全文获取类型
收费全文 | 101957篇 |
免费 | 4446篇 |
国内免费 | 2750篇 |
专业分类
化学 | 41184篇 |
晶体学 | 1073篇 |
力学 | 8129篇 |
综合类 | 109篇 |
数学 | 34557篇 |
物理学 | 24101篇 |
出版年
2024年 | 71篇 |
2023年 | 523篇 |
2022年 | 947篇 |
2021年 | 908篇 |
2020年 | 1007篇 |
2019年 | 992篇 |
2018年 | 11031篇 |
2017年 | 10808篇 |
2016年 | 7134篇 |
2015年 | 1970篇 |
2014年 | 1620篇 |
2013年 | 2081篇 |
2012年 | 6084篇 |
2011年 | 12705篇 |
2010年 | 7110篇 |
2009年 | 7419篇 |
2008年 | 8117篇 |
2007年 | 10126篇 |
2006年 | 1554篇 |
2005年 | 2419篇 |
2004年 | 2333篇 |
2003年 | 2583篇 |
2002年 | 1601篇 |
2001年 | 682篇 |
2000年 | 720篇 |
1999年 | 662篇 |
1998年 | 613篇 |
1997年 | 578篇 |
1996年 | 645篇 |
1995年 | 472篇 |
1994年 | 380篇 |
1993年 | 326篇 |
1992年 | 286篇 |
1991年 | 259篇 |
1990年 | 218篇 |
1989年 | 201篇 |
1988年 | 155篇 |
1987年 | 166篇 |
1986年 | 144篇 |
1985年 | 128篇 |
1984年 | 89篇 |
1983年 | 79篇 |
1982年 | 76篇 |
1981年 | 56篇 |
1980年 | 57篇 |
1979年 | 54篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Two new compounds from Zingiber officinale 总被引:1,自引:0,他引:1
Yu Zhao Qiao Feng Tao Rong Ping Zhang Chang Xin Zhou Hui Dou Shu Yun Shi Ye Cheng Xiao Lian Li Sun Su Zeng Ke Xin Huang Xiao Dong Zhang Xiao Kun Li 《中国化学快报》2007,18(10):1247-1249
A new cyclic diarylheptanoid,1,5-epoxy-3-hydroxy-1-(3-methoxy-4,5-dihydroxyphenyl)-7-(4-hydroxyphenyl)-heptane (1),as well as a new monoterpene,10-O-β-D-glucopyranosyl-hydroxy cineole (2) were isolated from the rhizomes of Zingiber officinale. The structures of compounds 1 and 2 were established based on their spectral data.In addition,the antioxidant activities of these compounds were also measured. 相似文献
992.
Y. Shi L. Sun J. E. S. Venart R. C. Prasad 《Journal of Thermal Analysis and Calorimetry》2006,86(3):585-590
The transient hot-wire technique is widely used for absolute measurements
of the thermal conductivity and thermal diffusivity of fluids. It is well
established that fluid radiation effects significantly influence these measurements,
especially those for the thermal diffusivity. Corrections for radiation effects
are based on the models developed and deviations of the measured data from
the ideal line source model. In this paper, the effect of fluid radiation
on the measurements of the thermal conductivity of n-pentane
is presented. For comparison, the influence of thermal radiation effect on
measurement of transparent fluids, such as argon is also shown. The difference
between the influence of natural convection and thermal radiation is also
demonstrated. 相似文献
993.
On the basis of the structures and properties of the ClO/ClO? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C1), 20.54 (EC2: C2, 2B), 20.69 (EC3: C1), 20.70 (EC4: Cs, 2A′), and 20.69 (EC.5: C2h, 2Bu) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
994.
Xin-hua Wan Hui-lin Tu Ying-feng Tu Dong Zhang Ling Sun Qi-feng Zhou Yu-ping Dong Mao Tang Department of Polymer Science & Engineering College of Chemistry Peking University Beijing China Department of Materials & Chemical Engineering Beijing Institute of Technology Beijing China 《高分子科学》1999,(2):189-192
The first TEMPO-mediated "living" free radical polymerization of liquid crystallinemonomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS), was carried out at 130℃ withBPO as an initiator. The molecular weight of the polymer can be varied from rather low values to highvalues while maintaining narrow polydispersity. It was observed that the polymerization of MPCSproceeded much faster than that of styrene. A tentative explanation for this fast polymerization wassuggested. 相似文献
995.
The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1–aminopyrene and pmpa=N–(2–pyridylmethylene)–1–pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, esták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
996.
The equilibrium constants, K
2, have been determined for the proton-transfer reactions of 1-phenacylquinolinium ion, PHQ+, with several amines {triethylamine (TEA), N,N,N′,N′-tetramethylethylenediamine (ED), N,N,N′, N′-tetramethylpropanediamine (PD), N,N,N′,N′-tetramethylbutanediamine (BD), and 1,8-bis(dimethylamino-naphthalene (DMAN)} in acetonitrile (AN), AN-tetrahydrofuran (THF)
and AN-ethanol (EtOH) mixtures. The reaction was followed spectrophotometrically using a stopped-flow technique. The K
2 value decreased for DMAN and increased for TEA with increasing vol-% of THF in AN-THF mixtures. The changes in the K
2 value for ED, PD and BD changed in the order: ED, PD and BD from a pattern similar to TEA to a pattern similar to DMAN. The
change in the K
2 value for DMAN with increasing vol-% of THF in AN-THF mixtures was explained by the effect of polarity on the stability of
P−Q+ (the deprotonated product of PHQ+). The effect of THF on the K
2 value is consistent with that of the peak wavelength of the absorption spectrum of P−Q+. The change in the K
2 value for TEA, ED, PD and BD depended on the structures of the protonated bases, one of the products for this reaction. The
effect of EtOH on the K
2 value for DMAN was examined in ternary EtOH-THF-AN mixtures that contain different amounts of EtOH and whose relative permittivities
were adjusted to that of EtOH. The K
2 value increased with increasing vol-% of EtOH because of the stabilization of P−Q+ upon the formation of the hydrogen-bonded complex with EtOH. The absorption spectrum of P−Q+ demonstrated a blue shift as the vol-% of EtOH increased. 相似文献
997.
The total energy of all π-electrons in a conjugated hydrocarbon (within the framework of HMO approximation) is the sum of the absolute value of all
the eigenvalues of its corresponding graph. In this paper, we consider “double hexagonal chains” as benzenoids constructed
by successive fusions of successive naphthalenes along a zig–zag sequence of triples of edges as appear on opposite sides
of each naphthalene unit. It is shown that if the fusions are such as to give a polyaceacene then the total π-electron energy
is the minimum from among all the double hexagonal chains with the same number of naphthalene units.
相似文献
998.
Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE. 相似文献
999.
Grażyna Janowska Teresa Mikołajczyk Dorota Wołowska-Czapnik M. Boguń 《Journal of Thermal Analysis and Calorimetry》2005,82(1):129-135
The paper discusses the thermal properties of alginate fibres made from alginic acid or sodium alginate and from alginates
substituted with divalent metal ions during the fibre-forming stage. Alginate fibres with an addition of silica nanoparticles
have also been examined. The selection of fibre-forming parameters was intended to obtain the best either sorption or strength
properties depending on the specific fibre application. Thermal curves of the fibres under investigations obtained by under
air atmosphere and differential scanning calorimetry (DSC) under neutral gas atmosphere have been interpreted from the view
of physical and chemical changes in the fibre-forming material. Based on thermogravimetric curves, the fibre thermal stability
indices have been determined. It has been found that the addition of silica nanoparticles exerts a positive influence on the
thermal properties of the examined fibres. 相似文献
1000.
Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy
Concepción López Rosa M. Claramunt M. Ángeles García José Elguero 《Central European Journal of Chemistry》2004,2(4):660-671
Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by13C and 15N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists. 相似文献