全文获取类型
收费全文 | 2048篇 |
免费 | 82篇 |
国内免费 | 37篇 |
专业分类
化学 | 1150篇 |
晶体学 | 35篇 |
力学 | 65篇 |
数学 | 375篇 |
物理学 | 542篇 |
出版年
2023年 | 15篇 |
2022年 | 13篇 |
2021年 | 36篇 |
2020年 | 37篇 |
2019年 | 34篇 |
2018年 | 26篇 |
2017年 | 27篇 |
2016年 | 53篇 |
2015年 | 36篇 |
2014年 | 53篇 |
2013年 | 112篇 |
2012年 | 145篇 |
2011年 | 154篇 |
2010年 | 92篇 |
2009年 | 67篇 |
2008年 | 112篇 |
2007年 | 94篇 |
2006年 | 105篇 |
2005年 | 81篇 |
2004年 | 79篇 |
2003年 | 66篇 |
2002年 | 56篇 |
2001年 | 46篇 |
2000年 | 53篇 |
1999年 | 48篇 |
1998年 | 22篇 |
1997年 | 36篇 |
1996年 | 20篇 |
1995年 | 33篇 |
1994年 | 28篇 |
1993年 | 38篇 |
1992年 | 46篇 |
1991年 | 34篇 |
1990年 | 31篇 |
1989年 | 27篇 |
1988年 | 15篇 |
1987年 | 15篇 |
1986年 | 18篇 |
1985年 | 26篇 |
1984年 | 22篇 |
1983年 | 6篇 |
1982年 | 13篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 17篇 |
1978年 | 12篇 |
1977年 | 7篇 |
1975年 | 5篇 |
1974年 | 11篇 |
1973年 | 7篇 |
排序方式: 共有2167条查询结果,搜索用时 382 毫秒
401.
Welz O Zádor J Savee JD Ng MY Meloni G Fernandes RX Sheps L Simmons BA Lee TS Osborn DL Taatjes CA 《Physical chemistry chemical physics : PCCP》2012,14(9):3112-3127
The branched C(5) alcohol isopentanol (3-methylbutan-1-ol) has shown promise as a potential biofuel both because of new advanced biochemical routes for its production and because of its combustion characteristics, in particular as a fuel for homogeneous-charge compression ignition (HCCI) or related strategies. In the present work, the fundamental autoignition chemistry of isopentanol is investigated by using the technique of pulsed-photolytic Cl-initiated oxidation and by analyzing the reacting mixture by time-resolved tunable synchrotron photoionization mass spectrometry in low-pressure (8 Torr) experiments in the 550-750 K temperature range. The mass-spectrometric experiments reveal a rich chemistry for the initial steps of isopentanol oxidation and give new insight into the low-temperature oxidation mechanism of medium-chain alcohols. Formation of isopentanal (3-methylbutanal) and unsaturated alcohols (including enols) associated with HO(2) production was observed. Cyclic ether channels are not observed, although such channels dominate OH formation in alkane oxidation. Rather, products are observed that correspond to formation of OH viaβ-C-C bond fission pathways of QOOH species derived from β- and γ-hydroxyisopentylperoxy (RO(2)) radicals. In these pathways, internal hydrogen abstraction in the RO(2)? QOOH isomerization reaction takes place from either the -OH group or the C-H bond in α-position to the -OH group. These pathways should be broadly characteristic for longer-chain alcohol oxidation. Isomer-resolved branching ratios are deduced, showing evolution of the main products from 550 to 750 K, which can be qualitatively explained by the dominance of RO(2) chemistry at lower temperature and hydroxyisopentyl decomposition at higher temperature. 相似文献
402.
Zhao X Ng WY Lau KC Collis AE Horváth IT 《Physical chemistry chemical physics : PCCP》2012,14(11):3909-3914
The reaction of sodium perfluoro-tert-butoxide with benzylic carbon-bromide bond(s) leads to the formation of (nonafluoro-tert-butoxy)methyl ponytail(s), which can enhance the fluorous solubility and partition of aromatics and heterocycles. 相似文献
403.
Swadźba-Kwaśny M Chancelier L Ng S Manyar HG Hardacre C Nockemann P 《Dalton transactions (Cambridge, England : 2003)》2012,41(1):219-227
Two stable nanofluids comprising of mixed valent copper(I,II) oxide clusters (<1 nm) suspended in 1-butyl-3-methylimidazolium acetate, [C(4)mim][OAc], and copper(II) oxide nanoparticles (<50 nm) suspended in trioctyl(dodecyl)phosphonium acetate, [P(8 8 8 12)][OAc], were synthesised in a facile one-pot reaction from solutions of copper(II) acetate hydrate in the corresponding ionic liquids. Formation of the nanostructures was studied using (13)C NMR spectroscopy and differential scanning calorimetry (DSC). From a solution of Cu(OAc)(2) in 1-ethyl-3-methylimidazolium acetate, [C(2)mim][OAc], crystals were obtained that revealed the structure of [C(2)mim][Cu(3)(OAc)(5)(OH)(2)(H(2)O)]·H(2)O, indicating the formation of copper hydroxo-clusters in the course of the reaction. Synthesised nanostructures were studied using transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Physical properties of the prepared IL-nanofluids were examined using IR and UV-VIS spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and densitometry. 相似文献
404.
405.
We devised a dangling cantilever optical lever setup with imaging that permits dynamical studies of superhydrophobic surfaces without the effects of gravitational acceleration for better insight into the mechanics. The setup enabled us to ascertain liquid loss and ascribe it to the interaction of liquid that just touched the superhydrophobic surface as it translated at various constant lateral speeds. At lower speeds (20-60 μm/s), the interactions were characterized by a strong initial liquid pin (at up to 0.6 nN force) and depin followed by a series of smaller force pin and depins before sufficient liquid loss led to total liquid detachment from the surface. At higher translation speeds (80-100 μm/s), the interactions were characterized by liquid pinning and depinning processes at a sustained force (around 0.7 nN) in which liquid loss was low enough to engender a much later liquid detachment (beyond 100 s). A linear reduction of the receding contact angle with time, but not with the advancing contact angle, was found up to the point of first liquid depinning. This suggested a stronger role played by the receding contact line in establishing liquid adherence to the superhydrophobic surface. The detachment process from the surface was also characterized by a liquid bridge driven to rupture by way of liquid being conveyed away from the bridge. 相似文献
406.
Mofakham H Shaabani A Mousavifaraz S Hajishaabanha F Shaabani S Ng SW 《Molecular diversity》2012,16(2):351-356
A novel and efficient method has been developed for the one-pot synthesis of bifunctional diazepine-tetrazole containing compounds. 1H-Tetrazolyl-1H-1,4-diazepine-2, 3-dicarbonitrile and 1H-tetrazolyl-benzo[b][1,4]diazepine derivatives were synthesized in good yields using 2,3-diaminomaleonitrile or an aromatic diamine, ketones, trimethylsilyl azide, and an isocyanide in the presence of p-toluenesulfonic acid as a catalyst in methanol at room temperature. 相似文献
407.
408.
In this study, classical molecular dynamics with the well-known van Beest, Kramer and van Santen potential are used for the first time to investigate the solid thermal conductivity of silica aerogel. Aerogel samples at various densities are obtained through negative pressure rupturing of dense silica samples, and reverse non-equilibrium molecular dynamics is employed to determine the thermal conductivity at each density. Results indicate that a power-law fit of the thermal conductivity obtained varies almost linearly with density, where decreasing density and increasing porosity led to an almost linear decrease in thermal conductivity. This is reflective of the trend observed in experimental bulk sintered silica aerogel. The results also showed that the thermal conductivity is of the same order of magnitude as bulk sintered aerogel. The power-law fit of the results also accurately reflected the variation found in bulk sintered aerogel. 相似文献
409.
Ying-Han Lai Pui-Kin So Samual Chun-Lap Lo Eddy Wing Yin Ng Terence Chuen Wai Poon Zhong-Ping Yao 《Analytica chimica acta》2012
A matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS)-based method has been developed for rapid differentiation between Panax ginseng and Panax quinquefolius, two herbal medicines with similar chemical and physical properties but different therapeutic effects. This method required only a small quantity of samples, and the herbal medicines were analyzed by MALDI-MS either after a brief extraction step, or directly on the powder form or small pieces of raw samples. The acquired MALDI-MS spectra showed different patterns of ginsenosides and small chemical molecules between P. ginseng and P. quinquefolius, thus allowing unambiguous differentiation between the two Panax species based on the specific ions, intensity ratios of characteristic ions or principal component analysis. The approach could also be used to differentiate red ginseng or P. quinquefolius adulterated with P. ginseng from pure P. ginseng and pure Panax quinquefolium. The intensity ratios of characteristic ions in the MALDI-MS spectra showed high reproducibility and enabled quantitative determination of ginsenosides in the herbal samples and percentage of P. quinquefolius in the adulterated binary mixture. The method is simple, rapid, robust, and can be extended for analysis of other herbal medicines. 相似文献
410.
Analyses of tocols (tocopherols and tocotrienols) in palm oil have been extensively reported in the past. However, due to the scarcity of individual tocotrienol standards, calibrations have mostly been carried out using only α-tocopherol as standard. Moreover, even if the individual tocotrienols are being used, their reliability is often questioned, because tocotrienols are highly susceptible to oxidation and deterioration. This paper reports on the study of the deterioration rate of individual tocotrienol standards upon storage as well as different calibration methods for the tocols in palm oil. 相似文献