全文获取类型
收费全文 | 12356篇 |
免费 | 2060篇 |
国内免费 | 1600篇 |
专业分类
化学 | 8947篇 |
晶体学 | 130篇 |
力学 | 804篇 |
综合类 | 159篇 |
数学 | 1477篇 |
物理学 | 4499篇 |
出版年
2024年 | 50篇 |
2023年 | 247篇 |
2022年 | 494篇 |
2021年 | 517篇 |
2020年 | 550篇 |
2019年 | 520篇 |
2018年 | 466篇 |
2017年 | 410篇 |
2016年 | 612篇 |
2015年 | 586篇 |
2014年 | 734篇 |
2013年 | 966篇 |
2012年 | 1092篇 |
2011年 | 1105篇 |
2010年 | 771篇 |
2009年 | 703篇 |
2008年 | 842篇 |
2007年 | 725篇 |
2006年 | 612篇 |
2005年 | 544篇 |
2004年 | 398篇 |
2003年 | 356篇 |
2002年 | 333篇 |
2001年 | 296篇 |
2000年 | 247篇 |
1999年 | 273篇 |
1998年 | 206篇 |
1997年 | 216篇 |
1996年 | 200篇 |
1995年 | 186篇 |
1994年 | 154篇 |
1993年 | 127篇 |
1992年 | 106篇 |
1991年 | 92篇 |
1990年 | 69篇 |
1989年 | 46篇 |
1988年 | 34篇 |
1987年 | 35篇 |
1986年 | 27篇 |
1985年 | 27篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 5篇 |
1981年 | 9篇 |
1980年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1959年 | 1篇 |
1957年 | 6篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
151.
Zhao Z Xiong S Liu X Xin B Wang G 《European journal of mass spectrometry (Chichester, England)》2003,9(3):203-211
We report the application of matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry, with delayed extraction in the reflectron mode, for the characterization of low molecular weight dendrimers. 20 dendrimer samples were measured and 4 typical dendrimers, as examples, are discussed in detail. Several factors that affect the analysis including the matrices used, the concentrations of sample, the solvents and cationization reagent used, were investigated in detail. Experimental results indicate that the type of solvent can greatly influence exact mass measurement. However, sample preparation is generally not very critical for dendrimer analysis using MALDI-ToF since many kinds of matrices and a wide range of sample concentrations can be used efficiently. In addition, the Cs(+) ion can be used to enhance the efficiency of cationization. Some reasons for this behavior are discussed on the basis of results of calculations using Gaussian94 software (a connected system of programs for performing a variety of semi-empirical and ab initio molecular orbital (MO) calculations). 相似文献
152.
Xuefang Shen Xiangyuan Chen Jing Wang Jing Liu Zhiyao Wang Qing Hua Qichao Wu Yanguang Su Huanzhong He Yuqin Hu Zhipeng Meng Wanxia Xiong Minmin Zhu 《Experimental & molecular medicine》2020,52(10):1715
Hyperglycemia-mediated endothelial inflammation participates in the pathogenesis of cardiovascular complications in subjects with diabetes. Previous studies reported that phosphatase and tensin homolog deleted on chromosome ten (PTEN) and SET8 participate in high glucose-mediated endothelial inflammation. In this study, we hypothesize that SET8 regulates PTEN expression, thus contributing to high glucose-mediated vascular endothelial inflammation. Our data indicated that plasma soluble intercellular adhesion molecule-1 (sICAM-1) and endothelial selectin (e-selectin) were increased in patients with diabetes and diabetic rats. PTEN expression was augmented in the peripheral blood mononuclear cells of patients with diabetes and in the aortic tissues of diabetic rats. Our in vitro study indicated that high glucose increased monocyte/endothelial adhesion, endothelial adhesion molecule expression and p65 phosphorylation in human umbilical vein endothelial cells (HUVECs). Moreover, high glucose led to endothelial inflammation via upregulation of PTEN. Furthermore, high glucose inhibited SET8 expression and histone H4 lysine 20 methylation (H4K20me1), a downstream target of SET8. SET8 overexpression reversed the effects of high-glucose treatment. shSET8-mediated endothelial inflammation was counteracted by siPTEN. Furthermore, SET8 was found to interact with FOXO1. siFOXO1 attenuated high glucose-mediated endothelial inflammation. FOXO1 overexpression-mediated endothelial inflammation was counteracted by siPTEN. H4K20me1 and FOXO1 were enriched in the PTEN promoter region. shSET8 increased PTEN promoter activity and augmented the positive effect of FOXO1 overexpression on PTEN promoter activity. Our in vivo study indicated that SET8 was downregulated and FOXO1 was upregulated in the peripheral blood mononuclear cells of patients with diabetes and the aortic tissues of diabetic rats. In conclusion, SET8 interacted with FOXO1 to modulate PTEN expression in vascular endothelial cells, thus contributing to hyperglycemia-mediated endothelial inflammation.Subject terms: Diabetes complications, Vascular diseases 相似文献
153.
The adsorption of H(2)O and its dissociation products, O, H, and OH, on Ag(100) has been studied using an ab initio embedding method. Results at different sites (atop, bridge, and hollow) are presented. The four-fold hollow site is found to be the most stable adsorption site for O, H, and OH, and the calculated adsorption energies are 87.1, 42.7, and 76.2 kcal mol(-1), respectively. The adsorption energy of water at the atop and bridge sites is almost identical with values of 11.1 and 12.0 kcal mol(-1), respectively. The formation of adsorbed OH species by adsorption of water on oxygen-precovered Ag(100) is predicted to be exothermic by 36 kcal mol(-1). 相似文献
154.
The cleavage of a disulfide bond and the redox equilibrium of thiol/disulfide are strongly related to the levels of glutathione (GSH)/oxidized glutathione (GSSG) or mixed disulfides in vivo. In this work, the cleavage of a disulfide bond in GSSG induced by a platinum(II) complex [Pt(Met)Cl2] (where Met = methionine) was studied and the cleavage fragments or their platinated adducts were identified by means of electrospray mass spectrometry, high-performance liquid chromatography, and ultraviolet techniques. The second-order rate constant for the reaction between [Pt(Met)Cl2] and GSSG was determined to be 0.4 M(-1) s(-1) at 310 K and pH 7.4, which is 100- and 12-fold faster than those of cisplatin and its monoaqua species, respectively. Different complexes were formed in the reaction of [Pt(Met)Cl2] with GSSG, mainly mono- and dinuclear platinum complexes with the cleavage fragments of GSSG. This study demonstrated that [Pt(Met)Cl2] can promote the cleavage of disulfide bonds. The mechanistic insight obtained from this study may provide a deeper understanding on the potential involvement of platinum complexes in the intracellular GSH/GSSG systems. 相似文献
155.
Recognition of sheared and normal DNA by a novel metal complex [Co(phen)2hpip]3+ (phen=1,10-phenanthroline, HPIP=2-(2-hydroxyphenyl)imidazole[4,5-f][1,10]phenanethroline) is studied by molecular modeling. Calculating results indicate that, this complex can specifically recognize DNA segment of sequence –MMNNMM– (M means mismatch base pairs and N means normal base pairs). Intercalating from minor groove between the middle normal duplex into the sheared DNA with the depth of 1.2 nm is of preference and enantioselectivity is observed. Comparison on the two DNA structures of optimal conformation and analysis on the interaction between DNA and the two tail ligands of the complex show that, the effect of the two neighboring mismatch duplexes on the structure of the middle normal base pairs and the steric interaction between the mismatch duplexes and the two tail ligands of the complex are the essential reason to the segment specificity. Investigation on the detailed energy terms indicate that, in effecting enantioselectivity, the electrostatic distribution of the complex is in the majority and steric interaction is at the next place. But, steric interaction is surely the only factor determining the intercalating from minor groove. 相似文献
156.
157.
Xingang Kong Jiarui Zhang Jianfeng Huang Jiayin Li Yi Qin Ting Zhao Qi Feng 《中国化学快报》2019,30(3):771-774
SnNb2O6 and Sn2Nb2O7 nanosheets were synthetized via microwave assisted hydrothermal method, and innovatively employed as anode materials for lithium-ion battery. Compared with Sn2Nb2O7 and the previously reported pure Sn-based anode materials, the SnNb2O6 electrode exhibited outstanding cycling performance. 相似文献
158.
YingXinLIU ZuoJunWEI JiXiangCHEN JiYanZHANG XinXueLI XiongHuiWEI 《中国化学快报》2005,16(4):531-533
A novel lanthana-promoted nickel catalyst supported on silica for the liquid phase hydrogenation of m-dinitrobenzene to m-phenylenediamine was prepared by an incipient wetness sequential impregnation method. It was found that Ni-La/SiO2 catalyst exhibited high activity and stability for m-dinitrobenzene hydrogenation. Over this catalyst, the conversion of m-dinitrobenzene and the yield of m-phenylenediamine were up to 97.1% and 93.5%, respectively,at 373 K and 2.6 MPa hydrogen pressure after reaction for 1 h. 相似文献
159.
Reaction of an arylacetylene with an azide in hot water gave 1,4-disubstituted 1,2,3-triazoles in high yields, while similar reaction between a terminal aliphatic alkyne and an azide (except m-nitroazidobenzene) afforded a mixture of regioisomers with the ratio of 1,4- to 1,5-isomers ranging from 3:1 to 28.6:1. Reactions of m-nitroazidobenzene with either arylalkynes or aliphatic alkynes formed only 1,4-disubstituted derivatives in excellent yields. 相似文献
160.
Furostanol saponins with inhibitory action against COX-2 production from Tupistra chinensis rhizomes
Kun Zou Jun Zhi Wang Jun Wu Yuan Zhou Chuang Liu Fei Jun Dan Ya Xiong Zhang Jin Yang 《中国化学快报》2007,18(10):1239-1242
Two furostanol saponins were obtained from the n-butanol fraction of methanol extract from Tupistra chinensis rhizomes,a folk medicine of Shennongjia Forest District of Hubei Province.Their structures were determined as (25S)-26-O-(β-D-glucopyranosyl)- furost-1β,3β,22α,26-tetrol-3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside (1) and (25R)- 26-O-(β-D-glucopyranosyl)-furost-1β,3β22α,26-tetrol 3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→2)-β-D-glu- copyranoside (2),on basis of chemical and spectroscopic evidences.1 and 2 displayed marked inhibitory action towards COX-2 production in macrophages of the rat abdomen induced by LPS at 20μg/mL. 相似文献