全文获取类型
收费全文 | 2732篇 |
免费 | 147篇 |
国内免费 | 10篇 |
专业分类
化学 | 2304篇 |
晶体学 | 12篇 |
力学 | 25篇 |
数学 | 285篇 |
物理学 | 263篇 |
出版年
2023年 | 21篇 |
2022年 | 26篇 |
2021年 | 34篇 |
2020年 | 51篇 |
2019年 | 39篇 |
2018年 | 28篇 |
2017年 | 22篇 |
2016年 | 101篇 |
2015年 | 103篇 |
2014年 | 88篇 |
2013年 | 140篇 |
2012年 | 206篇 |
2011年 | 234篇 |
2010年 | 140篇 |
2009年 | 85篇 |
2008年 | 184篇 |
2007年 | 169篇 |
2006年 | 157篇 |
2005年 | 165篇 |
2004年 | 162篇 |
2003年 | 127篇 |
2002年 | 114篇 |
2001年 | 68篇 |
2000年 | 37篇 |
1999年 | 34篇 |
1998年 | 27篇 |
1997年 | 32篇 |
1996年 | 29篇 |
1995年 | 27篇 |
1994年 | 17篇 |
1993年 | 18篇 |
1992年 | 21篇 |
1991年 | 12篇 |
1990年 | 14篇 |
1989年 | 9篇 |
1988年 | 23篇 |
1987年 | 15篇 |
1986年 | 7篇 |
1985年 | 13篇 |
1984年 | 18篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 13篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 13篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1969年 | 5篇 |
排序方式: 共有2889条查询结果,搜索用时 15 毫秒
91.
92.
93.
We have carried out zeta-potential measurements on two different OTS (octadecyl-trichlorosilane)-covered silicas (fused silica, quartz 0001) prepared under identical conditions. Streaming current measurements on the fused silica supported OTS sample indicate a well reproducible IEP of 3.5. The major part of the study focused on the quartz 0001 supported sample with an IEP lower than that of the fused silica support and in agreement with that found in a spectroscopic study. The IEP in water (on addition of HCl) was found at around pH 3, and appeared to shift to lower values in three subsequent measurements. A final measurement after a separate series in KCl media gave the same IEP as obtained in the very first measurement, suggesting that the experiments did not significantly change the interfacial properties despite a large number of experiments. In one series of measurements care was taken to exclude any cations other than protons from the measurements, such that protons are the only counter-ions to the negative net charge. While our IEPs with the quartz support agree well with recent estimates from sum frequency generation (SFG) investigations, none of the zeta-potential vs pH curves would mimic a pattern experimentally observed in the amplitude of the “ice-like” water band between pH 3.5 and 5 in that SFG study. Furthermore, our results do not indicate any significant chloride-ion adsorption in KCl systems, but instead the shift of the IEP with increasing KCl to higher pH values rather indicates specific effects of potassium ions. Under conditions more relevant to the spectroscopic study (i.e. in absence of potassium) no specific pattern reminiscent of the SFG results was found. When tested it was found that surface conductivity was negligible. 相似文献
94.
Chahinez Aouf Christine Le Guernevé Sylvain Caillol Hélène Fulcrand 《Tetrahedron》2013,69(4):1345-1353
The O-alkylation reaction by epichlorohydrin of some natural phenolic compounds such as 4-methylcatechol, gallic acid, protocatechuic acid, pyrogallol and resorcinol was investigated. Phenolic compounds reacted first with epichlorohydrin in the presence of benzyltriethylammonium chloride as phase transfer catalyst. Then, an aqueous solution of sodium hydroxide was added.It was demonstrated that the two competitive mechanisms involved in the O-alkylation reaction were highly dependent of the starting material. The O-alkylated products obtained in this reaction could be further used as bisphenol A substitutes in the synthesis of epoxy resins pre-polymers. 相似文献
95.
Andreea L. Turcu Antoine Versini Nadjib Khene Christine Gaillet Dr. Tatiana Cañeque Dr. Sebastian Müller Dr. Raphaël Rodriguez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(33):7369-7373
Cancer stem cells (CSC) constitute a cell subpopulation in solid tumors that is responsible for resistance to conventional chemotherapy, metastasis and cancer relapse. The natural product Salinomycin can selectively target this cell niche by directly interacting with lysosomal iron, taking advantage of upregulated iron homeostasis in CSC. Here, inhibitors of the divalent metal transporter 1 (DMT1) have been identified that selectively target CSC by blocking lysosomal iron translocation. This leads to lysosomal iron accumulation, production of reactive oxygen species and cell death with features of ferroptosis. DMT1 inhibitors selectively target CSC in primary cancer cells and circulating tumor cells, demonstrating the physiological relevance of this strategy. Taken together, this opens up opportunities to tackle unmet needs in anti-cancer therapy. 相似文献
96.
Dr. Christine Beemelmanns Dr. Dominik Nitsch Dr. Christoph Bentz Prof. Dr. Hans-Ulrich Reissig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8780-8789
A series of γ-indolylketones with fluorine, cyano or alkoxy substituents at the benzene moiety was prepared and subjected to samarium diiodide-promoted cyclization reactions. The desired dearomatizing ketyl cascade reaction forming two new rings proceeded in all cases with high diastereoselectivity, but with differing product distribution. In most cases, the desired annulated tetracyclic compounds were obtained in moderate to good yields, but as second product tetracyclic spirolactones were isolated in up to 29 % yield. The reaction rate was influenced by the substituents at the benzene moiety of the substrate as expected, with electron-accepting groups accelerating and electron-donating groups decelerating the cyclization process. In case of a difluoro-substituted γ-indolylketone a partial defluorination was observed. The intermediate samarium enolate of the tetracyclic products could be trapped by adding reactive alkylating agents as electrophiles delivering products with quarternary carbons. In the case of a dimethoxy-substituted tetracyclic cyclization product a subsequent reductive amination stereoselectively provided a pentacyclic compound that was subsequently N-protected and subjected to a regioselective elimination. The obtained functionalized pentacyclic product should be convertible into the alkaloid brucine by four well-established steps. Overall, the presented report shows that functionalized tetracyclic compounds with different substituents are rapidly available with the samarium diiodide cascade cyclization as crucial step. Hence, analogues of the landmark alkaloid strychnine, for example, with specific fluorine substitutions, should be easily accessible. 相似文献
97.
Ayda Khadhri Intidhar Bouali Chedia Aouadhi Marie‐Christine Lagel Eric Masson Antonio Pizzi 《Biomedical chromatography : BMC》2019,33(11)
This study aimed to investigate the effect of the maturation process of sweet marjoram (Origanum majorana L.) on essential oil composition, the phenolic profile of ethanolic extract and their antioxidant capacities. The essential oil composition was studied at three stages of maturity by GC–MS. Thirty compounds were detected representing 100% of the total essential oil. p‐Menth‐1‐en‐4‐ol was the major compound (37.15–76.94%) followed by cyclohexanol‐3,3,5 trimethyl (5.41–15.99%) and α‐terpineol (0.94–11.34%). During the maturation process, an accumulation of oxygenated monoterpenes was observed. The phenolic composition was studied using matrix‐assisted laser desorption/ionization time of flight. The analysis showed the presence of short flavonoid monomers at all stages of maturation. The antioxidant capacity of ethanolic extracts and essential oils was evaluated using the DPPH assay, iron chelating power and reducing power assay. The highest phenolic content and antioxidant capacity were found at flowering stage. These findings on essential oil composition, phenolic profile and antioxidant capacity of O. majorana at three different stages of development provide more information on how these secondary metabolites are accumulated. 相似文献
98.
99.
100.
Nonlinear Dynamics - An odd number of real Floquet multipliers greater than unity prevents the classical time delayed feedback control from stabilizing torsion-free orbits of nonautonomous systems.... 相似文献