全文获取类型
收费全文 | 11195篇 |
免费 | 1928篇 |
国内免费 | 1584篇 |
专业分类
化学 | 7862篇 |
晶体学 | 188篇 |
力学 | 739篇 |
综合类 | 151篇 |
数学 | 1464篇 |
物理学 | 4303篇 |
出版年
2024年 | 34篇 |
2023年 | 205篇 |
2022年 | 369篇 |
2021年 | 370篇 |
2020年 | 494篇 |
2019年 | 472篇 |
2018年 | 421篇 |
2017年 | 393篇 |
2016年 | 529篇 |
2015年 | 674篇 |
2014年 | 688篇 |
2013年 | 925篇 |
2012年 | 1094篇 |
2011年 | 1074篇 |
2010年 | 829篇 |
2009年 | 797篇 |
2008年 | 874篇 |
2007年 | 742篇 |
2006年 | 639篇 |
2005年 | 569篇 |
2004年 | 409篇 |
2003年 | 328篇 |
2002年 | 319篇 |
2001年 | 217篇 |
2000年 | 222篇 |
1999年 | 154篇 |
1998年 | 84篇 |
1997年 | 87篇 |
1996年 | 73篇 |
1995年 | 79篇 |
1994年 | 54篇 |
1993年 | 60篇 |
1992年 | 37篇 |
1991年 | 37篇 |
1990年 | 34篇 |
1989年 | 25篇 |
1988年 | 39篇 |
1987年 | 10篇 |
1986年 | 23篇 |
1985年 | 13篇 |
1984年 | 11篇 |
1983年 | 14篇 |
1982年 | 14篇 |
1981年 | 8篇 |
1980年 | 15篇 |
1979年 | 16篇 |
1978年 | 20篇 |
1977年 | 8篇 |
1973年 | 8篇 |
1971年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 8 毫秒
91.
“软平板印刷”微结构制备技术为微米和亚微米器件的制备提供了一条新的途径 [1] ,已被电子学家和材料学家所应用 ,近年来进入了生物学领域[2 ] .本实验室将这一方法与生物分子电子学相结合 ,提出了用于 DNA芯片在片合成的分子印章法 [3,4 ] .分子印章法的实质是接触压印与组合化学相结合的固相界面反应 .聚二甲氧基硅氧烷 ( PDMS)是一种软印刷的优良材料 [5] ,但是由于其疏水性和较差的机械性能 ,必须对其进行改性才能用来制备 DNA分子印章 [6 ] . 聚氨酯作为一种功能材料 ,由于分子中交替的软、硬链段及其不同的热动力学性能而形成… 相似文献
92.
Mid infrared spectroscopy is a non-destructive technique that can provide detailed information on important, molecule-specific features such as the conformation and functional groups of a large range of compounds. Infrared spectroscopy is now an established and frequently used technique for qualitative analysis, i.e. the identification of chemical constituents in a sample. In addition, its use for quantitative purposes has grown dramatically in recent years. It is important to realise that the analytical problem defines the mode of operation and implementation of the FTIR technique. This Highlight article focuses on the advantages and scope of on-line FTIR detection strategies. However, in common with all techniques, on-line FTIR detection has a number of potential shortcomings, which are also discussed. 相似文献
93.
Overgaard J Iversen BB Palii SP Timco GA Gerbeleu NV Larsen FK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(12):2775-2786
The structure and detailed electron density distribution (EDD) of the large octanuclear chromium-wheel host complex [Cr8F8(tBuCO2)16] (1) has been determined from synchrotron X-ray structure factors collected at 16(5) K. The complex has a central cavity with a minimum entry distance between carbon atoms of the pivalate methyl groups (pivalic acid = tBuCO2H) of 4.027(4) A on one side of the molecule and 7.273(4) A on the other. The screened side of the molecule can be "opened" by rotation of methyl groups to create a strained host structure, which is compensated for by improved host-guest and host-solvent interaction. The EDD of the 272-atom complex (1144 e-) was determined by multipole modeling based on the experimental structure factors. 3d orbital populations on the Cr atoms and topological analysis of the EDD show that the covalent part of the metal-ligand interactions consists mainly of sigma donation from the ligands, but that overall the interactions are predominantly electrostatic. The electrostatic potential (EP) has been calculated from the experimental EDD. Knowledge of the geometry of the naked complex 1 as well as the EP in the central cavity of this molecule allows us to deduce which characteristic properties guest molecules must have to be accepted into the void. To probe these predictions, a series of complexes of 1 with different guest inclusions were synthesized (2 = 1 + N,N'-dimethylformamide (DMF), 3 = 1 + N,N'-dimethylacetamide (DMA), 4 = 1 + DMA + DMF, 5 = 1 + 2CH3CN), and their structures were examined by using X-ray diffraction data measured at 120(1) K. Results of these studies indicate that in the crystalline state, the optimal guest molecule should be linear and possess a permanent dipole. Attempts to crystallize the host complex with cations incorporated into the cavity were fruitless, although electrospray ionization mass spectrometry showed that a [1 + potassium]+ entity pre-exists in solution and can be transferred intact into the gas phase. 相似文献
94.
Qiong Yu Lai Ji Zheng LuXiao Bo Su Xiao Yang Ji 《Journal of solid state chemistry》2002,165(2):312-316
Spinel compound LiNi1−xMnxVO4 (0≤x≤0.4) had been prepared by using the moist chemical method. X-ray diffraction spectra showed that the lattice constant increased with x in the LiNi1−xMnxVO4, XPS spectra indicating that Li1s had a chemical shift towards lesser binding energy, and manganese in LiNi1−xMnxVO4 existing as the mixed valence of Mn2+ and Mn3+. The electrochemical charge and discharge testing at a current density of 0.1 mA/cm2 between the potentials of 4.0 and 3.0 V vs Li/Li+ in 1 mol/dm3 LiPF6/EC+DEC (1:1 by volume) at 25°C showed that LiNi1−xMnxVO4 cell has a better rechargeability, but a lower cell voltage of 4.0 V vs Li/Li+ than that without the doping sample, and the capacity and the cycle efficiency of the Li/LiNi1−xMnxVO4 cells increased with x in the LiNi1−xMnxVO4. 相似文献
95.
通过X射线衍射分析和超导量子干涉磁强计(SQUID)磁性测量,研究了Co替代Fe含量对居里温度在室温以上的磁制冷材料La(Fe1-xCox)11.7Al1.3(x=0.072,0.081)磁结构和磁性能的影响。La(Fe1-xCox)11.7Al1.3材料的居里温度随Co的含量增加而增加,La(Fe0.919Co0.081)11.7Al1.3的居里温度为311 K。当外场变化为1.9 T时磁熵变达到3.6 J·kg^-1·K^-1,RCP值为168.6 J·kg^-1,虽然它的磁熵变小于具有巨磁熵变的磁制冷材料,但是它在磁场为1.9 T时的制冷能力与这些材料相当。 相似文献
96.
97.
The charge transport properties of mer-tris(8-hydroxyquinolinato)aluminum(III) (mer-Alq), which is the most widely used electron transport material in OLED, were investigated by quantum chemistry calculations within the framework of the charge hopping model and Marcus electron transfer theory. Internal reorganization energies of 0.276 and 0.242 eV were calculated by the DFT-B3LYP method employing a 6-31 G* basis set for the electrons lambdai(e) and holes lambdai(h), respectively. The relative distances and orientations of Alq molecules in amorphous film were simulated by those in the beta-phase. The intermolecular charge-transfer integrals, Hda(h) and Hda(e), along all 14 hopping pathways were then calculated by the Koopmans Theorem in conjunction with the Hartree-Fock method employing a 6-31 G* basis set as well as by the direct coupling method. The results showed that there were some Hda(e) that were 1 order of magnitude larger than any Hda(h), because hopping pathways with effective overlaps of LUMOs can occur and, thus, large Hda(e). On the other hand, effective overlap of HOMO was absent in all pathways, resulting in a relatively small Hda(h). This difference in the magnitudes of Hda(e) and Hda(h) would predict a 2 orders of magnitude difference in the electron-transfer rate constants and account for the observed 2 orders of magnitude difference in the mobilities of electrons and holes. 相似文献
98.
Cyril Prknyi Hui Liang Yuan Bo H. E. Strmberg Ariella Evenzahav 《Journal of heterocyclic chemistry》1992,29(4):749-753
The synthesis of ten new substituted 1,3,4-thiadiazolyl-4(3H)-quinazolinones 8–11, 13, 17 , and 20–23 is reported. Compounds 8–11 were prepared by condensation of 5-fluoro-2-methyl-3,1-benzoxazin-4-one (3) and 5-substituted 2-amino-1,3,4-thiadiazoles 4–7. Compound 13 was obtained by condensation of 5-fluoro-2-methyl-3,1-benzoxazin-4-one (3) with DL-α-amino-?-caprolactam (12) . Compound 17 was synthesized by condensation of 6-bromo-2-methyl-3,1-benzoxazin-4-one (16) and 2-amino-5-t-butyl-1,3,4-thiadiazole (5) . Compounds 20–23 were obtained by condensation of 5-chloro-6,8-dibromo-2-methyl-3,1-benzoxazin-4-one (19) and 5-substituted 2-amino-1,3,4-thiadiazoles 4–7, respectively. The substituted 3,1-benzoxazin-4-ones 3, 16, and 19 were obtained in good yield by refluxing the appropriate anthranilic acid, 1,15 , and 18 with acetic anhydride (2) . 相似文献
99.
SincethediscoveryofphosphoniumylidebyWittig',carbanionsstabilizedbyadjacentfifthorsixthgrouponiumionshavebeendevelopedasavaluablereactiveintermediate.However,despitethegreateffortsinylidechemistryinthepastfewdecades',relativelylittleisknownaboutthethermodynamicstabilitiesofylidecarbanions.Itiswellknowthatthequantitativemeasuresofthecarbanionstabilityhavecontributedagreatdealtothedevelopmentoforganicchemistry,thereforeitshouldbeexpectedthattheknowledgeaboutylidestabilitywillalsoprovidavaluableg… 相似文献
100.
The electric field gradient (EFG) tensors at the deuterons in the water molecules in BeSO4 · 4D2O at 25°C are reported. The quadrupole coupling constants (e2Q/h) and asymmetry parameters (η) for the two independent deuterons are 181.1(4) and 194.8(3) kHz, and 0.226(4) and 0.123(3), respectively. The EFG tensor corresponding to the smallest e2qQ/h is considerably distorted by the beryllium ion, which causes a high η value as well as a deviation of the y-principal axis by 21.8(6)° from the normal to the water molecule plane. A redetermination of the EFG tensors at the deuterons in the water molecule in Li2SO4 · D2O at 25°C and ?110°C is also reported. The e2Q/h and η values for the two deuterons are 236.6(1.2) and 239.8(1.1) kHz, and 0.091(8) and 0.126(7), respectively, at ?110°C. The corresponding e2qQ/h and η values for the averaged EFG tensor at 25°C are 125.8(1.1) kHz and 0.813(13), respectively. The results are in good agreement with those from the pioneer work by Ketudat and Pound, 20 years ago on the same compound. 相似文献