全文获取类型
收费全文 | 25790篇 |
免费 | 3951篇 |
国内免费 | 2388篇 |
专业分类
化学 | 17919篇 |
晶体学 | 311篇 |
力学 | 1532篇 |
综合类 | 109篇 |
数学 | 2914篇 |
物理学 | 9344篇 |
出版年
2024年 | 70篇 |
2023年 | 524篇 |
2022年 | 946篇 |
2021年 | 964篇 |
2020年 | 1006篇 |
2019年 | 991篇 |
2018年 | 826篇 |
2017年 | 727篇 |
2016年 | 1203篇 |
2015年 | 1151篇 |
2014年 | 1344篇 |
2013年 | 1790篇 |
2012年 | 2400篇 |
2011年 | 2412篇 |
2010年 | 1580篇 |
2009年 | 1499篇 |
2008年 | 1643篇 |
2007年 | 1505篇 |
2006年 | 1358篇 |
2005年 | 1151篇 |
2004年 | 839篇 |
2003年 | 648篇 |
2002年 | 607篇 |
2001年 | 443篇 |
2000年 | 435篇 |
1999年 | 514篇 |
1998年 | 426篇 |
1997年 | 437篇 |
1996年 | 454篇 |
1995年 | 360篇 |
1994年 | 308篇 |
1993年 | 234篇 |
1992年 | 235篇 |
1991年 | 198篇 |
1990年 | 169篇 |
1989年 | 143篇 |
1988年 | 97篇 |
1987年 | 110篇 |
1986年 | 87篇 |
1985年 | 82篇 |
1984年 | 47篇 |
1983年 | 43篇 |
1982年 | 35篇 |
1981年 | 18篇 |
1980年 | 11篇 |
1979年 | 10篇 |
1978年 | 6篇 |
1976年 | 9篇 |
1975年 | 11篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Xiao-Yu Miao Yong-Ji Hu Fu-Rao Liu Yuan-Yuan Sun Die Sun An-Xin Wu Yan-Ping Zhu 《Molecules (Basel, Switzerland)》2022,27(19)
A cascade 6-endo-dig cyclization reaction was developed for the switchable synthesis of halogen and non-halogen-functionalized pyrazolo[3,4-b]pyridines from 5-aminopyrazoles and alkynyl aldehydes via C≡C bond activation with silver, iodine, or NBS. In addition to its wide substrate scope, the reaction showed good functional group tolerance as well as excellent regional selectivity. This new protocol manipulated three natural products, and the arylation, alkynylation, alkenylation, and selenization of iodine-functionalized products. These reactions demonstrated the potential applications of this new method. 相似文献
942.
Wang Zhang Xinjie Liu Xun Sun Rongchun Han Nianjun Yu Juan Liang An Zhou 《Molecules (Basel, Switzerland)》2022,27(19)
It is generally believed that fresh Dendrobium officinale (FDO) has more significant pharmacological activity than dried Dendrobium officinale (DDO); however, the difference has not been clearly shown. Our study compared their antioxidant properties both in vitro and in vivo, and the molecular weight arrangement and monosaccharide composition of the fresh Dendrobium officinale polysaccharides (FDOPs) and the dried Dendrobium officinale polysaccharides (DDOPs) were analyzed by HPLC-GPC and GC-MS. The results showed that the FDO and its polysaccharides had more significant effects on scavenging DPPH, ABTS, and hydroxyl radicals than the DDO. In addition, both the FDO and DDO significantly reduced lipid peroxidation levels and increased the SOD, T-AOC, CAT, and GSH levels in mice with acute liver damage caused by CCl4, while the FDO and its polysaccharides were more effective. Histopathological analysis further verified the protective effect of the Dendrobium polysaccharides on CCl4-induced liver injury. The determination of the polysaccharides revealed that the polysaccharide and mannose contents of the FDO were significantly higher than their dried counterparts, and the homogeneous arrangement of the polysaccharides in the FDO was degraded into three polysaccharide fragments of different molecular weights in the DDO. Overall, our data identified differences in the antioxidant activities of the FDO and DDO, as well as the reasons for these differences. 相似文献
943.
944.
The adsorptive capacity and selectivity of a novel adsorbent with pyridyl group toward stevia glycosides were studied. The effect of polarity and physical structure of the sorbent on the selectivity was investigated in detail. Two separation methods were applied in the enrichment of rebaudioside A(RA). They were selective elution using methanol or ethanol solution as solvent, and dynamic chromatographic separation using pyridyl resin with high selectivity. Results show that the chromatographic separation method can effectively enrich RA from stevia glycoside with high content of stevioside. 相似文献
945.
An electrophoretically mediated microanalysis method for detection of yoctomole (ymol) alkaline phosphatase (ALP) was developed by a combination of on-capillary enzyme-catalyzed reaction and electrochemical detection. In this method, ALP molecules were electrokinetically injected into a capillary of 10 μm i.d. and then electromigrated to the section of the capillary immersed in a warm water bath of 37 °C, where ALP reacted for a certain time with disodium phenyl phosphate as the enzyme substrate. ALP could be measured through determining the electroactive product phenol of the enzyme-catalyzed reaction by using electrochemical detection. The phenol concentration was proportional to the mass of ALP. As a catalyst, ALP was not consumed during the reaction, which provided amplification of signal with prolonged the reaction time. In order to enhance the signal-to-noise ratio, the detection end of the capillary was etched to a horn-shape and a single carbon fiber microcylinder electrode of 6 μm in diameter as the working electrode was inserted into the detection end of the capillary. Under these conditions, the mass of ALP as low as 1.2 × 10−22 mol (72 molecules) or 4.0 × 10−23 mol (24 molecules) could be detected for the on-capillary reaction time of 15 min or 2 h. 相似文献
946.
Jinyu Sun Yaming Zhou Guangshan Zhu Rongjing Yang Dongyuan Zhao 《Journal of solid state chemistry》2006,179(4):1230-1236
A basic zinc nitrate, [Zn(OH)(NO3)]n with a novel framework reported herein is prepared by solvothermal synthesis, and holds a rare three-dimensional (10,3)-d net called by Wells. It crystallizes in orthorhombic, space group, Pna21 (No. 33), , , , Z=4, , , , 3.49<θ<27.51, , R1=0.029, wR2=0.0773 for 697 (I>2σ(I)) of 1728 [R(int)=0.0246] unique reflections and 59 parameters. GOF=1.073. Interestingly this basic zinc nitrate, [Zn(OH)(NO3)]n behaves well at removal capacity for hydrogen chloride gas, 20.3 g HCl/100 g, and its framework is not destroyed yet. This adsorption character may be useful for the removal of toxic gases in the environment. 相似文献
947.
Qing Zhang Huifang Wang Guosong Sun Kelin Huang Weiping Fang Yiquan Yang 《天然气化学杂志》2008,17(4):355-358
Activated carbon-supported Ni catalysts for vapor phase carbonylation of ethanol to propionic acid in the presence of ethyl iodide as promoter were investigated. Under optimum reaction conditions, the conversions of carbon monoxide and ethanol were measured to be 81.4% and 98.4%, respectively, while the selectivity for propionic acid was found to be 98.65%. The catalyst was stable within 48 h on stream. XRD and XPS methods were used to characterize the structures and surface properties of the fresh and tested catalysts. The characterization results indicated that aggregation of nickel particles and formation of nickel iodide on the catalyst surface should be responsible for the deactivation of the catalysts. 相似文献
948.
The sofid-state ECL behavior of a water-insoluble bis-cyclometalated (pq)2Ir(N-phMA) complex is presented, in which pq is a 2-phenylquinoline anion and N-phMA is N-phenyl methacrylamide, a monoanionic bidentate ligand. The MWNTs/(pq)2Ir(N-phMA) film, MWNTs/Ru(bpy)32+ film and (pq)2Ir(N-phMA) directly modified glassy carbon electrode were fabricated; only the MWNTs/(pq)2Ir(N-phMA) film can produce steady ECL in the presence of tri-n-propylamine as a coreactant. 相似文献
949.
The structures and stabilities of (Al2O3)n (n = 1-10 and 30) clusters were studied by means of first principles calculations. The calculated results reveal that the global minima of small (Al2O3)n (n = 1-5) clusters are cage structures with high symmetries, in which Al and O atoms are three- and two-coordinated, respectively, and are linked to neighbors via single bonds. Beyond (Al2O3)5, we calculated both cage and cage-dimer structures for (Al2O3)n (n = 6-10), and the results show that, at this size range, cage-dimer structures are more stable than cage structures. Furthermore, an onion-like motif for (Al2O3)10 was studied, and it is interesting to find that, at this size, the onion structure is more favorable than cage and cage-dimer structures. For large clusters, a shell structure of Al60O90 is suggested. Electronic properties and calculations on hydrogen adsorption of these aluminum oxide structures are reported, and we discuss their possible use as hydrogen storage materials. 相似文献
950.
A series of ruthenium(II) complexes, [Ru(tcterpy)(NCS)3](4-) (0H), [Ru(Htcterpy)(NCS)3](3-) (1H), [Ru(H2tcterpy)(NCS)3](2-) (2H), and [Ru(H3tcterpy)(NCS)3](-) (3H) (tcterpy = 4,4',4'-tricarboxy-2,2':6',2'-terpyridine), are investigated theoretically to explore their electronic structures and spectroscopic properties. The geometry structures of the complexes in the ground and excited states are optimized by the density functional theory and single-excitation configuration interaction methods, respectively. The absorption and emission spectra of the complexes in gas phase and solutions (ethanol and water) are predicted at the TDDFT(B3LYP) level. The calculations indicate that the protonation effect slightly affects the geometry structures of the complexes in the ground and excited states but leads to significant change in the electronic structures. In cases of both absorptions and emissions, the energy levels of HOMOs and LUMOs for 0H-3H decrease dramatically as a result of the introduction of the COOH groups. The protonation much stabilizes the unoccupied orbitals with respect to the occupied orbitals. Thus, both the absorptions and emissions are red-shifted from 0H to 3H. The phosphorescence of 0H-3H are attributed to tcterpyridine --> d(Ru)/NCS ((3)MLCT/(3)LLCT) transitions. The solvent media can influence the molecular orbital distribution of the complexes; as a consequence, the spectra calculated in the presence of the solvent are in good agreement with the experimental results. The MLCT/LLCT absorptions of 0H in ethanol and water are red-shifted relative to that in the gas phase. However, the MLCT/LLCT absorptions of the protonated complexes (1H-3H) are blue-shifted in ethanol and water with respect to the gas phase. Similarly, the solvent effect causes a blue-shift of the phosphorescent emission for 0H-3H. 相似文献