全文获取类型
收费全文 | 11080篇 |
免费 | 1925篇 |
国内免费 | 1396篇 |
专业分类
化学 | 6521篇 |
晶体学 | 229篇 |
力学 | 527篇 |
综合类 | 83篇 |
数学 | 507篇 |
物理学 | 5453篇 |
无线电 | 1081篇 |
出版年
2024年 | 34篇 |
2023年 | 132篇 |
2022年 | 224篇 |
2021年 | 314篇 |
2020年 | 380篇 |
2019年 | 371篇 |
2018年 | 353篇 |
2017年 | 364篇 |
2016年 | 484篇 |
2015年 | 424篇 |
2014年 | 480篇 |
2013年 | 1286篇 |
2012年 | 623篇 |
2011年 | 720篇 |
2010年 | 574篇 |
2009年 | 701篇 |
2008年 | 676篇 |
2007年 | 620篇 |
2006年 | 654篇 |
2005年 | 588篇 |
2004年 | 526篇 |
2003年 | 509篇 |
2002年 | 450篇 |
2001年 | 332篇 |
2000年 | 396篇 |
1999年 | 302篇 |
1998年 | 219篇 |
1997年 | 216篇 |
1996年 | 221篇 |
1995年 | 148篇 |
1994年 | 170篇 |
1993年 | 141篇 |
1992年 | 123篇 |
1991年 | 105篇 |
1990年 | 80篇 |
1989年 | 69篇 |
1988年 | 57篇 |
1987年 | 36篇 |
1986年 | 48篇 |
1985年 | 43篇 |
1984年 | 47篇 |
1983年 | 10篇 |
1982年 | 24篇 |
1981年 | 22篇 |
1980年 | 16篇 |
1979年 | 14篇 |
1978年 | 10篇 |
1977年 | 9篇 |
1976年 | 7篇 |
1973年 | 24篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
211.
M. Zakrzewski D. D. Klug J. A. Ripmeester 《Journal of inclusion phenomena and macrocyclic chemistry》1994,17(3):237-247
A high-pressure phase of the clathrate hydrate of tetrahydrofuran was prepared by freezing a liquid phase of overall composition THF · 7 H2O under a pressure of 3.0 kbar, or by pressurizing the solid structure II THF hydrate of 255K to 3.4 kbar. Unfortunately, the products recovered at 77K were always mixed phase materials as shown by X-ray powder diffraction. A number of diffraction lines could be indexed in terms of the cubic structure I hydrate with a slightly expanded lattice parameter, 12.08 Å, giving some support to Dyadin's idea that the high pressure phase transition involves a conversion of Structure II to Structure I. Other phases observed in the recovered product include Ice IX and amorphous materials. The reversion of the high pressure sample to the structure II hydrate was followed by differential scanning calorimetry. At ambient pressure, the high pressure sample converts slowly back to Structure II hydrate event at 77K.NRCC No. 35786. 相似文献
212.
The vaterite—calcite transition above 630 K has been studied by isothermal and non-isothermal differential scanning calorimetry. Vaterite samples prepared under different conditions were investigated. The transition temperature is strongly dependent on the sample preparation. The observed transition enthalpy Htr is nearly equal for different samples and experimental conditions. From 28 measurements a value of Htr–(3.12±0.11) kJ mol–1 was obtained. The activation energy for the polymorphic transition was calculated from the Arrhenius plot and by use of isoconversional methods, as a function of the degree of conversion. The influence of the kinetic model distortion and experimental uncertainties on the obtained data was discussed. The actual value of the activation energy was assessed at Ea=(250±10) kJ mol–1 for nearly all examined samples. Functions, corresponded to the model mechanism of nuclei formation and growth, provide the unambiguous consideration of the transition kinetic for the investigated vaterite samples. Differences in the dynamic behaviour of several samples at the transition are established.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
213.
We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature. 相似文献
214.
J.A. ColladoM.A.G. Aranda A. CabezaP. Olivera-Pastor S. Bruque 《Journal of solid state chemistry》2002,167(1):80-85
The La2W2−xMoxO9 series has been synthesized by the ceramic method. An alternative synthesis using microwave radiation is also reported. La2W2O9 has two polymorphs and the low-temperature phase (α) transforms to the high-temperature form (β) at 1077°C. The influence of the W/Mo substitution in this phase transition has been investigated by DTA. The β structure for x≥0.7 compositions can be prepared as single phase at any cooling rate. The β phase for 0.3≤x≤0.7 compounds can be prepared as single phase by quenching, whereas a mixture of α and β phases is obtained by slow cooling. The W/Mo ratio in both coexisting phases is different with the β-phase having a higher Mo content. The x=0.1 and 0.2 compounds have been prepared as mixtures of phases. The room temperature structure of β-La2W1.7Mo0.3O9 has been analyzed by the Rietveld method in P213 space group. The final R-factors were RWP=9.0% and RF=5.6% with a structure similar to that of β-La2Mo2O9. Finally, the thermal expansion of both types of structures has been determined from a thermodiffractometric study. The thermal expansion coefficients were 2.9×10−6 and 9.7×10−6°C−1 for α-La2W2O9 and β-La2W1.2Mo0.8O9, respectively. 相似文献
215.
216.
研究了过渡金属催化的炔烃衍生物的异构化反应.从α,β-炔酮、2-炔酸酯和2-炔酸酰胺可以生成相应的(E,E)-共轭双烯酮、双烯酸酯和双烯酸酰胺.首次从2-炔醇异构化为相应的2-烯酮或2-烯醛.这一反应具有简单、高产率和立体选择性的优点.假设反应烯经过连二烯中间体,然后再异构化成产物,这一反应提供了方便而有潜在应用价值的方法以制备天然产物合成时的重要中间体. 相似文献
217.
四(对—羟基苯基)卟啉过渡金属配合物的合成 总被引:15,自引:0,他引:15
四(对-羟基苯基)卟啉过渡金属配合物的合成师同顺*柳巍刘国发王杏乔王世颖(吉林大学化学系长春130023)关键词卟啉,过渡金属配合物,合成1997-10-17收稿,1998-03-20修回国家自然科学基金会资助四(对-羟基苯基)卟啉(H2THPP)可... 相似文献
218.
Russell G. Ross 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):227-233
The thermal conductivity and the heat capacity per unit volumec
p
have been measured for the urea-hexadecane inclusion compound using the transient hot-wire method. Measurements were made under isobaric conditions at a pressure of 0.1 GPa and in the temperature range of 100–300 K. There was evidence for a phase transition at a temperature of about 160 K, in reasonable agreement with previous work. For the high-temperature phase was independent of temperature within ±1%. The low-temperature phase showed a weak temperature dependence, with (d In/d InT)
p
= –0.13. It was inferred that interaction between acoustic phonons and low-frequency vibrational excitations of the guest molecules made a major contribution to the thermal resistivity. For the quantityc
p
a weak maximum was observed in the region of the phase transition temperature.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
219.
Energized molecules are the essential actors in chemical transformations in solution. As the rearrangement of bonds requires a movement of nuclei, vibrational energy is often the driving force for a reaction. Vibrational energy can be redistributed within the "hot" molecule, or relaxation can occur when molecules interact. Both processes govern the rates, pathways, and quantum yields of chemical transformations in solution. Unfortunately, energy transfer and the breaking, formation, and rearrangement of bonds take place on ultrafast timescales. This Review highlights experimental approaches for the direct, ultrafast measurement of photoinduced femtochemistry and energy flow in solution. In the first part of this Review, we summarize recent experiments on intra- and intermolecular energy transfer. The second part discusses photoinduced decomposition of large organic peroxides, which are used as initiators in free radical polymerization. The mechanisms and timescales of their decarboxylation determine the initial steps of polymerization and the microstructure of the polymer product. 相似文献
220.