全文获取类型
收费全文 | 33911篇 |
免费 | 5874篇 |
国内免费 | 4966篇 |
专业分类
化学 | 26078篇 |
晶体学 | 514篇 |
力学 | 1670篇 |
综合类 | 382篇 |
数学 | 3761篇 |
物理学 | 12346篇 |
出版年
2024年 | 76篇 |
2023年 | 625篇 |
2022年 | 839篇 |
2021年 | 1186篇 |
2020年 | 1420篇 |
2019年 | 1513篇 |
2018年 | 1255篇 |
2017年 | 1263篇 |
2016年 | 1690篇 |
2015年 | 1713篇 |
2014年 | 2138篇 |
2013年 | 2659篇 |
2012年 | 3206篇 |
2011年 | 3301篇 |
2010年 | 2509篇 |
2009年 | 2313篇 |
2008年 | 2490篇 |
2007年 | 2305篇 |
2006年 | 2094篇 |
2005年 | 1658篇 |
2004年 | 1205篇 |
2003年 | 994篇 |
2002年 | 981篇 |
2001年 | 883篇 |
2000年 | 706篇 |
1999年 | 648篇 |
1998年 | 466篇 |
1997年 | 388篇 |
1996年 | 337篇 |
1995年 | 308篇 |
1994年 | 289篇 |
1993年 | 225篇 |
1992年 | 192篇 |
1991年 | 182篇 |
1990年 | 161篇 |
1989年 | 121篇 |
1988年 | 93篇 |
1987年 | 69篇 |
1986年 | 72篇 |
1985年 | 56篇 |
1984年 | 24篇 |
1983年 | 25篇 |
1982年 | 21篇 |
1981年 | 8篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1971年 | 4篇 |
1959年 | 3篇 |
1957年 | 4篇 |
1936年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Four dinuclear and trinuclear Cu(I) complexes that contain 2-(2'-pyridyl)benzimidazolyl derivative ligands including 1,4-bis[2-(2'-pyridyl)benzimidazolyl]benzene (1,4-bmb), 1,3-bis[2-(2'-pyridyl)benzimidazolyl]benzene (1,3-bmb), 1,3,5-tris[2-(2'-pyridyl)benzimidazolyl]benzene (tmb), and 4,4'-bis[2-(2'-pyridyl)benzimidazolyl]biphenyl (bmbp) have been synthesized. The formulas of these complexes are [Cu(2)(1,4-bmb)(PPh(3))(4)][BF(4)](2) (1), [Cu(2)(1,3-bmb)(PPh(3))(4)][BF(4)](2) (2), [Cu(3)(tmb)(PPh(3))(6)][BF(4)](3) (3), and [Cu(2)(bmbp)(PPh(3))(4)][BF(4)](2) (4), respectively. The crystal structures of 2-4 have been determined by single-crystal X-ray diffraction analyses. The Cu(I) ions in the complexes have a distorted tetrahedral geometry. For 3, two structural isomers (syn and anti) resulted from two different orientations of the three 2-(2'-pyridyl)benzimidazolyl chelating units were observed in the crystal lattice. Variable-temperature (1)H NMR experiments established the presence of syn and anti isomers for 1-3 in solution which interconvert at ambient temperature. Complexes 1-4 have a weak MLCT absorption band in the 350-450 nm region and display a yellow-orange emission when irradiated by UV light. One unexpected finding is that the yellow-orange emission of complexes 1-4 has a very long decay lifetime (approximately 200 micros) at 77 K. An electroluminescent (EL) device using 4 as the emitter and PVK as the host was fabricated. However, the long decay lifetime of the copper complexes may limit their applications as phosphorescent emitters in EL devices. 相似文献
972.
We present a database of 21 bond dissociation energies for breaking metal-ligand bonds. The molecules in the metal-ligand bond energy database are AgH, CoH, CoO+, CoOH+, CrCH3+, CuOH2+, FeH, Fe(CO)5, FeO, FeS, LiCl, LiO, MgO, MnCH3NiCH2+, Ni(CO)4, RhC, VCO+, VO, and VS. We have also created databases of metal-ligand bond lengths and atomic ionization potentials. The molecules used for bond lengths are AgH, BeO, CoH, CoO+, FeH, FeO, FeS, LiCl, LiO, MgO, RhC, VO, and VS and the ionization potentials are for the following atoms: C, Co, Cr, Cu, Ni, O, and V. The data were chosen based on their diversity and expected reliability, and they are used along with three previously developed databases (transition metal dimer bond energies and bond lengths and main-group molecular atomization energies) for assessing the accuracy of several kinds of density functionals. In particular, we report tests for 42 previously defined functionals: 2 local spin density approximation (LSDA) functionals, 14 generalized gradient approximation (GGA) methods, 13 hybrid GGA methods, 7 meta GGA methods, and 8 hybrid meta GGA methods. In addition to these functionals, we also examine the effectiveness of scaling the correlation energy by testing 13 functionals with scaled or no gradient-corrected correlation energy, and we find that functionals of this kind are more accurate for metal-metal and metal-ligand bonds than any of the functionals already in the literature. We also present a readjusted GGA and a hybrid GGA with parameters adjusted for metals. When we consider these 57 functionals for metal-ligand and metal-metal bond energies simultaneously with main-group atomization energies, atomic ionization potentials, and bond lengths we find that the most accurate functional is G96LYP, followed closely by MPWLYP1M (new in this article), XLYP, BLYP, and MOHLYP (also new in this article). Four of these five functionals have no Hartree-Fock exchange, and the other has only 5%. As a byproduct of this work we introduce a convenient diagnostic, called the B1 diagnostic, for ascertaining the multireference character in a bond. 相似文献
973.
Chen Y Shortreed MR Peelen D Lu M Smith LM 《Journal of the American Chemical Society》2004,126(10):3016-3017
A major focus of current efforts in genomics is to elucidate the genetic variations extent within the human population, and to study the effects of these variations upon the human system. The most common type of genetic variations are the single nucleotide polymorphisms (SNPs), which occur every 500-1000 nt in the genome. Large-scale population association studies to study the biological or medical significance of such variations may require the analysis of hundreds of thousands of SNPs on thousands of individuals. We are pursuing development of an approach to large-scale SNP analysis that combines the specificity of invasive cleavage reactions with the parallelism of high density DNA arrays. A surface-immobilized probe oligonucleotide is specifically cleaved in the presence of a complementary target sequence in unamplified human genomic DNA, yielding a 5' phosphate group. High sensitivity detection of this reaction product on the surface is achieved by the use of rolling circle amplification, with an approximate concentration detection limit of 10 fM target DNA. This combination of very specific surface cleavage and highly sensitive surface detection will make possible the rapid and parallel analysis of genetic variations across large populations. 相似文献
974.
The nitrosyl-hemoglobin (HbNO) is the carrier of nitric oxide (NO) which is the important messenger molecule displaying multiple physiologic and pathophysiologic roles. However it is still not clear for the fate of HbNO molecules during the venous-arterial transit. In this letter, the HbNO transition in vitro was studied by using the electron paramagnetic resonance (EPR) spectra. It was found that HbNO molecules were stable when oxygen did not exist in the system but not stable in aerobic conditions. The absorption spectra further revealed that the methemoglobin (metHb) was the product of HbNO in aerobic environment, showing that the HbNO changed to metHb when there were enough oxygen molecules in the system. 相似文献
975.
A cytotoxic compound from the leaves of Juglans mandshurica 总被引:1,自引:0,他引:1
From Juglans mandshurica leaves, a new quinone compound was isolated through bioassay-guided fractionation. The structure elucidation of the compound was established based on spectroscopic studies, notably of the 2D NMR spectra. The compound exhibited moderate cytotoxic activities against Hela, MCF-7, BGC823 and 3T3-Llcell lines with IC50 ranges from 7.5 to 26.8 μmol/L. 相似文献
976.
977.
Ying WANG Su Juan WANG Shun Yan MO Shuai LI Yong Chun YANG Jian Gong SHI Institute of Materia Medica Chinese Academy of Medical Sciences Peking Union Medical College 《中国化学快报》2006,(4)
A new abietane diterpene 12-hydroxy-7-oxo-5, 8, 11, 13-tetraene-18, 6-abietanolide, together with a new natural sterol stigmasta-7, 22-diene-3β, 5α, 6α-triol have been isolated from the fruiting body of the fungus Phellinus igniarius. Their structures were elucidated by spectroscopic methods including 2D NMR techniques. 相似文献
978.
Three new serratane triterpenoids, (3α,14α,15α,21α)‐3,14,15,21,29‐pentahydroxyserratan‐24‐oic acid ( 1 ), (3α,21β)‐serrat‐14‐ene‐3,21,24,30‐tetraol ( 2 ), and (3α,21α)‐serrat‐14‐ene‐3,21,24,29‐tetraol ( 3 ), were isolated from Phlegmariurus squarrosus, together with eight known compounds. Their chemical structures were elucidated on the basis of in‐depth spectroscopic analyses. 相似文献
979.
Qing-Lun Wang Li-Na Zhu Dai-Zheng Liao Shi-Ping Yan Zong-Hui Jiang Peng Cheng Guang-Ming Yang 《Journal of Molecular Structure》2005,754(1-3):10-15
A new oxamato-bridged NiIICuIINiII species, [Ni(tacn)(H2O)]2[μ-Cu(pba)](ClO4)2·6H2O 1, (tacn=1,4,7-triazacyclononane; pba=1,3-propylenebis(oxamato)) has been synthesized and structurally as well as magnetically characterized. Complex 1 has a discrete trinuclear NiIICuIINiII structure: Two nickel(II) ions are bridged by [Cu(pba)]2− anion, macrocyclic ligand tacn works as terminal ligand of the nickel(II) center. The magnetic data of compound 1 was analyzed by means ofleading to gCu=2.19, gNi=2.18, J=−112.8 cm−1, D=±4.31 cm−1. The parameters are compared with the similar complexes and the irregular spin state structure of complex 1 is also described here. 相似文献
980.
Zhenshan Jia Xiang Zhang Gaihong Zhang Shaohua Huang Hao Fang Xiangqing Hu Yuliang Li Prof. Liangbing Gan Prof. Shiwei Zhang Prof. Daoben Zhu Prof. 《化学:亚洲杂志》2007,2(2):290-300
The Cs‐symmetric fullerene chlorohydrin C60(Cl)(OH)(OOtBu)4 reacts with 4‐dimethylaminopyridine (DMAP) and 1,4‐diazabicyclo[2.2.2]octane (DABCO) to yield two isomers with the formula C60(O)(OOtBu)4 in good yields. These isomers differ with respect to the location of the epoxy functionality. The one from DMAP is Cs symmetric, whereas that from DABCO is C1 symmetric with the epoxy group on the central pentagon. Two different mechanisms are proposed to explain the chemoselectivity of these reactions. The reaction with DMAP involves single‐electron transfer as the key step; DMAP acts as the electron donor. A combination of an oxygen‐atom shift and SN2′′ processes (boomerang substitution) are responsible for the formation of isomer with DACBO. Various related reactions support the proposed mechanisms. The structures of new fullerene derivatives were determined by spectroscopy, single‐crystal X‐ray analysis, and chemical correlation experiments. 相似文献