全文获取类型
收费全文 | 2837篇 |
免费 | 398篇 |
国内免费 | 284篇 |
专业分类
化学 | 1681篇 |
晶体学 | 23篇 |
力学 | 87篇 |
综合类 | 10篇 |
数学 | 242篇 |
物理学 | 675篇 |
无线电 | 801篇 |
出版年
2024年 | 6篇 |
2023年 | 83篇 |
2022年 | 99篇 |
2021年 | 130篇 |
2020年 | 147篇 |
2019年 | 121篇 |
2018年 | 98篇 |
2017年 | 88篇 |
2016年 | 122篇 |
2015年 | 152篇 |
2014年 | 167篇 |
2013年 | 203篇 |
2012年 | 266篇 |
2011年 | 275篇 |
2010年 | 186篇 |
2009年 | 180篇 |
2008年 | 172篇 |
2007年 | 141篇 |
2006年 | 152篇 |
2005年 | 110篇 |
2004年 | 87篇 |
2003年 | 57篇 |
2002年 | 60篇 |
2001年 | 27篇 |
2000年 | 48篇 |
1999年 | 49篇 |
1998年 | 48篇 |
1997年 | 45篇 |
1996年 | 43篇 |
1995年 | 36篇 |
1994年 | 27篇 |
1993年 | 9篇 |
1992年 | 15篇 |
1991年 | 15篇 |
1990年 | 17篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 4篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有3519条查询结果,搜索用时 156 毫秒
61.
Wei F Chen C Zhai L Zhang N Zhao XS 《Journal of the American Chemical Society》2005,127(15):5306-5307
Conventional single nucleotide polymorphism (SNP) assays, which based their detection on the stringency or temperature of the washing buffers, have encountered difficulties to distinguish a single base pair mismatch from a perfect match. In this study, scanning potential hairpin denaturation (SPHD) has been developed to detect SNP in a sensitive and reliable manner. Combined with hairpin oligonucleotide probes, scanning surface electric potential was used to induce a dissociation of double-stranded DNA around a unique "melting potential" (Vm), and it generated a high-contrast SNP recognition signal. A 21 base pair p53 gene segment was used to test this novel method. A single nucleotide mismatch to the hairpin probes caused an average of 400-800 mV difference in melting potential against the perfect match, while the error of this assay was lower than 20 mV. Experiments demonstrated that the hairpin stem was critical to the method. The concept of scanning potential hairpin denaturation could also be used extensively in different areas of nucleotide hybridization based assays. 相似文献
62.
Mechanical properties and stability measurement of cholesterol-containing liposome on mica by atomic force microscopy 总被引:1,自引:0,他引:1
The micromechanical properties of pure and cholesterol modified egg yolk phosphatidylcholine (EggPC) vesicles prepared by sonication were studied by atomic force microscopy (AFM) on mica surface. The force curves between an AFM tip and an unruptured vesicle were obtained by contact mode. During approach, two repulsion regions with two breaks were observed. The slopes of the two repulsive force regimes for the pure EggPC vesicles are determined to be several times lower than that of EggPC/cholesterol vesicles. The elastic properties from force plot analysis based on the Hertzian model showed that Young's modulus (E) and the bending modulus (kc) of cholesterol-modified vesicles increased several-fold compared with pure EggPC vesicles. The significant difference is attributed to the enhanced rigidity of the EggPC vesicles as a result of the incorporation of cholesterol molecules. The behavior of cholesterol-modified vesicles upon adsorption is different from that in solution as revealed by mechanical properties. The results indicate that AFM can provide a direct method to measure the mechanical properties of adsorbed small liposomes and to detect the stability change of liposomes. 相似文献
63.
Xiao‐Yuan Wu Quan‐Guo Zhai Li‐Juan Chen Can‐Zhong Lu 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(6):m261-m263
The title complex, poly[di‐μ3‐oxo‐hepta‐μ2‐oxo‐tetraoxobis(1,10‐phenanthroline)‐μ4‐terephthalato‐dicopper(II)tetramolybdate(VI)], [Cu2Mo4(C8H4O4)O13(C12H8N2)2], represents a novel two‐dimensional copper–molybdate compound with mixed ligands. Tetranuclear molybdenum oxide clusters are joined through corner‐sharing into a ribbon‐like chain, with [Cu(phen)]2+ (phen is 1,10‐phenanthroline) complexes grafted onto either side. The terephthalate ligand lies about an inversion centre and links these chains to form a layer via Cu—O and Mo—O bonds. Face‐to‐face π–π stacking interactions between adjacent phen ligands stabilize the structure. 相似文献
64.
Yi Long Zhu Li-Na Ding Bin Cheng Peng Liao Dai-Zheng Zhai Yu-Ping Yan Shi-Ping Jiang Zong-Hui 《Transition Metal Chemistry》2004,29(2):200-204
Two novel complexes, [Cu(HL)2(H2O)]2(OH)2(ClO4)2·1.5H2O (1) and [Cu(HL)2]Cl2·4H2O (2), have been prepared by reacting copper salts with the 4-amino-3-ethyl-1,2,4-triazole-5-thione (HL) ligand in neutral solution and in HCl (6 mol L–1) medium, respectively. They were characterized by FT-IR and u.v.–vis. spectra, and the structures were determined by single crystal X-ray diffraction techniques. In both complexes, the triazole ligand chelated the metal ions through the amine and thione substituents on the five-membered ring. Complex (1) has a square-pyramidal copper(II) ion coordinated by two triazole ligands and one water molecule. Unlike (1), the Cu2+ ion in (2) displays its characteristic Jahn–Teller distortion with the distance of the Cl– anions to metal ion further away than that of the triazole ligands. The most intriguing structural features of the title complexes are that the HL ligands chelate copper(II) ions through the N(1) and S(1) atoms, in a cis mode in (1) and a trans mode in (2). In both cases, self-assembled crystals, by supramolecular contacts simultaneously, form two multi-dimensional frameworks. 相似文献
65.
66.
67.
The paramagnetic complexes formed in Friedel‐Crafts alkylation reaction systems are invistigated by electron spin resonance (ESR) spectroscopy, in room temperature ionic liquids system 1‐butyl‐3‐methyl‐limidazolium chloride‐aluminium chloride ([bmim]Cl‐AlCl3). The results indicate that ESR spectra observed are due to polycyclic aromatic radical cations formed from their parent hydrocarbons. ESR spectrum of spin adduct is obtained in an ionic liquid system composed of [bmim]Cl‐AlCl3. In acidic solution the 14N hyperfine coupling constant of 4‐oxo‐TEMPO, 2.15 mT, is appreciably larger due to an adduct formed with AlCl3. 相似文献
68.
Zhai HJ Yang X Wang XB Wang LS Elliott B Boldyrev AI 《Journal of the American Chemical Society》2002,124(23):6742-6750
Although neutral and ionic O4(0/-/+) species have been observed experimentally and considered for energetic materials, O4(2-) and O5(2-) dianions have not yet been explored. O4(2-) is valent isoelectronic to the well-known ClO3- and SO3(2-) anions, and O5(2-) is valent isoelectronic to ClO4- and SO4(2-). All are stable, common anions in solutions and inorganic salts. In this article, we explore the possibility of making covalently bound O4(2-) and O5(2-) species stabilized in the forms of M+O4(2-) and M+O5(2-) (M = Li, Na, K, Cs) in the gas phase. Laser vaporization experiments using M-containing targets and an O2-seeded carrier gas yielded very intense mass peaks corresponding to MO4- and MO5-. To elucidate the structure and bonding of the newly observed MO4- and MO5- species, we measured their photoelectron spectra and then compared them with ab initio calculations and the spectra of ClO3-, Na+SO3(2-), ClO4-, and Na+SO4(2-). Careful analyses of the experimental and ab initio results showed, however, that the observed species are of the forms, O2-M+O2- and O2-M+O3-. The more interesting M+O4(2-) and M+O5(2-) species were found to be higher-energy isomers, but they are true minima on the potential energy surfaces, which suggests that it might be possible to synthesize bulk materials containing covalently bound tetra- and pentatomic oxygen building blocks. 相似文献
69.
Sem DS Bertolaet B Baker B Chang E Costache AD Coutts S Dong Q Hansen M Hong V Huang X Jack RM Kho R Lang H Ma CT Meininger D Pellecchia M Pierre F Villar H Yu L 《Chemistry & biology》2004,11(2):185-194
Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases. 相似文献
70.
食品中化学性有害物是导致食品安全问题的重要原因,质谱是对食品中化学性有害物进行定性定量分析的有效方法。该文按照化合物结构类别,综述了食品中重要化学性有害物的质谱软电离裂解机理,包括农药、兽药、真菌毒素,以及其他化学污染物。对于每类化合物,重点综述化合物质谱裂解产生的特征碎片、中性丢失等,以及这些质谱软电离裂解机理在食品中化学性有害物筛查及发现中的应用。研究化合物的质谱裂解机理可以帮助研究者对化合物进行结构解析和结构确证,为食品中同类结构新型化学性有害物的发掘提供理论依据。 相似文献