全文获取类型
收费全文 | 2492篇 |
免费 | 444篇 |
国内免费 | 316篇 |
专业分类
化学 | 1876篇 |
晶体学 | 30篇 |
力学 | 223篇 |
综合类 | 13篇 |
数学 | 318篇 |
物理学 | 792篇 |
出版年
2024年 | 11篇 |
2023年 | 72篇 |
2022年 | 126篇 |
2021年 | 114篇 |
2020年 | 150篇 |
2019年 | 106篇 |
2018年 | 119篇 |
2017年 | 103篇 |
2016年 | 150篇 |
2015年 | 158篇 |
2014年 | 157篇 |
2013年 | 203篇 |
2012年 | 199篇 |
2011年 | 204篇 |
2010年 | 142篇 |
2009年 | 121篇 |
2008年 | 129篇 |
2007年 | 120篇 |
2006年 | 108篇 |
2005年 | 90篇 |
2004年 | 66篇 |
2003年 | 55篇 |
2002年 | 79篇 |
2001年 | 69篇 |
2000年 | 52篇 |
1999年 | 45篇 |
1998年 | 49篇 |
1997年 | 37篇 |
1996年 | 41篇 |
1995年 | 24篇 |
1994年 | 20篇 |
1993年 | 26篇 |
1992年 | 21篇 |
1991年 | 18篇 |
1990年 | 15篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1964年 | 1篇 |
1957年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有3252条查询结果,搜索用时 31 毫秒
51.
铜(Ⅱ)和锌(Ⅱ)分别在0.1mol/LKH_2PO_4-Na_2HPO_4缓冲溶液(pH6.5)和0.25mol/LNH_4Cl溶液中,与氟哌酸形成良好的络合吸附波,峰电位分别为-0.26V和-1.28V(vs;SCE);络合比分别为1:3和1:2;峰电流与铜(Ⅱ)和锌(Ⅱ)的浓度均在4.0×10 ̄(-7)~5.0×10 ̄(-6)mol/L范围内呈线性关系,检测限分别为7.0×10 ̄(-8)和5.0×10 ̄(-8)mol/L。用线性扫描和循环伏安法等手段研究体系的行为,表明均具吸附性,而铜(Ⅱ)-氟哌酸体系属络合物中铜(Ⅱ)的两电子还原的可逆过程。 相似文献
52.
The synthesis and anion binding properties of new ruthenium(II) and cobalt(II) phenanthroline complexes, containing two amide
subunits are described. Evidence for anion binding in dimethyl sulfoxide (DMSO) solution was obtained from u.v.–vis titration
experiments. Results indicated that these receptors showed strong affinity for F− and AcO−, and showed weak affinity for OH− and H2PO
4
−
, and showed no affinity for Cl−, Br−, I−. These receptors interacted with various anions examined through hydrogen-bond formation. 相似文献
53.
Qi Zhang Yunlong Shao Boye Li Yuanyuan Wu Jingying Dong Dongtang Zhang Yanan Wang Yong Yan Xiayan Wang Qiaosheng Pu Guangsheng Guo 《Chemical science》2021,12(11):4111
The analysis of single living cells, including intracellular delivery and extraction, is essential for monitoring their dynamic biochemical processes and exploring intracellular heterogeneity. However, owing to the 2D view in bright-field microscopy and optical distortions caused by the cell shape and the variation in the refractive index both inside and around the cells, achieving spatially undistorted imaging for high-precision manipulation within a cell is challenging. Here, an accurate and visual system is developed for single-cell spatial manipulation by correcting the aberration for simultaneous bright-field triple-view imaging. Stereo information from the triple view enables higher spatial resolution that facilitates the precise manipulation of single cells. In the bright field, we resolved the spatial locations of subcellular structures of a single cell suspended in a medium and measured the random spatial rotation angle of the cell with a precision of ±5°. Furthermore, we demonstrated the visual manipulation of a probe to an arbitrary spatial point of a cell with an accuracy of <1 pixel. This novel system is more accurate and less destructive for subcellular content extraction and drug delivery.We achieved the low-damage spatial puncture of single cells at specific visual points with an accuracy of <65 nm. 相似文献
54.
Xiaofeng Wu Jong Min An Jizhen Shang Eugene Huh Sujie Qi Eunhye Lee Haidong Li Gyoungmi Kim Huimin Ma Myung Sook Oh Dokyoung Kim Juyoung Yoon 《Chemical science》2020,11(41):11285
Acetylcholinesterase (AChE) is an extremely critical hydrolase tightly associated with neurological diseases. Currently, developing specific substrates for imaging AChE activity still remains a great challenge due to the interference from butyrylcholinesterase (BChE) and carboxylesterase (CE). Herein, we propose an approach to designing specific substrates for AChE detection by combining dimethylcarbamate choline with a self-immolative scaffold. The representative P10 can effectively eliminate the interference from CE and BChE. The high specificity of P10 has been proved via imaging AChE activity in cells. Moreover, P10 can also be used to successfully map AChE activity in different regions of a normal mouse brain, which may provide important data for AChE evaluation in clinical studies. Such a rational and effective approach can also provide a solid basis for designing probes with different properties to study AChE in biosystems and another way to design specific substrates for other enzymes.In this work, a new approach was developed for designing the representative P10 with high selectivity and sensitivity for imaging AChE activity in the cells and normal mouse brain. 相似文献
55.
56.
57.
Guangdong Zhou Zhanlin Xu Xiaohong Guo Hong Zhuang Yanan Li Xueju Lü Tiexin Cheng Wenxing Li Kaiji Zhen 《Reaction Kinetics and Catalysis Letters》2005,85(1):57-64
Summary The oxidation of hexanol in the presence of the Keggin-type heteropoly compounds (HPCs) H3PMonW12-nO40 (denoted as PMonW12-n, n=0,1) and Na5PW11ZO39 (denoted as PW11Z, Z = Mn, Fe, Co, Ni, Cu and Zn) was carried out to produce hexanal and hexanoic acid. The reaction was conducted in tert-butanol (t-BuOH), using cetylpyridinium bromide (CPB) salts of HPA and 15% aqueous H2O2 as oxidant under mild condition. The PMoW11 catalyst showed higher hexanol conversion of 25%, the lowest selectivity to hexanal of 64.4% and an efficient utilization of H2O2 of 34%. Over the transition metal substituted PW11Z catalysts decomposition of H2O2 was rapid. For these PW11Z catalysts, the efficient utilization of H2O2 decreased to 9% or even lower. By means of IR, UV-visible and GC-MS techniques the catalysts were characterized. 相似文献
58.
Yang M Wang GJ Wang SJ Li XT Xu YP Wang SP Xiang JD Pan SR Cao GX Ye WC 《Rapid communications in mass spectrometry : RCM》2005,19(12):1619-1623
23-Hydroxybetulinic acid is a newly isolated derivative of betulinic acid. The agent exhibits potential anti-tumor activity and functions in this regard via apoptosis. In support of pharmacokinetic and toxicological evaluations, a new assay based on liquid chromatography/mass spectrometry (LC/MS) was developed for the quantitative analysis of 23-hydroxybetulinic acid. Sample preparation consisted of extraction of the plasma by the addition of methylene chloride followed by centrifugation. Aliquots of the supernatant were analyzed using an isocratic reversed-phase high-performance liquid chromatography (HPLC) system coupled to a negative ion electrospray mass spectrometer. Molecules of 23-hydroxybetulinic acid and the internal standard limonin were detected using selected ion monitoring at m/z 471 and 469, respectively. The limit of detection of 23-hydroxybetulinic acid was 0.05 pg (0.11 fmol) injected on-column (10 pg/mL, 5 microL injection volume), and the limit of quantitation was 10 pg (21.19 fmol, 2 ng/mL, 5 muL injection volume). 23-Hydroxybetulinic acid was stable in plasma samples at -20 degrees C for at least 3 weeks. The intra-day and inter-day coefficients of variation of the assay were 3.0 and 4.8%, respectively. The utility of the assay was demonstrated by measuring 23-hydroxybetulinicacid in mouse plasma following intragastric administration (IG) in vivo. Pharmacokinetic parameters were calculated using the 3P97 pharmacokinetic software package. A two-compartment, first-order model was selected for pharmacokinetic modeling. The result showed that after IG of 200 mg/kg 23-hydroxybetulinic acid, the plasma concentrations reached peaks at 2 h with C(max) of 3.1 microg/mL. The 200 mg/kg 23-hydroxybetulinic acid suspension IG doses were found to have long elimination half-lives of 25.6 h and low bioavailability of 2.3%. No interference was noted due to endogenous substances. These analytical methods should be of value in future studies related to the development and characterization of 23-hydroxybetulinic acid. 相似文献
59.
Three photocatalytic oxidation (PCO) systems: C7H16-O2, SO2-O2 and C7H16-SO2-O2 were carried out with the aid of UV-illuminated TiO2 nanoparticles at room temperature in a batch reactor. In C7H16-O2-TiO2 system, no catalyst deactivation was observed, while for SO2-O2-TiO2 and C7H16-SO2-O2-TiO2 systems, the photocatalytic activity of used TiO2 powder showed decreasing and eventually no activity after used consecutively. The reaction products such as sulfur trioxide or sulfuric acid adsorbed onto the surface of TiO2 catalyst were poisoning species. Photocatalytic activity of the deactivated TiO2 powder could be regenerated by sonicating treatment with water and methanol for the two systems, respectively. 相似文献
60.
Yulong Bai Wang Wan Yanan Huang Wenhan Jin Haochen Lyu Qiuxuan Xia Xuepeng Dong Zhenming Gao Yu Liu 《Chemical science》2021,12(24):8468
Co-aggregation of multiple pathogenic proteins is common in neurodegenerative diseases but deconvolution of such biochemical process is challenging. Herein, we developed a dual-color fluorogenic thermal shift assay to simultaneously report on the aggregation of two different proteins and quantitatively study their thermodynamic stability during co-aggregation. Expansion of spectral coverage was first achieved by developing multi-color fluorogenic protein aggregation sensors. Orthogonal detection was enabled by conjugating sensors of minimal fluorescence crosstalk to two different proteins via sortase-tag technology. Using this assay, we quantified shifts in melting temperatures in a heterozygous model protein system, revealing that the thermodynamic stability of wild-type proteins was significantly compromised by the mutant ones but not vice versa. We also examined how small molecule ligands selectively and differentially interfere with such interplay. Finally, we demonstrated these sensors are suited to visualize how different proteins exert influence on each other upon their co-aggregation in live cells.A little leak will sink a great ship! We prepared a series of multi-color protein aggregation sensors and developed a dual-color thermal shift assay to simultaneously and quantitatively report on protein co-aggregation of two different proteins. 相似文献