全文获取类型
收费全文 | 889篇 |
免费 | 38篇 |
国内免费 | 3篇 |
专业分类
化学 | 555篇 |
晶体学 | 5篇 |
力学 | 37篇 |
数学 | 99篇 |
物理学 | 234篇 |
出版年
2023年 | 9篇 |
2022年 | 20篇 |
2021年 | 22篇 |
2020年 | 29篇 |
2019年 | 34篇 |
2018年 | 38篇 |
2017年 | 25篇 |
2016年 | 45篇 |
2015年 | 30篇 |
2014年 | 51篇 |
2013年 | 88篇 |
2012年 | 57篇 |
2011年 | 72篇 |
2010年 | 36篇 |
2009年 | 50篇 |
2008年 | 47篇 |
2007年 | 36篇 |
2006年 | 26篇 |
2005年 | 19篇 |
2004年 | 20篇 |
2003年 | 5篇 |
2002年 | 12篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1996年 | 11篇 |
1995年 | 3篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 10篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 6篇 |
1965年 | 3篇 |
1957年 | 4篇 |
1944年 | 4篇 |
排序方式: 共有930条查询结果,搜索用时 31 毫秒
91.
In this article, a multiobjective problem with a feasible set defined by inequality, equality and set constraints is considered, where the objective and constraint functions are locally Lipschitz. Several constraint qualifications are given and the relations between them are analyzed. We establish Kuhn-Tucker and strong Kuhn-Tucker necessary optimality conditions for (weak) quasi e?ciency in terms of the Clarke subdifferential. By using two new classes of generalized convex functions, su?cient conditions for local (weak) quasi e?cient are also provided. Furthermore, we study the Mond-Weir type dual problem and establish weak, strong and converse duality results. 相似文献
92.
Mohammad Behbahani Hamid Sadeghi Abandansari Mani Salarian Meysam Babapour Akbar Bagheri Mohammad Reza Nabid 《Mikrochimica acta》2014,181(1-2):129-137
We have designed and synthesized a thermosensitive tri-block copolymer for selective trace extraction of Pb(II) ions from biological and food samples. The polymer was characterized by Fourier transform IR and NMR spectroscopy, and by gel permeation chromatography. The critical aggregation concentration and lower critical solution temperature were determined via fluorescence and UV spectrophotometry, respectively. The effects of solution pH value, amount of copolymer, of the temperature on extraction and on phase separation, and of the matrix on the extraction of Pb(II) were optimized. Pb(II) ions were then quantified by FAAS. The use of this copolymer resulted in excellent figures of merit including a calibration plot extending from 0.5 to 160 μg L?1 (with an R2 of >0.99), a limit of detection (LOD) as low as 90 pg L?1, an extraction efficiency of >98 %, and relative standard deviations of <4 % for eight separate extraction experiments. Figure
In this paper, for the first time an intelligent system using a thermosensitive tri-block copolymer for selective trace removal of Pb(II) in biological and food samples was designed and its determination was carried out by flame atomic absorption spectrometry. 相似文献
93.
Precise measurements of density and sound velocity at different temperatures ranging from 283.15 to 308.15 K for solutions of PEGDME250, PEGDME500 and PEGDME2000 in water and of PEGDME500 in aqueous solutions of 0.500 mol kg−1 ammonium di-hydrogen phosphate ((NH4)H2PO4) and di-ammonium hydrogen phosphate ((NH4)2HPO4), binodal curves at temperature ranges 293.15-318.15 K for the aqueous PEGDME500 + (NH4)2HPO4, PEGDME500 + (NH4)3PO4, PEGDME2000 + (NH4)H2PO4, PEGDME2000 + (NH4)2HPO4, PEGDME2000 + (NH4)3PO4 and PPG400 + (NH4)2HPO4 two-phase systems, and liquid-liquid equilibrium data at temperature ranges 298.15-318.15 K for the aqueous PEGDME500 + (NH4)2HPO4 and PEGDME2000 + (NH4)2HPO4 two-phase systems have been taken. From the experimental density and sound velocity data, the apparent specific volume, excess specific volume, isentropic compressibility and isentropic compressibility deviation values have been determined and the effect of temperature, charge on the anion of electrolytes and molar mass of PEGDME on the volumetric and compressibility properties of the investigated polymer solutions as well as on the salting-out effect of PEGDMEs produced by ammonium phosphate salts has been studied. 相似文献
94.
Three novel diterpene glycosides were isolated for the first time from the commercial extract of the leaves of Stevia rebaudiana, along with several known steviol glycosides, namely stevioside, rebaudiosides A-F, rubusoside and dulcoside A. The new compounds were identified as 13-[(2-O-β-D-glucopyranosyl-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy] ent-kaur-15-en-19-oic acid, 13-[(2-O-β-D-glucopyranosyl-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]-16β-hydroxy-ent-kauran-19-oic acid and 13-methyl-16-oxo-17-nor-ent-kauran-19-oic acid-β-D-glucopyranosyl ester on the basis of extensive 2D NMR and MS spectroscopic data as well as chemical studies. 相似文献
95.
Balamurugan M Mayilmurugan R Suresh E Palaniandavar M 《Dalton transactions (Cambridge, England : 2003)》2011,40(37):9413-9424
Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) ?) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) ?) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) ?) is shorter than the Ni-N(py) bond (2.074(4) ?) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly coordinating -NMe(2) or -NEt(2) donor nitrogen atom the catalytic activity decreases slightly with no change in the selectivity. In contrast, upon replacing the pyridyl nitrogen donor by the strongly σ-bonding imidazolyl or sterically demanding quinolyl/benzimidazolyl nitrogen donor, both the catalytic activity and selectivity decrease, possibly due to destabilization of the intermediate [(4N)(CH(3)CN)Ni-O˙](+) radical species. Adamantane is selectively (3°/2°, 12-17) oxidized to 1-adamantanol, 2-adamantanol and 2-adamantanone while cumene is selectively oxidized to 2-phenyl-2-propanol. In contrast to cyclohexane oxidation, the incorporation of sterically hindering quinolyl/benzimidazolyl donors around Ni(ii) leads to a high 3°/2° bond selectivity for adamantane oxidation. A linear correlation between the metal-ligand covalency parameter (β) and the turnover number has been observed. 相似文献
96.
Mani L Petek S Valentin A Chevalley S Folcher E Aalbersberg W Debitus C 《Natural product research》2011,25(20):1923-1930
The compound haliclonacyclamine A was isolated from the Haliclona sponge at Solomon Islands. It acts as a powerful in?vitro and in?vivo anti-plasmodial agent against the chloroquine-resistant Plasmodium falciparum strain FCB1and Plasmodium vinckei petteri-infected mice, respectively. 相似文献
97.
Morra S Valetti F Sadeghi SJ King PW Meyer T Gilardi G 《Chemical communications (Cambridge, England)》2011,47(38):10566-10568
[FeFe]-hydrogenases are efficient natural catalysts that can be exploited for hydrogen production. Immobilization of the recombinant [FeFe]-hydrogenase CaHydA was achieved for the first time on an anatase TiO(2) electrode. The enzyme is able to interact and exchange electrons with the electrode and to catalyze hydrogen production with an efficiency of 70%. 相似文献
98.
Semigroup Forum - Let S be a foundation topological semigroup and $$M_a(S)$$ the space of all measures $$\mu \in M(S)$$ for which the maps $$x\longmapsto |\mu |*\delta _{x}$$ and $$x\longmapsto... 相似文献
99.
Akshay Mathkar T. N. Narayanan Lawrence B. Alemany Paris Cox Patrick Nguyen Guanhui Gao Patricia Chang Rebeca Romero‐Aburto Sendurai A. Mani P. M. Ajayan 《Particle & Particle Systems Characterization》2013,30(3):266-272
The richly functionalized basal plane bonded to polar organic moieties makes graphene oxide (GO) innately hydrophilic. Here, a methodology to synthesize fluorinated graphene oxide by oxidizing the basal plane of fluorinated graphite, allowing for tunable hydrophobicity of GO, is reported. Fluorine exists as tertiary alkyl fluorides covalently bonded to graphitic carbons, and using magic‐angle spinning (MAS) 13C NMR as a primary tool chemical structures for the two types of synthesized fluorinated graphene oxides (FGOs) with significantly different fluorine contents are proposed. The low surface energy of the C–F bond drastically affects GO's wetting behavior, leading to amphiphobicity in its highly fluorinated form. Ease of solution processing enables the fabrication of inks that are spray‐painted on various porous/non‐porous substrates. These coatings maintain amphiphobicity for solvents with surface tensions down to 59 dyn/cm, thus bypassing existing lithographic means to create similar surfaces. The approach towards fluorinating GO and fabricating graphene‐based surfaces with tunable wettability opens the path towards unique, accessible, carbon‐based amphiphobic coatings. 相似文献
100.
In this study, alumina nanoparticles and film were synthesized by sol–gel method and thermally grown. The chemical composition, morphology, and structural properties of the grain nanostructures of the nanoaggregate aluminum atoms on the silicon surface are characterized by X-ray diffraction, energy dispersive spectroscopy, and scanning electron microscopy techniques which show that the atomic ratio of Al and O elements is about 60:45 and the mass ratio is about 70:31. This point reveals that there is no intermediate layer between Al2O3 and the silicon substrate. In conclusion, this nanoparticle shows good electron conductivity at the surface of a carbon paste electrode that shows its ability in the preparation of a nanosensor in morphine analysis. The linear response range and detection limit were found to be 0.1–550 and 0.03 μmol L?1, respectively. The proposed sensor was successfully applied for the determination of morphine in real samples such as human urine and drug. 相似文献