全文获取类型
收费全文 | 539篇 |
免费 | 0篇 |
国内免费 | 6篇 |
专业分类
化学 | 424篇 |
晶体学 | 3篇 |
力学 | 10篇 |
数学 | 38篇 |
物理学 | 70篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 9篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 5篇 |
2015年 | 8篇 |
2014年 | 8篇 |
2013年 | 16篇 |
2012年 | 31篇 |
2011年 | 32篇 |
2010年 | 14篇 |
2009年 | 21篇 |
2008年 | 42篇 |
2007年 | 41篇 |
2006年 | 39篇 |
2005年 | 50篇 |
2004年 | 41篇 |
2003年 | 24篇 |
2002年 | 30篇 |
2001年 | 4篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 12篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 3篇 |
1989年 | 1篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 10篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1971年 | 1篇 |
排序方式: 共有545条查询结果,搜索用时 15 毫秒
31.
This concept article provides a brief outline of the concept of flash chemistry for carrying out extremely fast reactions in organic synthesis by using microreactors. Generation of highly reactive species is one of the key elements of flash chemistry. Another important element of flash chemistry is the control of extremely fast reactions to obtain the desired products selectively. Fast reactions are usually highly exothermic, and heat removal is an important factor in controlling such reactions. Heat transfer occurs very rapidly in microreactors by virtue of a large surface area per unit volume, making precise temperature control possible. Fast reactions often involve highly unstable intermediates, which decompose very quickly, making reaction control difficult. The residence time can be greatly reduced in microreactors, and this feature is quite effective in controlling such reactions. For extremely fast reactions, kinetics often cannot be used because of the lack of homogeneity of the reaction environment when they are conducted in conventional reactors such as flasks. Fast mixing using micromixers solves such problems. The concept of flash chemistry has been successfully applied to various organic reactions including a) highly exothermic reactions that are difficult to control in conventional reactors, b) reactions in which a reactive intermediate easily decomposes in conventional reactors, c) reactions in which undesired byproducts are produced in the subsequent reactions in conventional reactors, and d) reactions whose products easily decompose in conventional reactors. The concept of flash chemistry can be also applied to polymer synthesis. Cationic polymerization can be conducted with an excellent level of molecular-weight control and molecular-weight distribution control. 相似文献
32.
Fukuoka A Kimura J Oshio T Sakamoto Y Ichikawa M 《Journal of the American Chemical Society》2007,129(33):10120-10125
Preferential oxidation (PROX) of CO is an important practical process to purify H2 for use in polymer electrolyte fuel cells. Although many supported noble metal catalysts have been reported so far, their catalytic performances remain insufficient for operation at low temperature. We found that Pt nanoparticles in mesoporous silica give unprecedented activity, selectivity, and durability in the PROX reaction below 353 K. We also studied the promotional effect of mesoporous silica in the Pt-catalyzed PROX reaction by infrared spectroscopy using the isotopic tracer technique. Gas-phase O2 is not directly used for CO oxidation, but the oxygen of mesoporous silica is incorporated into CO2. These results suggest that CO oxidation is promoted by the attack of the surface OH groups to CO on Pt without forming water. 相似文献
33.
Sun Z Zheng X Hoshi T Kashiwagi Y Anzai J Li G 《Analytical and bioanalytical chemistry》2004,380(3):545-550
Ligustrazine is one of the active ingredients contained in Ligusticum chuanxiong Hort. (Umbelliferae), which is widely used in traditional Chinese medicine for the treatment of cardiovascular problems. In this work, the electrochemistry of Ligustrazine hydrochloride (LZC) and its determination are investigated. The detection limit is estimated to be 8.0×10–8 M, with three linear ranges from 1.0×10–6 to 1.0×10–4 M, 1.0×10–4 to 5.0×10–4 M, and 6.5×10–4 to 1.6×10–3 M. The method has been proved to be highly sensitive, selective, and stable, and has been successfully applied to determining LZC in LZC injections. 相似文献
34.
Eiji Kobayashi Larisa S. Plashnitsa Takayuki Doi Shigeto Okada Jun-ichi Yamaki 《Electrochemistry communications》2010,12(7):894-896
All-solid-state phosphate symmetric cells using Li3V2(PO4)3 for both the positive and negative electrodes with the phosphate Li1.5Al0.5Ge1.5(PO4)3 as the solid electrolyte were proposed. Amorphous Li1.5Al0.5Ge1.5(PO4)3 was added into the electrode to increase the interface area between the active materials and the electrolyte. Any other phases were not formed at the electrode/electrolyte interface even after hot pressing at 600 °C. The discharge capacity was 92 mAh g? 1 at 22 µA cm? 2 at 80 °C, and 38 mAh g? 1 at 25 °C, respectively. Symmetric cell configuration leads to simplify the fabrication process for all-solid-state batteries and will reduce manufacturing costs. 相似文献
35.
One-pot substitution of a C-H bond at the position next to the nitrogen atom of lactams with alkyl malonates proceeded effectively by dehydrogenation of lactams with N-tert-butylbenzenesulfinimidoyl chloride, followed by Mannich-type addition of alkyl malonates. 相似文献
36.
Akutsu H Akutsu-Sato A Turner SS Day P Canadell E Firth S Clark RJ Yamada J Nakatsuji S 《Chemical communications (Cambridge, England)》2004,(1):18-19
Three conducting BEDT-TTF charge-transfer salts with tris(oxalato)metallate anions have unit cells containing both[small alpha] and [small beta][double prime] donor packing motifs. 相似文献
37.
Ando K Tsuji E Ando Y Kunitomo J Kobayashi R Yokomizo T Shimizu T Yamashita M Ohta S Nabe T Kohno S Ohishi Y 《Organic & biomolecular chemistry》2005,3(11):2129-2139
Variable benzo[b]furan derivatives having (E)- and (Z)-2-alkylcarbamoyl-1-methylvinyl groups at the 2-, 4- and 5-positions and a carboxylpropoxy or (1-phenyl)ethoxy group at the 7-position were prepared to find novel and selective leukotriene B4(LTB4) receptor antagonists. (E)-2-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (4v) showed selective inhibition to the human BLT2 receptor (hBLT2). On the other hand, (E)-2-acetyl-4-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (7v) inhibited both human BLT(1) receptor (hBLT1) and hBLT2. The (E)-2-(2-diethylcarbamoyl-1-methylvinyl) group lay on approximately the same plane as the benzo[b]furan ring, whereas the (E)-4-(2-diethylcarbamoyl-1-methylvinyl) group had the torsion angle (45.7 degree) from the benzo[b]furan ring plane. However, the (Z)-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans were inactive. The inhibitory activity depended on the conformation of the 2-diethylcarbamoyl-1-methylvinyl group. 相似文献
38.
Lars J. Wesenberg Erika Diehl Till J. B. Zähringer Carolin Dörr Dr. Dieter Schollmeyer Dr. Akihiro Shimizu Prof. Dr. Jun-ichi Yoshida Prof. Dr. Ute A. Hellmich Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17574-17580
The efficient production of many medicinally or synthetically important starting materials suffers from wasteful or toxic precursors for the synthesis. In particular, the aromatic non-protected primary amine function represents a versatile synthetic precursor, but its synthesis typically requires toxic oxidizing agents and transition metal catalysts. The twofold electrochemical amination of activated benzene derivatives via Zincke intermediates provides an alternative sustainable strategy for the formation of new C−N bonds of high synthetic value. As a proof of concept, we use our approach to generate a benzoxazinone scaffold that gained attention as a starting structure against castrate-resistant prostate cancer. Further improvement of the structure led to significantly increased cancer cell line toxicity. Thus, exploiting environmentally benign electrooxidation, we present a new versatile and powerful method based on direct C−H activation that is applicable for example the production of medicinally relevant compounds. 相似文献
39.
Low-temperature electrochemical oxidation of ArSSAr was carried out to generate a pool of "ArS(+)". Spectroscopic studies ((1)H NMR and CSI-MS) of the resulting solution revealed the accumulation of ArS(ArSSAr)(+). The resulting "ArS(+)" pool reacted with alkenes and alkynes to give diarylthio-substituted products. The "ArS(+)" pool rapidly reacted with thioacetals to give the corresponding alkoxycarbenium ion pools, which reacted with various carbon nucleophiles (indirect cation pool method). The reaction of the alkoxycarbenium ion pools with stilbene derivatives in the presence of ArSSAr gave thiochroman derivatives. In addition to such stoichiometric reactions, a catalytic amount of "ArS(+)" serves as an initiator and a chain carrier of some cationic chain reactions involving intramolecular carbon-carbon bond formation. In situ generation of "ArS(+)" by electrochemical oxidation of ArSSAr with a catalytic amount of electricity in the presence of a substrate is also effective for such cationic chain reactions. 相似文献
40.
Ueda J Takeshita K Matsumoto S Yazaki K Kawaguchi M Ozawa T 《Photochemistry and photobiology》2003,77(2):165-170
The reaction of singlet oxygen (1O2) generated by ultraviolet-A (UVA)-visible light (lambda > 330 nm) irradiation of air-saturated solutions of hematoporphyrin with phenolic compounds in the presence of a spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), gave an electron spin resonance (ESR) spectrum characteristic of the DMPO-hydroxyl radical spin adduct (DMPO-*OH). In contrast, the ESR signal of 5,5-dimethyl-2-pyrrolidone-N-oxyl, an oxidative product of DMPO, was observed in the absence of phenolic compounds. The ESR signal of DMPO-*OH decreased in the presence of either a *OH scavenger or a quencher of *O2 and under anaerobic conditions, whereas it increased depending on the concentration of DMPO. These results indicate both 1O2- and DMPO-mediated formation of free *OH during the reaction. When DMPO was replaced with 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO), no DEPMPO adduct of oxygen radical species was obtained. This suggests that 1O2, as an oxidizing agent, reacts little with DEPMPO, in which a strong electron-withdrawing phosphoryl group increases the oxidation potential of DEPMPO compared with DMPO. A linear correlation between the amounts of DMPO-*OH generated and the oxidation potentials of phenolic compounds was observed, suggesting that the electron-donating properties of phenolic compounds contribute to the appearance of *OH. These observations indicate that 1O2 reacts first with DMPO, and the resulting DMPO-1O2 intermediate is immediately decomposed/reduced to give *OH. Phenolic compounds would participate in this reaction as electron donors but would not contribute to the direct conversion of 1O2 to *OH. Furthermore, DEPMPO did not cause the spin-trapping agent-mediated generation of *OH like DMPO did. 相似文献