全文获取类型
收费全文 | 2837篇 |
免费 | 153篇 |
专业分类
化学 | 1967篇 |
晶体学 | 11篇 |
力学 | 114篇 |
数学 | 414篇 |
物理学 | 484篇 |
出版年
2023年 | 25篇 |
2022年 | 29篇 |
2021年 | 37篇 |
2020年 | 48篇 |
2019年 | 46篇 |
2018年 | 56篇 |
2017年 | 46篇 |
2016年 | 93篇 |
2015年 | 87篇 |
2014年 | 94篇 |
2013年 | 176篇 |
2012年 | 229篇 |
2011年 | 266篇 |
2010年 | 114篇 |
2009年 | 98篇 |
2008年 | 207篇 |
2007年 | 170篇 |
2006年 | 165篇 |
2005年 | 160篇 |
2004年 | 134篇 |
2003年 | 108篇 |
2002年 | 79篇 |
2001年 | 36篇 |
2000年 | 35篇 |
1999年 | 22篇 |
1998年 | 25篇 |
1997年 | 17篇 |
1996年 | 23篇 |
1995年 | 16篇 |
1994年 | 24篇 |
1993年 | 21篇 |
1992年 | 20篇 |
1991年 | 20篇 |
1990年 | 22篇 |
1989年 | 16篇 |
1988年 | 10篇 |
1987年 | 12篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1982年 | 20篇 |
1981年 | 12篇 |
1980年 | 16篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 12篇 |
1976年 | 11篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 6篇 |
1969年 | 6篇 |
排序方式: 共有2990条查询结果,搜索用时 437 毫秒
31.
This numerical simulation paper focuses on the adsorption/desorption of water in disordered mesoporous silica glasses (Vycor-like). The numerical adsorbent was previously obtained by off lattice method, and was shown to reproduce quite well the micro- and mesotextural properties of real Vycor, as well as morphological (pore size distribution) and topological (pore interconnections) disorder. The water-water interactions are described by the SPC model while water-silica interactions are calculated in the framework of the PN-TrAZ model. The water adsorption/desorption isotherms and the configurational energies are calculated by the Grand Canonical Monte Carlo simulation method. The low pressure results compare well with experiments, showing the good transferability of the intermolecular potential. It is shown that if the hysteresis loop observed in the adsorption/desorption isotherm is considered as a true phase transition (which is actually still an open question in the case of disordered porous materials), then it is possible to calculate the grand potential by applying the thermodynamic integration scheme. The grand potential is shown to be multivalued for low (subcritical) temperature, and continuous for high (supercritical) temperature. A coexistence point is found within the hysteresis loop, actually close to the vertical desorption line. Below the equilibrium chemical potential, the gaslike branch is stable whereas the liquidlike branch is metastable. The situation is reversed above the coexistence point. 相似文献
32.
Noëlle Martine Gosselet Horacio NaranjoEstelle Renard Catherine AmielBernard Sebille 《European Polymer Journal》2002,38(4):649-654
An acrylic polymer with pendent adamantyl groups was synthesized and its properties in an aqueous solution with a β-cyclodextrin (βCD) epichlorhydrin polymer examined. Viscosity properties of precursor and modified polymers show differences at low concentrations, but not at higher concentration probably due to very important hydrogen bonds which prevent the formation of intermolecular hydrophobic bonds. The association of both complementary polymers through the inclusion of adamantyl groups is evidenced by phases separation occurrence. Phase diagrams were established at two different concentrations of polymers. We have shown a maximal association of both polymers at these two concentrations, for the same ratio βCD moles/adamantyl groups: 2.4. Salt addition favors this association and displaces the two phases zone to smaller concentrations of modified polymer. Further, 4-nitrophenol can be extracted by the concentrated phase resulting from mixture of solutions of guest and host polymers, pointing out the availability of the associated phase to trap organic molecules. 相似文献
33.
Abdennbi Lekchiri Joëlle Morcellet Michel Morcellet 《Journal of polymer science. Part A, Polymer chemistry》1987,25(8):2231-2240
The complexes formed between palladium (II) and a polymeric ligand derived from L -asparagine, poly(N-methacryloyl-L -asparagine) (PNMAsn) have been investigated by electronic absorption and circular dichroism. N-isobutyroyl-L -asparagine (NIBAsn) was also synthesized and studied with the purpose of comparison with its polymeric analog. NIBAsn gives two complexes: at low pH, an optically active complex between one carboxylate and one secondary amide nitrogen (so-called 1N complex), and at higher pH, a 2N complex involving the primary and secondary amide group. This complex is also optically active. PNMAsn gives at low pH a 1N complex similar to that of NIBAsn, but at higher pH the 2N complex is formed between two carboxylate groups and two secondary amide groups of two different side chains of the polymer. At very high pH this 2N complex is hydrolyzed, i.e., the carboxylate-palladium bonds are replaced by hydroxyle-palladium bonds, and the complex becomes optically inactive. 相似文献
34.
3-Nitro-4-chlorocoumarin forms 3-nitro-4-substituted coumarins when it reacts with an equimolar quantity of benzyl mercaptan or thiosalicylic acid; with excess benzyl mercaptan, it forms 3,4-di-S-benzyl coumarin. 3-Nitro-4-methoxycoumarin under the same conditions, with an equimolar ratio of reagents, forms a mixture of monosubstituted and disubstituted products. A mechanism is proposed for these reactions.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1476–1479, November, 1991. 相似文献
35.
[reaction: see text] A simple procedure for the cleavage of triethylsilyl (TES) ethers in the presence of 10 wt % Pd/C in methanol or 95% ethanol is reported. This method allows selective removal of alkyl TES ethers in the presence of aromatic TES ethers or tert-butyldimethylsilyl (TBS) protecting groups. 相似文献
36.
We have studied the diffusion inside the silica network of sodium atoms initially located outside the surfaces of an amorphous silica film. We have focused our attention on structural and dynamical quantities, and we have found that the local environment of the sodium atoms is close to the local environment of the sodium atoms inside bulk sodo-silicate glasses obtained by quench. This is in agreement with recent experimental results. 相似文献
37.
Joëlle Mayrargue Michel Duchon D'Engenires Marcel Miocque 《Journal of heterocyclic chemistry》1978,15(2):263-267
By cyclization in aqueous media, 2-aminomethyl 1-alcynyl 1-cyclohexanols lead to perhydroisoindolinium or perhydroisoquinolinium salts. The stereochemistry of isolated diastereoisomers is elucidated. A stereoselectivity favouring trans junction of the rings is pointed out. 相似文献
38.
This paper describes a novel approach for the surface modification of a cation-exchange membrane, bearing sulfonate groups, by a cationic layer. The modification procedure involved the chlorosulfonation of the sulfonate groups of the base membrane with thionyl chloride, followed by a reaction with a diamine to yield a sulfonamide bond and a terminal amine. The latter could be quaternized by reaction with methyl iodide or protonated by soaking in acidic media. The membranes were characterized in detail by attenuated total reflectance Fourier transform infrared and X-ray photoelectron spectroscopies as well as elemental analysis to confirm that the above reactions occurred. The selectivity of these membranes toward the electrochemically assisted transport of protons versus Zn2+ metallic cations was determined during an electrodialysis in a two-compartment electrochemical cell. The data indicate a significant decrease of the transport of the metallic cations following modification of the membrane with the cationic layer. The later allows for the transport of protons from the catholyte to the anolyte compartment with much improved selectivity since the divalent cations are excluded from the membrane due to the electrostatic barrier of the cationic layer. 相似文献
39.
A way of using gravity flow to induce a linear convection within a microfluidic system is presented. It is shown and mathematically supported that tilting a 1 cm long covered microchannel is enough to generate flow rates up to 1000 nL.min(-1), which represents a linear velocity of 2.4 mm.s(-1). This paper also presents a method to monitor the microfluidic events occurring in a covered microchannel when a difference of pressure is applied to force a solution to flow in said covered microchannel, thanks to electrodes inserted in the microfluidic device. Gravity-induced flow monitored electrochemically is applied to the performance of a parallel-microchannel enzyme-linked immunosorbent assay (ELISA) of the thyroid-stimulating hormone (TSH) with electrochemical detection. A simple method for generating and monitoring fluid flows is described, which can, for instance, be used for controlling parallel assays in microsystems. 相似文献
40.