全文获取类型
收费全文 | 7501篇 |
免费 | 1543篇 |
国内免费 | 947篇 |
专业分类
化学 | 5442篇 |
晶体学 | 172篇 |
力学 | 502篇 |
综合类 | 112篇 |
数学 | 697篇 |
物理学 | 3066篇 |
出版年
2024年 | 38篇 |
2023年 | 187篇 |
2022年 | 320篇 |
2021年 | 347篇 |
2020年 | 460篇 |
2019年 | 395篇 |
2018年 | 339篇 |
2017年 | 323篇 |
2016年 | 479篇 |
2015年 | 527篇 |
2014年 | 563篇 |
2013年 | 703篇 |
2012年 | 746篇 |
2011年 | 736篇 |
2010年 | 514篇 |
2009年 | 431篇 |
2008年 | 446篇 |
2007年 | 398篇 |
2006年 | 313篇 |
2005年 | 304篇 |
2004年 | 230篇 |
2003年 | 188篇 |
2002年 | 195篇 |
2001年 | 150篇 |
2000年 | 86篇 |
1999年 | 74篇 |
1998年 | 58篇 |
1997年 | 40篇 |
1996年 | 38篇 |
1995年 | 18篇 |
1994年 | 26篇 |
1993年 | 25篇 |
1992年 | 28篇 |
1991年 | 19篇 |
1990年 | 26篇 |
1989年 | 17篇 |
1988年 | 17篇 |
1987年 | 12篇 |
1986年 | 13篇 |
1985年 | 15篇 |
1984年 | 14篇 |
1983年 | 19篇 |
1982年 | 12篇 |
1981年 | 16篇 |
1980年 | 12篇 |
1979年 | 15篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1974年 | 9篇 |
1973年 | 5篇 |
排序方式: 共有9991条查询结果,搜索用时 15 毫秒
81.
High-resolution solid-state 29Si NMR has been applied to the study of partially exchanged Li, K, and Cs NaY zeolites. The order of the 29Si chemical shifts of dehydrated samples is Li, Na-Y < Na-Y < K, Na-Y. The correlation between the 29Si chemical shift and the Li or K loading on Li, Na-Y or K, Na-Y was rationalized in terms of the interaction between the framework and the cations inside the small cages. Because of the restrictive migration of large Cs+ ions from the supercages to the small cages, the 29Si chemical shift of Cs, Na-Y was found to be similar to that of Na-Y. 相似文献
82.
Hui Chao Yi-Xian Yuan Feng Zhou Liang-Nian Ji Jian Zhang 《Transition Metal Chemistry》2006,31(4):465-469
A novel dinuclear ruthenium(II) complex [(phen)2Ru(mbpibH2)Ru(phen)2]4+ [phen = 1,10-phenanthroline; mbpibH2 = 1,3-bis(1,10-phenanthroline[5,6-d]imidazol-2-yl)-benzene] has been synthesized and characterized. The DNA-binding behavior
of this complex has been studied by spectroscopic and viscosity measurements. Results suggest that the dinuclear ruthenium(II)
complex intercalates into DNA base pairs via its bridging moiety. It has also been found that the dinuclear ruthenium(II) complex displays the enantiopreferential DNA-binding
after equilibrium dialysis. 相似文献
83.
InitiationMechanismofPolymerizationofAcryl-amidebyCericIon/2-BenzoylAcetanilideSystemDONGJian-hua,DENGChao,QIUKun-yuanandFENG... 相似文献
84.
A homologous series of first-to third-generation dendritic polyamides 2a, 3, and 5 with tris(aminoethyl) amine (TREA) as the core and the protected amino functional groups at the periphery were synthesized
via active ester route from “Schlüter” type dendron 1a. Their structures were characterized by 1H-NMR and mass spectra. Based on the efficient synthesis of the first generation dendrimer 2a (yield 75%), the synthesis of second-generation dendrimer 3 was found to be more efficient via the convergent method (yield 69%), while the mixed strategy was applied efficiently for the synthesis of the higher generation
dendrimer 5 (yield 37%). The overall yield for the third generation dendrimer 5 from Schlüter dendron is 12%.
__________
Translated from Huaxue Tongbao (Chemistry), 2005, 68(12) (in Chinese) 相似文献
85.
86.
87.
Chao Chen Yu-Lin Yang Kun-Lin Huang Zhen-Hua Sun Wei Wang Zhuo Yi Yun-Ling Liu Wen-Qin Pang 《Polyhedron》2004,23(18):3033-3042
With a hydrothermal technique, a layered titanium phosphate with the formula Ti2(H2PO4)(HPO4)(PO4)2 · 0.5C6N2H16 (denoted TP-J2) has been prepared by treating the Ti/H3PO4/H2O/1-methylpiperazine system directly. The as-synthesized products were characterized by powder X-ray diffraction, CP-MAS solid-state 31P NMR spectroscopy, thermogravimetric and differential thermal analyses (TG-DTA). The structure was solved by single-crystal X-ray diffraction analysis and it presents an extended γ-phase intercalated with organic amine. Crystal data: triclinic, , a = 8.106 (2) Å, b = 8.197 (2) Å, c = 11.658 (2) Å. = 78.32 (3)°, β = 80.85 (3)°, γ = 77.90 (3)°, Z = 2. Additionally, the intercalation behavior of TP-J2 with n-alkyl monoamine (n = 2, 3, 4, 6, 8, 10 and 12) was investigated. Owing to the strong brønsted base, N,N′-dimethylpiperazine, resides in the interlayer, it presented unusual features of TP-J2 in contrast with that of γ-Tip. 相似文献
88.
[reaction: see text] The intramolecular Mannich reaction of delta-amino beta-keto esters with aldehydes and ketones is a new methodology for the synthesis of polysubstituted piperidines and is illustrated by the concise asymmetric synthesis of the dendrobate alkaloid (+)-241D and its C-4 epimer. 相似文献
89.
Blackwell HE Sadowsky JD Howard RJ Sampson JN Chao JA Steinmetz WE O'Leary DJ Grubbs RH 《The Journal of organic chemistry》2001,66(16):5291-5302
Heptapeptides containing residues with terminal olefin-derivatized side chains (3 and 4) have been treated with ruthenium alkylidene 1 and undergone facile ring-closing olefin metathesis (RCM) to give 21- and 23-membered macrocyclic peptides (5 and 6). The primary structures of peptides 3 and 4 were based upon a previously studied heptapeptide (2), which was shown to adopt a predominantly 3(10)-helical conformation in CDCl(3) solution and an alpha-helical conformation in the solid state. Circular dichroism, IR, and solution-phase (1)H NMR studies strongly suggested that acyclic precursors 3 and 4 and the fully saturated macrocyclic products 7 and 8 also adopted helical conformations in apolar organic solvents. Single-crystal X-ray diffraction of cyclic peptide 8 showed it to exist as a right-handed 3(10)-helix up to the fifth residue. Solution-phase NMR structures of both acyclic peptide 4 and cyclic peptide 8 in CD(2)Cl(2) indicated that the acyclic diene assumes a loosely 3(10)-helical conformation, which is considerably rigidified upon macrocyclization. The relative ease of introducing carbon-carbon bonds into peptide secondary structures by RCM and the predicted metabolic stability of these bonds renders olefin metathesis an exceptional methodology for the synthesis of rigidified peptide architectures. 相似文献
90.
An electrochemical synthesis of oxazol‐2‐ones and imidazol‐2‐ones has been developed via 5‐exo‐dig cyclization of propargylic carbamates‐ and ureas‐derived amidyl radicals. The electrosynthesis relies on the dual function of 2,2,6,6‐tetramethylpiperidin‐ 1‐yl)oxyl (TEMPO) as a redox mediator for amidyl radical formation and an oxygen atom donor. The reactions are conducted under mild conditions using a simple setup and provide convenient access to functionalized oxazol‐2‐ones and imidazol‐2‐ones from readily available materials. 相似文献