全文获取类型
收费全文 | 5290篇 |
免费 | 220篇 |
国内免费 | 850篇 |
专业分类
化学 | 5303篇 |
晶体学 | 86篇 |
力学 | 72篇 |
综合类 | 36篇 |
数学 | 70篇 |
物理学 | 793篇 |
出版年
2024年 | 10篇 |
2023年 | 29篇 |
2022年 | 82篇 |
2021年 | 92篇 |
2020年 | 135篇 |
2019年 | 87篇 |
2018年 | 130篇 |
2017年 | 162篇 |
2016年 | 177篇 |
2015年 | 138篇 |
2014年 | 206篇 |
2013年 | 562篇 |
2012年 | 236篇 |
2011年 | 286篇 |
2010年 | 230篇 |
2009年 | 292篇 |
2008年 | 318篇 |
2007年 | 350篇 |
2006年 | 349篇 |
2005年 | 324篇 |
2004年 | 332篇 |
2003年 | 256篇 |
2002年 | 201篇 |
2001年 | 155篇 |
2000年 | 133篇 |
1999年 | 126篇 |
1998年 | 102篇 |
1997年 | 102篇 |
1996年 | 101篇 |
1995年 | 102篇 |
1994年 | 105篇 |
1993年 | 88篇 |
1992年 | 83篇 |
1991年 | 35篇 |
1990年 | 29篇 |
1989年 | 33篇 |
1988年 | 31篇 |
1987年 | 16篇 |
1986年 | 26篇 |
1985年 | 12篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 15篇 |
1980年 | 16篇 |
1979年 | 12篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1972年 | 4篇 |
排序方式: 共有6360条查询结果,搜索用时 15 毫秒
101.
Optical fiber (OF) sensors are often limited by the immobilization technique used to associate a specific sensing ligand with the OF surface. This is particularly true when the ligand is biologically active as, for example, in the case of immobilized haptens or antibodies. The dynamic modification protocol is a regenerable and experimentally simple way to immobilize a variety of sensing molecules on an OF surface. Furthermore, the protocol is immune to hydrolysis and not limited by diffusion through a membrane or sol–gel. In this publication the approach is extended by immobilizing the hydrophobic hapten (octadecyl 6-(2,4 dinitrophenyl)aminohexanoic acid) as a means to prepare an OF sensor for antibodies specific for 2,4 dinitrophenyl (DNP). The LOD for anti-DNP is 0.5 nanomolar and the Kapparent is 1.0±0.2×106. Nonspecific antibody adsorption is problematic in this sensing approach and was found to limit the quantitative capabilities of the sensor. However, time discrimination can be used to allow the nonspecific antibody to desorb prior to measurement thus minimizing the influence of nonspecific binding on sensor performance. 相似文献
102.
Joseph A. Rard Kirk J. Staggs S. Dan Day Susan A. Carroll 《Journal of solution chemistry》2006,35(8):1187-1215
Boiling temperature measurements have been made at ambient pressure for saturated ternary solutions of NaCl + KNO3 + H2O, NaNO3 + KNO3 + H2O, and NaCl + Ca(NO3)2 + H2O over the full composition range, along with those of the single salt systems. Boiling temperatures were also measured for the four component NaCl + NaNO3 + KNO3 + H2O and five component NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O mixtures, where the solute mole fraction of Ca(NO3)2, x{Ca(NO3)2}, was varied between 0 and 0.25. The maximum boiling temperature found for the NaCl + KNO3 + H2O system is ≈134.9 ∘C; for the NaNO3 + KNO3 + H2O system is ≈165.1 ∘C at x(NaNO3) ≈ 0.46 and x(KNO3) ≈ 0.54; and for the NaCl + Ca(NO3)2 + H2O system is 164.7 ± 0.6 ∘C at x{NaCl} ≈ 0.25 and x{Ca(NO3)2} ≈ 0.75. The NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O system forms molten salts below their maximum boiling temperatures and the temperatures corresponding to the cessation of boiling (dry-out temperatures) of these liquid mixtures were determined. These dry-out temperatures range from ≈300 ∘C when x{Ca(NO3)2} = 0 to ≥ 400 ∘C when x{Ca(NO3)2} = 0.20 and 0.25. Mutual deliquescence/efflorescence relative humidity (MDRH/MERH) measurements were also made for the NaNO3 + KNO3 and NaCl + NaNO3 + KNO3 salt mixture from 120 to 180 ∘C at ambient pressure. The NaNO3 + KNO3 salt mixture has a MDRH of 26.4% at 120 ∘C and 20.0% at 150 ∘C. This salt mixture also absorbs water at 180 ∘C, which is higher than expected from the boiling temperature experiments. The NaCl + NaNO3 + KNO3 salt mixture was found to have a MDRH of 25.9% at 120 ∘C and 10.5% at 180 ∘C. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control brine composition due to the deliquescence of salts formed in dust deposited on waste canisters in the proposed nuclear repository at Yucca Mountain, Nevada. 相似文献
103.
The new nickel selenite chloride, Ni5(SeO3)4Cl2, was obtained by high-temperature solid state reaction of NiCl2, Ni2O3 and SeO2 in a 1:2:4 molar ratio at 700 °C in an evacuated quartz tube. Its structure was established by single-crystal X-ray diffraction. Ni5(SeO3)4Cl2 crystallizes in the triclinic system, space group P-1 (No. 2) with cell parameters of a=8.076(2), b=9.288(2), c=9.376(2) Å, α=101.97(3), β=105.60(3), γ=91.83(3)° and Z=2. All nickel(II) ions in Ni5(SeO3)4Cl2 are octahedrally coordinated by selenite oxygens or/and chloride anions (([Ni(1)O5Cl], [Ni(2)O4Cl2], [Ni(3)O5Cl], [Ni(4)O6] and [Ni(5)O4Cl]). The structure of the title compound features a condensed three-dimensional (3D) network built by Ni(II) ions interconnected by SeO32− anions as well as Cl− anions. Magnetic property measurements show strong antiferromagnetic interaction between nickel(II) ions. 相似文献
104.
Phenyltrimethylsilane possesses a higher HOMO energy (–9.34 eV) than nonsubstituted benzene (>0.41 eV). The π electron of the phenyltrimethylsilane localizes on the benzene ring at the ipso position rather than at the para position. Two center energies calculated by the MNDO-PM3 method indicate that the C? Si bond is facilitated to cleave in comparison with the C? H (para position) one of the benzene ring. Phenyltrimethylsilane and phenyl bis(trimethylsilane) were polymerized with sulfur chloride through the cationic oxidative polymerization. The product is isolated as oligo(p-phenylene sulfide), with a melting point of 150–190°C. An electrophile attacks the carbon atom linked to the Si atom in phenyltrimethylsilane. The new synthetic route of PPS can be established on the basis of the computational calculation. 相似文献
105.
Polyvinyl chloride (PVC) is widely used in industry, but it is difficult to find any extensive discussion of theological relations that describe it. The present paper discusses the behaviour of rigid PVC in extensional deformations at various temperatures. In the tests, a step elongation was applied at an initial time, then after a delay the specimen was cut, permitting recoil. Both linear and nonlinear strain regimes were studied; the linear relaxation properties (relaxation function, storage modulus) were cross-checked with eccentric-disk measurements. In the non-linear strain regime a single-integral constitutive equation of the KBKZ Wagner type was used. Separability of time and strain effects was demonstrated in our tests and so a damping function could be found which was only a function of strain. Video recordings of recoil were made, and detailed predictions of the strain-time behaviour were checked against experiments.Various constitutive equation proposals were used in the comparison, and the separated kernel integral irreversible model performed reasonably well; some other models of a differential type, and a Doi-Edwards model were not as accurate.Dedicated to Professor Arthur S. Lodge on the occasion of his 70th birthday and his retirement from the University of Wisconsin. 相似文献
106.
U. M. Dzhemilev A. G. Ibragimov A. B. Morozov R. R. Muslukhov G. A. Tolstikov 《Russian Chemical Bulletin》1992,41(6):1089-1093
A new stereoselective method is developed for the synthesis of 1-chloro-, 1-alkoxy-, and 1-N,N-dialkylaminoalumino-cyclopentanes from -olefins, metallic magnesium, and aluminum halides (AlCl3, RO-AlCl2, R2N-AlCl2) in the presence of catalytic amounts of Cp2ZrCl2 (Cp=5-C5H5). The products from hydrolysis and deuterolysis of the Al-substituted 3,4-dialkylaluminocyclopentanes (ACP) have the threo configuration.For Communication 8, see [1].Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 450054 Ufa. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1393–1397, June, 1992. 相似文献
107.
Ravil I. Khusnutdinov Tatyana M. Egorova Rishat I. Aminov Yulia Yu. Mayakova Ekaterina S. Mescheryakova 《合成通讯》2020,50(4):564-570
AbstractFeCl3·6H2O-catalyzed Ritter amidation of deltacyclene and hexacyclic norbornadiene dimers containing both a double bond and a three-carbon ring in the molecule with acetonitrile and water was performed. Depending on the hydrocarbon structure, the reaction proceeds via C-C bond cleavage in the three-carbon ring or at the double bond to form the corresponding N-acetamides. 相似文献
108.
109.
Catalytic gas-phase abatement of air containing 250 ppm of isopropanol (IPA) was carried out with a novel dielectric barrier
discharge (DBD) reactor with the inner catalytic electrode made of sintered metal fibers (SMF). The optimization of the reactor
performance was carried out by varying the voltage from 12.5 to 22.5 kV and the frequency in the range 200–275 Hz. The performance
was significantly improved by modifying SMF with Mn and Co oxide. Under the experimental conditions used, the MnO
x
/SMF showed a higher activity towards total oxidation of IPA as compared to CoO
x
/SMF and SMF electrodes. The complete destruction of 250 ppm of IPA was attained with a specific input energy of ∼235 J/L
using the MnO
x
/SMF catalytic electrode, whereas, the total oxidation was achieved at 760 J/L. The better performance of the MnO
x
/SMF compared to other catalytic electrodes suggests the formation of short-lived active species on its surface by the in-situ
decomposition of ozone. 相似文献
110.
A fiber forming PZT gel containing 58.5 wt% PZT was synthesized by using zirconium-n-propylate, titanium-iso-propylate, lead acetate and butoxyethanol. Unseeded PZT gels and gels containing 0.5 wt% PZT perovskite seeds (Ø = 200–300 nm) could be extruded through a monofilament nozzle (Ø = 100 m) at pressures between 50 and 150 bar, whereas PZT gels, containing 1 and 2 wt% PZT particles, were pressed through the nozzle at higher pressures (200–300 bar). The microstructure of unseeded and seeded (0.5, 1, 2 wt% PZT) PZT fibers was characterized by SEM. Unseeded fibers had three different shells at 450°C: an external dense shell (approx. 200 nm thick), a middle shell consisting of a porous structure (1.5m thick) and the center of the fiber, characterized by a matrix containing globular particles. At 700°C, a 200–250 nm thick and dense external shell and a porous fiber interior were be observed. 2 wt% of PZT seeds was necessary to densify the fiber completely. The seeds were located in the center of each PZT perovskite rosette. 相似文献