全文获取类型
收费全文 | 39639篇 |
免费 | 6623篇 |
国内免费 | 4416篇 |
专业分类
化学 | 21985篇 |
晶体学 | 350篇 |
力学 | 1814篇 |
综合类 | 139篇 |
数学 | 3012篇 |
物理学 | 12635篇 |
无线电 | 10743篇 |
出版年
2024年 | 190篇 |
2023年 | 1066篇 |
2022年 | 1357篇 |
2021年 | 1736篇 |
2020年 | 1721篇 |
2019年 | 1650篇 |
2018年 | 1390篇 |
2017年 | 1283篇 |
2016年 | 1894篇 |
2015年 | 1937篇 |
2014年 | 2426篇 |
2013年 | 2926篇 |
2012年 | 3482篇 |
2011年 | 3487篇 |
2010年 | 2349篇 |
2009年 | 2336篇 |
2008年 | 2648篇 |
2007年 | 2196篇 |
2006年 | 2145篇 |
2005年 | 1751篇 |
2004年 | 1235篇 |
2003年 | 1036篇 |
2002年 | 1010篇 |
2001年 | 839篇 |
2000年 | 663篇 |
1999年 | 832篇 |
1998年 | 721篇 |
1997年 | 672篇 |
1996年 | 684篇 |
1995年 | 567篇 |
1994年 | 472篇 |
1993年 | 370篇 |
1992年 | 363篇 |
1991年 | 274篇 |
1990年 | 238篇 |
1989年 | 177篇 |
1988年 | 109篇 |
1987年 | 85篇 |
1986年 | 110篇 |
1985年 | 76篇 |
1984年 | 45篇 |
1983年 | 50篇 |
1982年 | 33篇 |
1981年 | 25篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1957年 | 4篇 |
1923年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Three inorganic–organic composite sandwich-type phosphotungstates [Ni(tepa)(H2O)]4H2[Ni4(H2O)2(α-B-PW9O34)2]·8H2O (1), (enH2)3[Ni2(H2O)10][Ni4(H2O)2(α-B-PW9O34)2]·en·8H2O (2) and (enH2)10[Mn4(H2O)2(α-B-PW9O34)2]2·20H2O (3) (tepa=tetraethylenepentamine and en=ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW9O34]9− with Ni2+ or Mn2+ ions in the presence of tepa or en and structurally characterized by IR spectra, elemental analysis, thermogravimetric analysis and variable temperature magnetic susceptibility. X-ray crystallographic analyses indicate that they all contain the classical tetra-M sandwiched polyoxoanions [M4(H2O)2(α-B-PW9O34)2]10− (M=Ni2+ or Mn2+) and nickel-organoamine cations or organoamine cations work as the charge balance ions. The tetra-M clusters in 1, 2 and 3 exhibit the familiar structural type of a β-junction at the sites of metal incorporation. The study of magnetic property of 1 is indicative of a typical ferromagnetic coupling between Ni2+ cations. 相似文献
992.
Jian‐Hua Zhao Hsuan‐Liang Liu Hsin‐Yi Lin Chih‐Hung Huang Hsu‐Wei Fang Shau‐Wei Tsai 《中国化学会会志》2007,54(4):835-842
In this study, we present the results from the semiempirical molecular orbital calculations for the acylation step in the lipase‐catalyzed ester hydrolysis. The results reveal that the lowest energy path for the formation of the tetrahedral intermediate is for the serine residue of the catalytic triad to attack the substrate, followed by coupling heavy atom movement and proton transfer. The calculations of four active site models show that the cooperation of the aspartate group and the oxyanion hole is capable of lowering the activation energy by about 16 kcalmol?1. Our results further suggest that the lipase‐catalyzed ester hydrolysis adopts the single proton transfer mechanism. 相似文献
993.
Understanding effect of wall structure on the hydrothermal stability of mesostructured silica SBA-15
Zhang F Yan Y Yang H Meng Y Yu C Tu B Zhao D 《The journal of physical chemistry. B》2005,109(18):8723-8732
Mesostructured silica SBA-15 materials with different structural parameters, such as pore size, pore volume, and wall thickness, etc., were prepared by varying the postsynthesis hydrothermal treatment temperature and adding inorganic salts. The hydrothermal stabilities of these materials in steam (100% water vapor) were systematically investigated using a variety of techniques including powder X-ray diffraction, transmission electron microscopy, nitrogen sorption, and (29)Si solid-state NMR. The effect of the pore size, microporosity or mesoporosity, and wall thickness on the stability was discussed. The results show that all of the SBA-15 materials have a good hydrothermal stability under steam of 600 degrees C for at least 24 h. N(2) sorption measurements show that the Brumauer-Emmett-Teller surface area of SBA-15 materials is decreased by about 62% after treatment under steam at 600 degrees C for 24 h. The materials with thicker walls and more micropores show relatively better hydrothermal stability in steam of 600 degrees C. Interestingly, we found that the microporosity of the mesostructured silica SBA-15 is a very important factor for the hydrothermal stability. To the materials with more micropores, the recombination of Si-O-Si bonds during the high-temperature steam treatment may not cause direct destruction to the wall structure. As a result, SBA-15 materials with more micropores show better stability in pure steam of 600 degrees C. Nevertheless, these materials are easily destroyed in steam of 800 degrees C for 6 h. Two methods to effectively improve the hydrothermal stability are introduced here: one is a high-temperature treatment, and another is a carbon-propping thermal treatment. Thermal treatment at 900 degrees C can enhance the polymerization degree of Si-O-Si bonds and effectively improve the hydrothermal stability of these SBA-15 materials in 800 degrees C steam for 12 h. But, this approach will cause very serious shrinkage of the mesopores, resulting in smaller pore diameter and low surface area. A carbon-propping thermal treating method was employed to enhance the polymerization of Si-O-Si bonds and minimize the serious shrinkage of mesopores at the same time. It was demonstrated to be an effective method that can greatly improve the hydrothermal stability of SBA-15 materials in 800 degrees C steam for 12 h. Furthermore, the SBA-15 materials obtained by using the carbon-propping method possess larger pores and higher surface area after the steam treatment at 800 degrees C compared to the materials from the direct thermal treatment method after the steam treatment. 相似文献
994.
There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions. 相似文献
995.
Zhao L Zhu G Zhang D Di Y Chen Y Terasaki O Qiu S 《The journal of physical chemistry. B》2005,109(2):764-768
Using 1,2-bis(trimethoxysilyl)ethane as organosiloxane precursor and a triblock copolymer surfactant, Pluronic F127, as template, a highly ordered mesoporous organosilica with large cagelike pores has been successfully synthesized. Its structure was resolved to be 3-D cubic Fmm by high-resolution transmission electron microscopy. The intergrowth of hexagonal close-packed and cubic close-packed phases was observed in this material. The effect of different siliceous precursors on the mesostructure was also investigated. 相似文献
996.
After mixing a methylbenzene 4 with “magic blue” solution in F113 (CClF2CCl2F) containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl}nitroxide 2 and perfluoro-1-nitroso-1-[1-(2-fluorosulfonyl)ethoxy]ethane 3 at room temperature, benzylic H-atom of 4 could be selectively abstracted by 2, and benzyl radical 5 thus generated was immediately trapped by 3. Based on hyper-fine splitting constants (hfsc), the structure of the spin adducts perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl benzyl nitroxides 6 derived from seven methylbenzenes have been identified. The mechanism of the H-abstraction/spin trapping process is also discussed. 相似文献
997.
Xu X Zhao J Jiang D Kong J Liu B Deng J 《Analytical and bioanalytical chemistry》2002,374(7-8):1261-1266
A novel hydrogen peroxide biosensor was developed based on the immobilization of horseradish peroxidase (HRP) in a TiO(2) sol-gel matrix on an electropolymerized phenazine methosulfate (PMS) modified electrode surface. Such membranes are of interest due to their high surface area, biological compatibility, and ease of fabrication. HRP entrapped in the TiO(2) matix was stable and retained its activity to a large extent. Cyclic voltammetry and amperometric measurements were employed to demonstrate the feasibility of electron transfer between immobilized HRP and the glassy carbon electrode via electropolymerized PMS. The influence of various experimental parameters such as operating potential, pH, temperature, and stability was investigated for optimum analytical performance. The biosensor provided a wide linear calibration range from 4.0x10(-6) M to 1.0x10(-3) M, with a detection limit of 8.0x10(-7) M at a signal-to-noise ratio of 3. The sensor retained 80% of its original activity after two months of operation. 相似文献
998.
A rapid flow-injection method with chemiluminescence (CL) detection is described for the determination of glutathione (GSH).
The method is based on the CL reaction of luminol and hydrogen peroxide. GSH can greatly enhance the chemiluminescence intensity
in 0.1 mol/L borax–sodium hydroxide buffer solution (pH = 9.7). The maximum CL intensity was directly proportional to the
concentration of GSH in the range 3.0 × 10−7–2.0 × 10−5 mol/L, and the detection limit was 6.8 × 10−8 mol/L. The relative standard deviation was 3.4% for 5.0 × 10−6 mol/L of GSH (n = 11).
Received October 23, 2001; accepted June 18, 2002 相似文献
999.
使用密度泛函理论B3LYP方法和6-31G(d,p)、6-31+G(d,p)、6-311G(d,p)及6-311+G(d,p)基组,分别对2-C5H10+和1-C5H10+的各种构象进行了几何构型优化,并用B3LYP/6-311G(d,p)进行了频率分析计算.计算预言1-C5H10+具有非平面构型,与以往报导的从头算计算结论相反.在两个自由基阳离子的各种构象的B3LYP几何构型上,进行了B3LYP和UMP2(full)方法的超精细偶合常数计算,得到了比以往更好的结果. 相似文献
1000.
The photostimulated reaction of halonaphthalene with a series of carbanions derived from,propionic acid derivatives in liquid ammonia led to the naphthylation at a-carbon of the carbanions inan isolated yield ranging from 25% to 86%.In all cases,the dehalonaphthalenes were found to,be by-products and the reaction was inhibited by p-dinitrobenzere.An electron transfer from thecarbanion to the halonaphthalene followed by ejection of halogen led to naphtbyl radical,as predictedby comparing the LUMOs of the carbanions and the halonaphthalenes,was involved in the process.Absence of the alkylnaphthalene and 1,2-dinaphthylalkane in the products indicates the smoothelectron transfer between(Naph-Nu)~+ and Naph-X.C-vs.O-naphthylation is fully addressed interms of MNDO calculations and acid-base principle. 相似文献