全文获取类型
收费全文 | 1937篇 |
免费 | 78篇 |
国内免费 | 12篇 |
专业分类
化学 | 1584篇 |
晶体学 | 15篇 |
力学 | 30篇 |
数学 | 108篇 |
物理学 | 290篇 |
出版年
2023年 | 23篇 |
2022年 | 21篇 |
2021年 | 26篇 |
2020年 | 39篇 |
2019年 | 49篇 |
2018年 | 39篇 |
2017年 | 21篇 |
2016年 | 48篇 |
2015年 | 62篇 |
2014年 | 71篇 |
2013年 | 111篇 |
2012年 | 121篇 |
2011年 | 124篇 |
2010年 | 85篇 |
2009年 | 71篇 |
2008年 | 125篇 |
2007年 | 114篇 |
2006年 | 138篇 |
2005年 | 135篇 |
2004年 | 115篇 |
2003年 | 82篇 |
2002年 | 70篇 |
2001年 | 25篇 |
2000年 | 24篇 |
1999年 | 23篇 |
1998年 | 15篇 |
1997年 | 11篇 |
1996年 | 11篇 |
1995年 | 11篇 |
1994年 | 12篇 |
1993年 | 13篇 |
1992年 | 14篇 |
1991年 | 18篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 6篇 |
1987年 | 10篇 |
1986年 | 10篇 |
1985年 | 22篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 12篇 |
1980年 | 12篇 |
1979年 | 8篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1975年 | 9篇 |
1974年 | 7篇 |
1973年 | 7篇 |
排序方式: 共有2027条查询结果,搜索用时 10 毫秒
121.
A simple and sensitive high-performance liquid chromatography (HPLC) method was developed to quantitate imatinib in human plasma. Imatinib and the internal standard dasatinib were separated using a mobile phase of 0.5% KH(2)PO(4) (pH3.5)-acetonitrile-methanol (55:25:20, v/v/v) on a CAPCELL PAK C18 MG II column (250 mm × 4.6 mm) at a flow rate of 0.5 mL/min and measurement at UV 265 nm. Analysis required 100 μL of plasma and involved a solid phase extraction with an Oasis HLB cartridge, which gave recoveries of imatinib from 73% to 76%. The lower limit of quantification for imatinib was 10 ng/mL. The linear range of this assay was between 10 and 5000 ng/mL (regression line r(2) > 0.9992). Inter- and intra-day coefficients of variation were less than 11.9% and accuracies were within 8.3% over the linear range. The plasma concentrations of imatinib obtained by our present method were almost the same as those assayed by an LC-MS-MS method at the Toray Research Center, Inc. This method can be applied effectively to measure imatinib concentrations in clinical samples. 相似文献
122.
123.
Mallik AK Qiu H Sawada T Takafuji M Ihara H 《Chemical communications (Cambridge, England)》2011,47(37):10341-10343
A molecular gel system was assembled on carrier particles and the integrated effect of weak interaction sites enabled highly efficient separation of the bioactive and shape-constrained isomers of tocopherols, β-carotene, and polycyclic aromatic hydrocarbons (PAHs) by multiple interaction mechanisms. 相似文献
124.
Mitsumoto K Oshiro E Nishikawa H Shiga T Yamamura Y Saito K Oshio H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9612-9618
Cyanide‐bridged metal complexes of [Fe8M6(μ‐CN)14(CN)10 (tp)8(HL)10(CH3CN)2][PF6]4?n CH3CN?m H2O (HL=3‐(2‐pyridyl)‐5‐[4‐(diphenylamino)phenyl]‐1H‐pyrazole), tp?=hydrotris(pyrazolylborate), 1 : M=Ni with n=11 and m=7, and 2 : M=Co with n=14 and m=5) were prepared. Complexes 1 and 2 are isomorphous, and crystallized in the monoclinic space group P21/n. They have tetradecanuclear cores composed of eight low‐spin (LS) FeIII and six high‐spin (HS) MII ions (M=Ni and Co), all of which are bridged by cyanide ions, to form a crown‐like core structure. Magnetic susceptibility measurements revealed that intramolecular ferro‐ and antiferromagnetic interactions are operative in 1 and in a fresh sample of 2 , respectively. Ac magnetic susceptibility measurements of 1 showed frequency‐dependent in‐ and out‐of‐phase signals, characteristic of single‐molecule magnetism (SMM), while desolvated samples of 2 showed thermal‐ and photoinduced intramolecular electron‐transfer‐coupled spin transition (ETCST) between the [(LS‐FeII)3(LS‐FeIII)5(HS‐CoII)3(LS‐CoIII)3] and the [(LS‐FeIII)8(HS‐CoII)6] states. 相似文献
125.
Hayasaka T Goto-Inoue N Sugiura Y Zaima N Nakanishi H Ohishi K Nakanishi S Naito T Taguchi R Setou M 《Rapid communications in mass spectrometry : RCM》2008,22(21):3415-3426
We recently developed a matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight (MALDI-QIT-TOF)-based imaging mass spectrometry (IMS) system. This system enables us to perform structural analyses using tandem mass spectrometry (MS/MS), as well as to visualize phospholipids and peptides in frozen sections. In the retina, phototransduction is regulated by the light-sensitive interaction between visual pigment-coupled receptor proteins, such as rhodopsin, and G proteins, such as transducin. There are some reports that the conformation of rhodopsin is influenced by the composition of phospholipids in the lipid bilayer membrane. However, these results were based on in vitro experiments and have not been analyzed in vivo. In this study, we visualized and identified phospholipids in mouse retinal sections with the MALDI-QIT-TOF-based IMS system. From a spectrum obtained by raster-scanned analysis of the sections, ions with high signal intensities were selected and analyzed by MS/MS. As a result, sixteen ions were identified as being from four diacyl-phosphatidylcholine (PC) species, i.e., PC (16:0/16:0), PC (16:0/18:1), PC (16:0/22:6), and PC (18:0/22:6), with different ion forms. The ion images revealed different distributions on the retinal sections: PC (16:0/18:1) was distributed in the inner nuclear layer and outer plexiform layer, PC (16:0/16:0) in the outer nuclear layer and inner segment, and both PC (16:0/22:6) and PC (18:0/22:6) in the outer segment and pigment epithelium. In conclusion, our in vivo IMS analyses demonstrated a three-zone distribution of PC species on the retinal sections. This approach may be useful for analyzing lipid changes and their contribution to phototransduction in the retina. 相似文献
126.
Soga S Shirai H Kobori M Hirayama N 《Journal of chemical information and modeling》2008,48(8):1679-1685
The idea that there should be a specific site on a protein for a particular functional small molecule is widespread. It is, however, usually not so easy to understand what characteristics of the site determine the binding ability of the functional small molecule. We have focused on the concurrence rate of the 20 standard amino acids at such binding sites. In order to correlate the concurrence rate and the specific binding site, we have analyzed high-quality X-ray structures of complexes between proteins and small molecules. A novel index characterizing the binding site based on the concurrency rate has been introduced. Using this index we have identified that there is a specific concavity designated as a chemocavity where a specific group of small molecules, i.e., canonical molecular group, is highly inclined to be bound. This study has demonstrated that a chemocavity is reserved for a specific canonical molecular group, and the prevalent idea has been confirmed. 相似文献
127.
Takahashi T Asami Y Kitamura E Suzuki T Wang X Igarashi J Morohashi A Shinojima Y Kanou H Saito K Takasu T Nagase H Harada Y Kuroda K Watanabe T Kumamoto S Aoyama T Matsumoto Y Bando T Sugiyama H Yoshida-Noro C Fukuda N Hayashi N 《Chemistry & biology》2008,15(8):829-841
Pyrrole-imidazole polyamide (PIP) is a nuclease-resistant novel compound that inhibits gene expression through binding to the minor groove of DNA. Human aurora kinase-A (AURKA) and -B (AURKB) are important regulators in mitosis during the cell cycle. In this study, two specific PIPs (PIP-A and PIP-B) targeting AURKA and AURKB promoter regions were designed and synthesized, and their biological effects were investigated by several in vitro assays. PIP-A and PIP-B significantly inhibited the promoter activities, mRNA expression, and protein levels of AURKA and AURKB, respectively, in a concentration-dependent manner. Moreover, 1:1 combination treatment with both PIPs demonstrated prominent antiproliferative synergy (CI value [ED(50)] = 0.256) to HeLa cells as a result of inducing apoptosis-mediated severe catastrophe of cell-cycle progression. The novel synthesized PIP-A and PIP-B are potent and specific gene-silencing agents for AURKA and AURKB. 相似文献
128.
Otomo T Iwase H Kameda Y Matubayasi N Itoh K Ikeda S Nakahara M 《The journal of physical chemistry. B》2008,112(15):4687-4693
Neutron diffraction measurements were carried out on H/ D isotopically substituted water in the low-density supercritical condition (T = 673 K, P = 26.3 MPa, and rho = 0.0068 molecules.A-3) in order to obtain direct information on the intermolecular partial structure functions, gHH inter(r), gOH inter(r), and gOO inter(r). In correspondence to the high-density supercritical water previously reported, the intermolecular nearest neighbor peaks in gHH inter(r), gOH inter(r), and gOO inter(r) are diffuse compared with the ambient ones. The nearest neighbor O...O distance (3.3 A) and its coordination number (2.6) were determined from the observed gOO inter(r). These results indicate that the orientational correlation between neighboring water molecules is considerably lost in low-density supercritical water. Small clusters involving a few water molecules are preferentially formed in low-density supercritical water, which is consistent with results obtained by previous IR and NMR studies. 相似文献
129.
Kenji ArimitsuSayo Nomura Hiroki IwasakiMinoru Ozeki Masayuki Yamashita 《Tetrahedron letters》2011,52(52):7046-7048
The first total synthesis of (±)-adunctin B (1), a natural product isolated from Piper aduncum (Piperaceae) and having antibacterial activity, was achieved in 1.26% overall yield in 15 steps from 5,7-dimethoxycoumarin-3-carboxylate (8). 相似文献
130.