全文获取类型
收费全文 | 2504篇 |
免费 | 121篇 |
国内免费 | 25篇 |
专业分类
化学 | 1801篇 |
晶体学 | 19篇 |
力学 | 51篇 |
数学 | 348篇 |
物理学 | 431篇 |
出版年
2023年 | 22篇 |
2022年 | 35篇 |
2021年 | 51篇 |
2020年 | 67篇 |
2019年 | 67篇 |
2018年 | 49篇 |
2017年 | 58篇 |
2016年 | 105篇 |
2015年 | 82篇 |
2014年 | 95篇 |
2013年 | 162篇 |
2012年 | 156篇 |
2011年 | 190篇 |
2010年 | 116篇 |
2009年 | 96篇 |
2008年 | 145篇 |
2007年 | 122篇 |
2006年 | 126篇 |
2005年 | 109篇 |
2004年 | 91篇 |
2003年 | 65篇 |
2002年 | 77篇 |
2001年 | 31篇 |
2000年 | 30篇 |
1999年 | 31篇 |
1998年 | 14篇 |
1997年 | 16篇 |
1996年 | 37篇 |
1995年 | 16篇 |
1994年 | 15篇 |
1993年 | 26篇 |
1992年 | 17篇 |
1991年 | 10篇 |
1990年 | 13篇 |
1989年 | 14篇 |
1988年 | 8篇 |
1987年 | 12篇 |
1985年 | 16篇 |
1984年 | 9篇 |
1983年 | 21篇 |
1982年 | 11篇 |
1980年 | 8篇 |
1979年 | 10篇 |
1978年 | 17篇 |
1977年 | 12篇 |
1976年 | 11篇 |
1972年 | 9篇 |
1970年 | 11篇 |
1967年 | 7篇 |
1958年 | 7篇 |
排序方式: 共有2650条查询结果,搜索用时 15 毫秒
51.
Juglomycin A has been synthesized in four steps from 5-methoxy-1-naphthol. 相似文献
52.
Ordered porous silicas with unprecedented loadings of pendant vinyl groups have been synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and triethoxyvinylsilane (TEVS) under basic conditions in the presence of cetyltrimethylammonium surfactant. The resulting organosilicate-surfactant composites exhibited at least one low-angle X-ray diffraction (XRD) peak up to the TEVS:TEOS molar ratio of 7:3 (70% TEVS loading) in the synthesis gel. The surfactant was removed from these composites without any structural collapse. Nitrogen adsorption provided strong evidence of the presence of uniformly sized pores and the lack of phase separation up to TEVS:TEOS ratios as high as 13:7 (65% TEVS loading), whereas (29)Si MAS NMR and high-resolution thermogravimetry showed essentially quantitative incorporation of the organosilane. Thus, a hitherto unachieved loading level for pendant groups, considered by many to be impossible to achieve for stable organosilicas because of the expected framework connectivity constraints, has been obtained. The resulting vinyl-functionalized silicas exhibited gradually decreasing pore diameter (from 2.8 to 1.7 nm for TEVS loadings of 25-65%) and pore volume as the loading of pendant groups increased, but the specific surface area was relatively constant. Because of the reactivity of vinyl groups, ordered silicas with very high loadings of these groups are expected to be robust starting materials for the synthesis of other organic-functionalized ordered microporous materials. Herein, we demonstrate that these starting materials can also be transformed via calcination into ordered microporous silicas with pore diameters tailorable from 2.5 to as little as 1.4 nm simply by using an appropriate loading of the vinyl-functionalized precursor. This ease of the micropore size adjustment and the attained degree of structural ordering (as judged from XRD) have not been reported before. The novel ordered microporous materials reported herein are promising as adsorbents and catalyst supports. 相似文献
53.
Reaction of trienes with α,β-unsaturated aldehydes produces bicyclic products via a tandem Diels-Alder/ene reaction. The adduct from tiglic aldehyde was converted into isoligularone by conversion to a furan followed by benzylic oxidation. 相似文献
54.
1-Deoxy-D-galactohomonojirimycin was synthesized in seven steps from optically pure allenylstannane 4 and L-lactate-derived aldehyde 5 in 48% overall yield. The key step was the Lewis acid catalyzed reaction of 4 and 5 to give the syn-amino alcohol in excellent yield and very high diastereoselectivity. 相似文献
55.
Kizek R Masarik M Kramer KJ Potesil D Bailey M Howard JA Klejdus B Mikelova R Adam V Trnkova L Jelen F 《Analytical and bioanalytical chemistry》2005,381(6):1167-1178
The electroanalytical determination of avidin in solution, in a carbon paste, and in a transgenic maize extract was performed in acidic medium at a carbon paste electrode (CPE). The oxidative voltammetric signal resulting from the presence of tyrosine and tryptophan in avidin was observed using square-wave voltammetry. The process could be used to determine avidin concentrations up to 3 fM (100 amol in 3 l drop) in solution, 700 fM (174 fmol in 250 l solution) in an avidin-modified electrode, and 174 nM in a maize seed extract. In the case of the avidin-modified CPE, several parameters were studied in order to optimize the measurements, such as electrode accumulation time, composition of the avidin-modified CPE, and the elution time of avidin. In addition, the avidin-modified electrode was used to detect biotin in solution (the detection limit was 7.6 pmol in a 6 l drop) and to detect biotin in a pharmaceutical drug after various solvent extraction procedures. Comparable studies for the detection of biotin were developed using HPLC with diode array detection (HPLC-DAD) and flow injection analysis with electrochemical detection, which allowed biotin to be detected at levels as low as 614 pM and 6.6 nM, respectively. The effects of applied potential, acetonitrile content, and flow rate of the mobile phase on the FIA-ED signal were also studied. 相似文献
56.
Nitrogen desorption scanning hysteresis loops (DSHLs) for large-pore MCM-41 silicas (pore diameter from 4.0 to 6.5 nm) are reported for the first time. DSHLs for MCM-41 were compared with those of conventional mesoporous silicas and no appreciable differences were found, although hysteresis loops and DSHLs for the latter were usually broader. Since desorption behavior of conventional porous silicas is appreciably influenced by pore connectivity, the observed similarity in hysteresis behavior suggests single-pore blocking effects for MCM-41 due to variation of pore diameter along its nonintersecting channels. It was also shown that the steepness of nitrogen desorption branches at relative pressures close to 0.4 often results from proximity of the lower pressure limit of adsorption-desorption irreversibility and consequently it is not justified to consider it as an indication of narrow pore size distribution. Thus, application of desorption data in calculations of pore size distributions may be grossly misleading. 相似文献
57.
I. Michalík 《Journal of Radioanalytical and Nuclear Chemistry》1985,95(4):263-268
The multiphase character of phosphate uptake kinetics was stated in the experiments with intact maize roots depending on different phosphorus concentration in the external solution /from 0.0001 to 50 mM P/. The single phases are characterized by different Km and Vmax values as well as by transition points /T/. The separate phases of the multiphase isotherm of phosphates uptake are distinguished by transition points. T determines the critical concentration of phosphorus as a function of active membrane transport system /i.e. T1–2=0.39 mM; T2–3=1.96 mM; T3–4=10 mM; T4–5=33 mM/. 相似文献
58.
Chodkiewicz ML 《The Journal of chemical physics》2005,122(22):224107
A new method for generating a compact multipolar representation of the electrostatic potential (EP) for flexible molecules is presented. The method is based on a constrained minimization of the difference between the quantum mechanical and the classical EP. The fitting procedure used adopts the least absolute shrinkage and selection operator technique [R. Tibshirani, J. Roy. Stat. Soc. B 58, 267 (1996)] which can be seen as penalized ordinary least squares. The penalty function optimized for the particular molecule of interest effectively removes redundant multipoles. It is shown that the use of multiple conformations is crucial for the predictive ability of the EP model for flexible molecules. The multipole local coordinate systems are chosen in a way that best reflects the key conformational changes. It was demonstrated that such an approach improves the predictive ability of EP models. It also allows to exploit equivalence of atoms in the calculation of multipoles components. In the case of polar flexible molecules, the augmentation of the EP model based on charges by higher multipoles decreases the relative root mean square error by a factor of 1.5-5. The corresponding effect of enlargement of the set of multipoles was significantly reduced. 相似文献
59.
Lewis acid-mediated Diels-Alder reactions of quinol lactone 2 gave regioselectivity opposite to that of the uncatalyzed reaction. Compound 12 is proposed as the reactive intermediate generated by the reaction of 2 with stannic chloride. 相似文献
60.
A new phenolic glucoside gallate, vanillic acid 4-O-beta-D-(6'-O-galloyl) glucopyranoside (1) was isolated from the bark of Terminalia macroptera Guill.et Perr., together with 3,3',4'-tri-O-methylellagic acid (2) and two triterpene glucopyranosyl esters, 24-deoxysericoside (3) and chebuloside II (4). Compounds 2-4, not described previously for this plant, showed antimicrobial activities against Bacillus subtilis, while 3 and 4 possessed haemolytic properties. In both assays 1 was found to be inactive. 相似文献