters as flow, amount of reagents, irradiation time, and chromatographic conditions were optimized. The continuous analysis using the MW–HPLC–UV system provided high sensitivity and reduced both the amount of reagent used and the analysis times. This proposed method can be used for the routine analysis of FAs contained in water–microemulsion–oil systems, to quantify the total acid fraction in each phase. 相似文献
28.
Thompson RS Guler LP Nelson ED Yu YQ Kenttämaa HI 《The Journal of organic chemistry》2002,67(15):5076-5084
The 1,3-dioxolane-2-phosphenium ion, 1,3-benzodioxole-2-phosphenium ion, and o-biphenylenephosphenium ion are reported to react in a stereoselective manner with cis- and trans-1,2-diaminocyclohexanes in the gas phase in a Fourier transform ion cyclotron resonance mass spectrometer. Elimination of NH3 from an addition product was observed only for the trans isomer. Several reaction mechanisms were experimentally and computationally examined (B3LYP/6-31G(d)//HF/6-31G(d) + ZPVE level of theory). The most plausible mechanism is initiated by addition of one of the amino groups to the electrophilic phosphorus atom followed by proton transfer between the amino groups. A change to a diaxial conformation for the trans isomer facilitates anchimeric assistance by the now nucleophilic phosphorus atom as the C-N bond breaks to release NH3. Intramolecular proton transfer competes with the conformational change and ultimately leads to ethylene glycol elimination. The transition states for the critical steps of these two reactions are calculated to be nearly equal in magnitude, which rationalizes the observation of both reactions for the trans-diamine. In contrast, the adduct of the cis isomer can eliminate NH3 via a concerted 1,2-hydride shift without a need for a conformational change. However, the barrier associated with this reaction was found to be substantially greater than for proton transfer between the N- and O-atoms. The latter reaction dominates and ultimately leads to ethylene glycol elimination. 相似文献
29.
Sequence-specific phenylacetylene oligomers consisting of functionalized monomers (hexyl benzoate, hexyl phenyl ether, benzonitrile, and tert-butylphenyl) are synthesized in gram quantities using solid-phase methods. Growing oligomers are attached to a divinylbenzene cross-linked polystyrene support by the 1-aryl-3-propyl-3-(benzyl-supported) triazene moiety. This linkage is obtained by reaction of arenediazonium tetrafluoroborate salts with a n-propylamino-modified Merrifield resin. Condensation strategies are described, producing oligomers with higher yields and simplified procedures compared to solution-phase methods. Terminal acetylene is protected with a trimethylsilyl group. After deprotection of the resin-bound terminal acetylene, an aryl iodide monomer or an aryl iodide-terminated oligomer is coupled to the supported oligomer using a palladium(0) catalyst. The cycle can be repeated to produce sequence-specific oligomers of varying length and functionality. The resulting oligomers are liberated from the polymer support by cleavage of the 1-aryl-3-propyl-3-(benzyl-supported) triazene group by reaction with iodomethane producing an aryl iodide. 相似文献
30.
Dynamic light scattering has been used to determine the hydrodynamic thickness of poly(ethylene oxide) (PEO) adsorbed on synthetic anisotropic clay particles (Laponite) as a function of molecular weight. The layer thicknesses, and their increase with molecular weight, indicate that the conformation of the adsorbed layer is very compact and is much smaller than those normally observed for polymer adsorption on flat interfaces. The aggregation kinetics of the polymer coated particles in 5 mM NaCl was analyzed in a quantitative manner, revealing that the potential barrier to aggregation is strongly enhanced when polymer is present. 相似文献