全文获取类型
收费全文 | 719篇 |
免费 | 25篇 |
国内免费 | 2篇 |
专业分类
化学 | 629篇 |
晶体学 | 5篇 |
力学 | 6篇 |
数学 | 39篇 |
物理学 | 67篇 |
出版年
2023年 | 9篇 |
2022年 | 27篇 |
2021年 | 20篇 |
2020年 | 16篇 |
2019年 | 17篇 |
2018年 | 15篇 |
2017年 | 15篇 |
2016年 | 23篇 |
2015年 | 21篇 |
2014年 | 24篇 |
2013年 | 37篇 |
2012年 | 46篇 |
2011年 | 72篇 |
2010年 | 23篇 |
2009年 | 33篇 |
2008年 | 56篇 |
2007年 | 53篇 |
2006年 | 30篇 |
2005年 | 36篇 |
2004年 | 19篇 |
2003年 | 19篇 |
2002年 | 16篇 |
2001年 | 10篇 |
2000年 | 11篇 |
1999年 | 5篇 |
1997年 | 3篇 |
1994年 | 2篇 |
1993年 | 6篇 |
1992年 | 2篇 |
1991年 | 6篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1984年 | 6篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 7篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1973年 | 4篇 |
1969年 | 2篇 |
1968年 | 2篇 |
1967年 | 2篇 |
1954年 | 2篇 |
1937年 | 2篇 |
1928年 | 1篇 |
1922年 | 1篇 |
排序方式: 共有746条查询结果,搜索用时 15 毫秒
11.
Stereocontrolled syntheses of dictyopterene B (hormosirene) (1) and its enantiomer (ent-1) are reported. Key steps are highly stereoselective ScN′ reactions of esters of alcohols 2 and 5 derived from (+)-camphor. 相似文献
12.
13.
Sitnikova NL Sprik R Wegdam G Eiser E 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7083-7089
We studied the spontaneous emulsification and droplet growth mechanism in trans-anethol/water/ethanol solutions, also known as the beverage ouzo, using dynamic light scattering spectroscopy. This simple ternary mixture is a generic example of a system that forms microemulsions spontaneously when brought into the two-phase region. The volume fraction of the dispersed phase was found to profoundly affect the growth rates of the droplets, which is a new finding that has not been predicted by the Lifshitz-Slyozov-Wagner theory. Time-dependent measurements show that the droplet growth is governed by Ostwald ripening (OR), and no coalescence was observed. Furthermore, the OR rates increase with increasing oil concentration at low alcohol content. We attribute this behavior to enhanced droplet-droplet interactions. At high ethanol concentrations, we found that the measured rates decreased as the oil concentration increased. The OR growth mechanism completely correlates with changes in droplet size. The kinetics of droplet growth shows that the ripening has a saturation limit at a droplet radius of about 1.5 mum. Thus, formed emulsions remain stable for months. 相似文献
14.
Yoshizumi Ishikawa Hideyasu Honda Yoshiyuki Sugahara 《Journal of Sol-Gel Science and Technology》2000,19(1-3):365-369
The conversion of tetrakis(diethylamino)titanium (Ti(NEt2)4) into titania via either a combination of hydrolysis (Ti(NEt2)4 : THF : H2O = 1 : 10 : x, x = 2, 4, 10) at ambient conditions and calcination (method A) or hydrolysis in a water-tetrahydrofuran (THF) mixture (Ti(NEt2)4 : THF : H2O = 1 : 10 : 100) at reflux (method B) was investigated. Titanium tertiary butoxide (Ti(O
t
Bu)4) was also used as a substitute for Ti(NEt2)4. The hydrolysis via method A resulted in the formation of amorphous solids containing organics. Thermal analyses showed that the hydrolysis products showed mass losses up to 500°C probably due to the presence of diethylamine (Et2NH) formed via the hydrolysis of Ti(NEt2)4 in the hydrolysis products, while a mass loss of the hydrolysis product from Ti(O
t
Bu)4 was completed up to about 200°C. After calcination at 600°C, anatase or a mixture of anatase and rutile was obtained. The crystallization behavior of the hydrolysis products from Ti(NEt2)4 was different from that of the hydrolysis product from Ti(O
t
Bu)4. The hydrolysis via method B gave only an amorphous material from Ti(NEt2)4, while a crystalline titania (anatase and brookite) formed from Ti(O
t
Bu)4. 相似文献
15.
The effect of the conformation of a polymeric pseudostationary phase on performance and selectivity in electrokinetic chromatography was studied using an amphiphilic pH-responsive polymer that forms compact intramolecular aggregates (unimer micelles) at low pH and a more open conformation at high pH. The change in conformation was found to affect the electrophoretic mobility, retention, selectivity, and separation efficiency. The low-pH conformer has higher electrophoretic mobility and greater affinity for most solutes. The unimer micelle conformation was also found to provide a solvation environment more like that of micelles and other amphiphilic self-associative polymers studied previously. It was not possible to fully characterize the effect of conformation on efficiency, but very hydrophobic solutes with long alkyl chains appeared to migrate with better efficiency when the unimer micelle conformation was employed. The results imply that polymers with a carefully optimized lipophilic-hydrophilic balance that allow self-association will perform better as pseudostationary phases. In addition, the results show that electrokinetic chromatography is a useful method for determining the changes in solvation environment provided by stimuli-responsive polymers with changes in the conditions. 相似文献
16.
Shlomo Margel Erika Wiesel 《Journal of polymer science. Part A, Polymer chemistry》1984,22(1):145-158
Monodisperse polyacrolien (PA) microspheres were obtained by a single step process via two mechanisms: (a) aqueous polymerization of acrolein under alkaline conditions and (b) aqueous radical polymerization of acrolein by irradiation with a cobalt source. The diameter of the former microspheres can be varied from 0.04 up to 8 μm. The monodispersity of the system is also discussed. The diameter of the latter microspheres can be varied up to 0.2 μm. Hybrido PA microspheres were formed by grafting PA microspheres of average diameter of 0.1 μm obtained by irradiation onto the surface of PA microspheres produced by the alkaline mechanism. The aldehyde content of the microspheres prepared by irradiation is much higher than those of the microspheres formed under alkaline conditions. The aldehyde groups were used for the covalent binding of ligands containing primary amino groups, such as proteins and drugs, in a single step under physiological pH. 相似文献
17.
Biomineral formation is a common trait and prominent for soil Actinobacteria, including the genus Streptomyces. We investigated the formation of nickel-containing biominerals in the presence of a heavy-metal-resistant Streptomyces mirabilis P16B-1. Biomineralization was found to occur both in solid and liquid media. Minerals were identified with Raman spectroscopy and TEM-EDX to be either Mg-containing struvite produced in media containing no nickel, or Ni-struvite where Ni replaces the Mg when nickel was present in sufficient concentrations in the media. The precipitation of Ni-struvite reduced the concentration of nickel available in the medium. Therefore, Ni-struvite precipitation is an efficient mechanism for tolerance to nickel. We discuss the contribution of a plasmid-encoded nickel efflux transporter in aiding biomineralization. In the elevated local concentrations of Ni surrounding the cells carrying this plasmid, more biominerals occurred supporting this point of view. The biominerals formed have been quantified, showing that the conditions of growth do influence mineralization. This control is also visible in differences observed to biosynthetically synthesized Ni-struvites, including the use of sterile-filtered culture supernatant. The use of the wildtype S. mirabilis P16B-1 and its plasmid-free derivative, as well as a metal-sensitive recipient, S. lividans, and the same transformed with the plasmid, allowed us to access genetic factors involved in this partial control of biomineral formation. 相似文献
18.
Momoko Ishida Rika Ohara Fuka Miyagawa Hiroe Kikuzaki Kosuke Nishi Hiroyuki Onda Nanami Yoshino Takuya Sugahara 《Molecules (Basel, Switzerland)》2022,27(13)
Cuminum cyminum L. (cumin) is an annual plant of the Umbelliferae family native to Egypt. We previously showed that the aqueous extract of cumin seeds suppresses degranulation by downregulating the activation of antigen-induced intracellular signaling molecules in rat basophilic leukemia RBL-2H3 cells. However, the active substances in the extract have not yet been identified. Accordingly, herein, we aimed to ascertain the water-soluble substances present in cumin seeds that inhibit degranulation, which led to the identification of umbelliferose, a characteristic trisaccharide present in plants of the Umbelliferae family. Our study is the first to reveal the degranulation-suppressing activity of umbelliferose, and quantification studies suggest that cumin seed powder contains 1.6% umbelliferose. Raffinose, an isomer of umbelliferose, was also found to significantly suppress antigen-induced degranulation, but less so than umbelliferose. Both umbelliferose and raffinose contain sucrose subunits in their structures, with galactose moieties bound at different sites. These differences in structure suggest that the binding of galactose to the sucrose subunit at the α1-2 bond contributes to its strong degranulation-inhibiting properties. 相似文献
19.
Saulius Armalis Inga Krikŝĉiuniene Erika Kubiliene Nii-Kotey Djane Kuria Ndungu Lennart Mathiasson 《International journal of environmental analytical chemistry》2013,93(1-4):233-242
Abstract The performance of a flow-through mercury coated reticulated vitreous carbon (RVC) electrode in the potentiometric stripping analysis (PSA) of trace metals has been examined. A wall-jet glassy carbon cell was used for the comparative experiments. Experimental parameters influencing the stripping signals have been optimised in order to use the stripping analysis after the preconcentration and matrix isolation by supported liquid membrane (SLM) technique. The SLM with di-2-ethylhexyl-phosphoric acid (DEHPA) as the extractant in the membrane liquid for proton driven transport of trace metals across the membrane has been chosen. Results presented for lead determination in river water demonstrate the analytical advantages of coupled technique SLM-PSA. 相似文献
20.
Erika Cerutti Annelaure Damont Frédéric Dollé Simona Baroni Silvio Aime 《Magnetic resonance in chemistry : MRC》2013,51(2):116-122
DPA‐713 is the lead compound of a recently reported pyrazolo[1,5‐a]pyrimidineacetamide series, targeting the translocator protein (TSPO 18 kDa), and as such, this structure, as well as closely related derivatives, have been already successfully used as positron emission tomography radioligands. On the basis of the pharmacological core of this ligands series, a new magnetic resonance imaging probe, coded DPA‐C6‐(Gd)DOTAMA was designed and successfully synthesized in six steps and 13% overall yield from DPA‐713. The Gd‐DOTA monoamide cage (DOTA = 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid) represents the magnetic resonance imaging reporter, which is spaced from the phenylpyrazolo[1,5‐a]pyrimidineacetamide moiety (DPA‐713 motif) by a six carbon‐atom chain. DPA‐C6‐(Gd)DOTAMA relaxometric characterization showed the typical behavior of a small‐sized molecule (relaxivity value: 6.02 mM?1 s?1 at 20 MHz). The good hydrophilicity of the metal chelate makes DPA‐C6‐(Gd)DOTAMA soluble in water, affecting thus its biodistribution with respect to the parent lipophilic DPA‐713 molecule. For this reason, it was deemed of interest to load the probe to a large carrier in order to increase its residence lifetime in blood. Whereas DPA‐C6‐(Gd)DOTAMA binds to serum albumin with a low affinity constant, it can be entrapped into liposomes (both in the membrane and in the inner aqueous cavity). The stability of the supramolecular adduct formed by the Gd‐complex and liposomes was assessed by a competition test with albumin. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献