全文获取类型
收费全文 | 520篇 |
免费 | 27篇 |
国内免费 | 1篇 |
专业分类
化学 | 429篇 |
晶体学 | 3篇 |
力学 | 4篇 |
数学 | 20篇 |
物理学 | 92篇 |
出版年
2022年 | 2篇 |
2021年 | 9篇 |
2020年 | 8篇 |
2019年 | 14篇 |
2018年 | 4篇 |
2017年 | 4篇 |
2016年 | 13篇 |
2015年 | 13篇 |
2014年 | 12篇 |
2013年 | 23篇 |
2012年 | 33篇 |
2011年 | 28篇 |
2010年 | 18篇 |
2009年 | 10篇 |
2008年 | 36篇 |
2007年 | 37篇 |
2006年 | 31篇 |
2005年 | 42篇 |
2004年 | 35篇 |
2003年 | 32篇 |
2002年 | 16篇 |
2001年 | 8篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 11篇 |
1995年 | 4篇 |
1994年 | 8篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 7篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 6篇 |
1987年 | 9篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有548条查询结果,搜索用时 187 毫秒
1.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
2.
3.
N Murakami T Tanase S Nagai Y Sato T Ueda J Sakakibara H Ando Y Hotta K Takeya 《Chemical & pharmaceutical bulletin》1991,39(8):1962-1966
The Diels-Alder reactions of a cardiac glycoside, proscillaridin (1), with some dienophiles were investigated. The reaction of 1 with alkenes such as methyl vinyl ketone and methyl acrylate afforded 3-oxo-2-oxabicyclo[2.2.2]oct-7-enes (2-5) and para-substituted benzene derivatives (6 and 7), while 1 reacted with alkynes (3-butyn-2-one, methyl propiolate) to yield para- or meta-substituted benzene derivatives (6-9). The biological activities of the resulting derivatives were evaluated by the use of isolated guinea-pig papillary muscle preparations and Na+,K(+)-adenosine triphosphatase (ATPase) preparation from dog kidney. Among the proscillaridin derivatives, compounds 4 and 7 moderately inhibited Na+,K(+)-ATPase activity. Furthermore, the concentration range of 7 over which its positive inotropic effect on guinea-pig papillary muscle preparations, increased from 5% to 95% of maximum was broader than that of 1, i.e., concentration dependency was maintained over a greater range of concentration. 相似文献
4.
The high structural similarity of decarboxylase antibody 21D8 and esterase antibody 48G7 suggests that 21D8 might also possess hydrolytic activity. Kinetic investigations show that 21D8 does promote the selective hydrolysis of methyl 4‐nitrophenyl carbonate and sodium 4‐(acetoxy)benzenesulfonate with catalytic proficiencies (kcat/Km)/kun of ca. 105 M ?1. The ability of 21D8 to accelerate a reaction for which it was not developed suggests that certain antibody scaffolds are intrinsically predisposed toward catalysis, a property that can be enhanced and refined during affinity maturation in response to a transition‐state analog. At the same time, however, the restricted structural diversity of the immune system may ultimately limit the catalytic efficiency that can be achieved. 相似文献
5.
Bond IA Budding E Conway MJ Fenton KB Fujii H Fujii Z Fujimoto M Hasegawa H Hayashida N Honda M Hotta N Humble JE Kabe S Kasahara K Kifune T Masaike A Matsubara Y Mitsui K Miura Y Mori M Murakami K Muraki Y Nagano M Nakamura K Nakamura T Norris PM Ohashi Y Okada A Saito T Sakata M Sato H Shibata S Shima M Storey JR Tanimori T Teshima M Torii S Uchino K Watase Y Woodhams MD Yamamoto Y Yock PC Yuda T 《Physical review letters》1988,61(20):2292-2295
6.
7.
Calcium-induced alginate gel beads (Alg-Ca) containing various polysaccharides, including an alginate hydrolysate, were prepared and the drug release profiles were investigated. Hydrocortisone (HC) was gradually released from Alg-Ca into the mimic gastric fluid, while in intestinal fluid, it was quickly released with the dissolution of Alg-Ca. However, with Alg-Ca containing 5% chitin (CT), dissolution of Alg-Ca was not observed, and release of HC showed apparent zero-order kinetics. Furthermore, addition of the alginate hydrolysate altered the HC-release profile for Alg-Ca. 相似文献
8.
Fumio Hamada Kyoko Ishikawa Riko Ito Hisanori Shibuya Sanyo Hamai Iwao Suzuki Tetsuo Osa Akihiko Ueno 《Journal of inclusion phenomena and macrocyclic chemistry》1994,20(1):43-51
-Cyclodextrin with two sodium anthranilate moieties (1) has been prepared as a sensor for detecting organic compounds including terpenoids and steroids. Compound1 shows a pure monomer fluorescence whose intensity is increased or decreased upon addition of the guest species examined. In this system, the sodium anthranilate moieties act either as a spacer, which enables the cyclodextrin to form a 1:1 host-guest complex by narrowing the -cyclodextrin cavity, or as a hydrophobic cap.1 recognizes steroids with much higher sensitivity than terpenoids, in which the appended moieties act as a hydrophobic cap for terpenoids and a spacer for steroids, respectively. 相似文献
9.
10.
The IR and Raman spectra of ethyl trichloroacetate (E-TCA) and its deuterate (E-TCA-d5) have been measured in the liquid, glassy and crystalline states. Vibrational assignment was made by referring to isotopic wavenumber-shift, characteristic group frequencies of related esters and with the aid of a normal coordinate calculation on E-TCA and E-TCA-d5. It is suggested that in the liquid and glassy states there exist two molecular forms (trans—trans—trans and trans—trans—gauche) with regard to the internal rotations about the ClC---C---O---CH2CH3 axis, and that the former persists in the crystalline state. The band pairs of E-TCA and the other ethyl esters are discussed in relation to the nature and number of rotational axes, effect of the heavy trichloromethyl group, and enhancement of band intensity by vibrational coupling. 相似文献