全文获取类型
收费全文 | 26020篇 |
免费 | 4305篇 |
国内免费 | 3026篇 |
专业分类
化学 | 12978篇 |
晶体学 | 254篇 |
力学 | 1224篇 |
综合类 | 187篇 |
数学 | 1961篇 |
物理学 | 8056篇 |
无线电 | 8691篇 |
出版年
2024年 | 121篇 |
2023年 | 597篇 |
2022年 | 823篇 |
2021年 | 1100篇 |
2020年 | 1026篇 |
2019年 | 927篇 |
2018年 | 856篇 |
2017年 | 888篇 |
2016年 | 1170篇 |
2015年 | 1262篇 |
2014年 | 1550篇 |
2013年 | 1933篇 |
2012年 | 2174篇 |
2011年 | 2288篇 |
2010年 | 1686篇 |
2009年 | 1687篇 |
2008年 | 1808篇 |
2007年 | 1645篇 |
2006年 | 1555篇 |
2005年 | 1314篇 |
2004年 | 956篇 |
2003年 | 809篇 |
2002年 | 744篇 |
2001年 | 623篇 |
2000年 | 565篇 |
1999年 | 468篇 |
1998年 | 393篇 |
1997年 | 370篇 |
1996年 | 320篇 |
1995年 | 327篇 |
1994年 | 278篇 |
1993年 | 239篇 |
1992年 | 168篇 |
1991年 | 140篇 |
1990年 | 137篇 |
1989年 | 97篇 |
1988年 | 64篇 |
1987年 | 53篇 |
1986年 | 48篇 |
1985年 | 35篇 |
1984年 | 22篇 |
1983年 | 26篇 |
1982年 | 15篇 |
1981年 | 8篇 |
1980年 | 10篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1975年 | 3篇 |
1971年 | 2篇 |
1957年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Wu X Ding S Ding Q Gray NS Schultz PG 《Journal of the American Chemical Society》2002,124(49):14520-14521
Purmorphamine, which is a 2,6,9-trisubstituted purine compound, was discovered through cell-based high-throughput screening from a heterocycle combinatorial library. It differentiates multipotent mesenchymal progenitor cells into an osteoblast lineage. It will serve as a unique chemical tool to study the molecular mechanisms of osteogenesis of stem cells and bone development. 相似文献
52.
53.
54.
55.
Determination of amino acids in a complex matrix without derivatization is advantageous, however, difficulties are found in both the detection and the separation of those compounds. In this study, a rapid and reliable LC-MS-MS method for the quantitation of underivatized amino acids in exocellular media was established. Injections were made directly after centrifugation of the samples, without further preparation. The separation of seven underivatized amino acids was achieved on a reversed-phase C18 column with pentadecafluorooctanoic acid as a volatile ion-pair reagent, and the specific detection of most amino acids was achieved by MS-MS of the specific transitions [M + H]+-->[M + H - 46]+. The calibration curves of all analytes were linear over the range of 1.0-1000 microg ml(-1) and the detection limits ranged from 0.1 to 5 ng ml(-1), with an injection volume of 20 microl. The inter-day and intra-day precisions ranged from 2.6 to 5.7% and 4.8 to 8.2%, respectively; the mean recoveries of the seven analytes were 81-104%, 91-107% and 93-101% respectively at the spiked level of 10, 40 and 200 microg ml(-1). A large number of fermentation samples were analysed using this method. The technique is simple, rapid, selective and sensitive, and shows potential for the high-throughput quantitation of amino acids from other biological matrices. 相似文献
56.
The role of tunneling for two proton-transfer steps in the reactions catalyzed by triosephosphate isomerase (TIM) has been studied. One step is the rate-limiting proton transfer from Calpha in the substrate to Glu 165, and the other is an intrasubstrate proton transfer proposed for the isomerization of the enediolate intermediate. The latter, which is not important in the wild-type enzyme but is a useful model system because of its simplicity, has also been examined in the gas phase and in solution. Variational transition-state theory with semiclassical ground-state tunneling was used for the calculation with potential energy surface determined by an AM1 method specifically parametrized for the TIM system. The effect of tunneling on the reaction rate was found to be less than a factor of 10 at room temperature; the tunneling becomes more important at lower temperature, as expected. The imaginary frequency (barrier) mode and modes that have large contributions to the reaction path curvature are localized on the atoms in the active site, within 4 A of the substrate. This suggests that only a small number of atoms that are close to the substrate and their motions (e.g., donor-acceptor vibration) directly determine the magnitude of tunneling. Atoms that are farther away influence the effect of tunneling indirectly by modulating the energetics of the proton transfer. For the intramolecular proton transfer, tunneling was found to be most important in the gas phase, to be similar in the enzyme, and to be the smallest in water. The major reason for this trend is that the barrier frequency is substantially lower in solution than in the gas phase and enzyme; the broader solution barrier is caused by the strong electrostatic interaction between the highly charged solute and the polar solvent molecules. Analysis of isotope effects showed that the conventional Arrenhius parameters are more useful as experimental criteria for determining the magnitude of tunneling than the widely used Swain-Schaad exponent (SSE). For the primary SSE, although values larger than the transition-state theory limit (3.3) occur when tunneling is included, there is no clear relationship between the calculated magnitudes of tunneling and the SSE. Also, the temperature dependence of the primary SSE is rather complex; the value of SSE tends to decrease as the temperature is lowered (i.e., when tunneling becomes more significant). For the secondary SSE, the results suggest that it is more relevant for evaluating the "coupled motion" between the secondary hydrogen and the reaction coordinate than the magnitude of tunneling. Although tunneling makes a significant contribution to the rate of proton transfer, it appears not to be a major aspect of the catalysis by TIM at room temperature; i.e., the tunneling factor of 10 is "small" relative to the overall rate acceleration by 10(9). For the intramolecular proton transfer, the tunneling in the enzyme is larger by a factor of 5 than in solution. 相似文献
57.
The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis.We herein report an efficient method to reduce e... 相似文献
58.
59.
In recent decades, emotion recognition has received considerable attention. As more enthusiasm has shifted to the physiological pattern, a wide range of elaborate physiological emotion data features come up and are combined with various classifying models to detect one’s emotional states. To circumvent the labor of artificially designing features, we propose to acquire affective and robust representations automatically through the Stacked Denoising Autoencoder (SDA) architecture with unsupervised pre-training, followed by supervised fine-tuning. In this paper, we compare the performances of different features and models through three binary classification tasks based on the Valence-Arousal-Dominance (VAD) affection model. Decision fusion and feature fusion of electroencephalogram (EEG) and peripheral signals are performed on hand-engineered features; data-level fusion is performed on deep-learning methods. It turns out that the fusion data perform better than the two modalities. To take advantage of deep-learning algorithms, we augment the original data and feed it directly into our training model. We use two deep architectures and another generative stacked semi-supervised architecture as references for comparison to test the method’s practical effects. The results reveal that our scheme slightly outperforms the other three deep feature extractors and surpasses the state-of-the-art of hand-engineered features. 相似文献
60.
Huaquan Guan Wenbin Luo Beihua Bao Yudan Cao Fangfang Cheng Sheng Yu Qiaoling Fan Li Zhang Qinan Wu Mingqiu Shan 《Molecules (Basel, Switzerland)》2022,27(10)
Polyphenolic acids are the widely occurring natural products in almost each herbal plant, among which rosmarinic acid (RA, C18H16O8) is well-known, and is present in over 160 species belonging to many families, especially the Lamiaceae. Aside from this herbal ingredient, dozens of its natural derivatives have also been isolated and characterized from many natural plants. In recent years, with the increasing focus on the natural products as alternative treatments, a large number of pharmacological studies have been carried out to demonstrate the various biological activities of RA such as anti-inflammation, anti-oxidation, anti-diabetes, anti-virus, anti-tumor, neuroprotection, hepatoprotection, etc. In addition, investigations concerning its biosynthesis, extraction, analysis, clinical applications, and pharmacokinetics have also been performed. Although many achievements have been made in various research aspects, there still exist some problems or issues to be answered, especially its toxicity and bioavailability. Thus, we hope that in the case of natural products, the present review can not only provide a comprehensive understanding on RA covering its miscellaneous research fields, but also highlight some of the present issues and future perspectives worth investigating later, in order to help us utilize this polyphenolic acid more efficiently, widely, and safely. 相似文献