全文获取类型
收费全文 | 1615篇 |
免费 | 64篇 |
国内免费 | 7篇 |
专业分类
化学 | 1271篇 |
晶体学 | 15篇 |
力学 | 18篇 |
数学 | 99篇 |
物理学 | 283篇 |
出版年
2023年 | 6篇 |
2022年 | 16篇 |
2021年 | 19篇 |
2020年 | 33篇 |
2019年 | 27篇 |
2018年 | 22篇 |
2017年 | 10篇 |
2016年 | 34篇 |
2015年 | 30篇 |
2014年 | 43篇 |
2013年 | 106篇 |
2012年 | 82篇 |
2011年 | 118篇 |
2010年 | 54篇 |
2009年 | 54篇 |
2008年 | 106篇 |
2007年 | 107篇 |
2006年 | 104篇 |
2005年 | 71篇 |
2004年 | 66篇 |
2003年 | 59篇 |
2002年 | 43篇 |
2001年 | 36篇 |
2000年 | 22篇 |
1999年 | 24篇 |
1998年 | 17篇 |
1997年 | 20篇 |
1996年 | 16篇 |
1995年 | 15篇 |
1994年 | 20篇 |
1993年 | 19篇 |
1992年 | 15篇 |
1991年 | 12篇 |
1990年 | 18篇 |
1989年 | 23篇 |
1988年 | 19篇 |
1987年 | 14篇 |
1986年 | 12篇 |
1985年 | 20篇 |
1984年 | 14篇 |
1983年 | 14篇 |
1982年 | 11篇 |
1981年 | 17篇 |
1980年 | 16篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 6篇 |
1975年 | 13篇 |
1974年 | 6篇 |
1973年 | 13篇 |
排序方式: 共有1686条查询结果,搜索用时 15 毫秒
31.
5-Fluorouracil derivatives with serum protein binding potencies 总被引:1,自引:0,他引:1
S Yamashita Y Suda M Masada T Nadai M Sumi 《Chemical & pharmaceutical bulletin》1989,37(10):2861-2863
To develop an optimal delivery system for 5-fluorouracil (5FU) using serum protein as a drug carrier, a series of its benzyl derivatives was synthesized. Then their binding to the serum protein was investigated by equilibrium dialysis. The benzyl derivatives of 5FU were strongly bound to rat plasma protein or human serum albumin. The bound percentage increased with increasing hydrophobicity. It was suggested that the benzyl derivative of 5FU existed in the blood as a complex with serum albumin and circulated for a long time as a polymeric drug does. 相似文献
32.
[reaction in text] The first total synthesis of (+/-)-linderol A, a hexahydrodibenzofuran isolated from Lindera umbellata bark, with potent inhibitory activity on melanin biosynthesis of cultured B-16 melanoma cells was achieved via a 20-step of reaction in 7.64% overall yield starting from 4,6-dimethoxysalicylaldehyde. 相似文献
33.
Knöevenagel-type reaction between diketene and aldehydes proceeded in the presence of Ti(O-i-Pr)4. This reaction proceeded via titanium enolate derived from Ti(O-i-Pr)4 and diketene. As for the stereoselectivity of the products, E-isomers were produced predominantly in the case of aromatic aldehydes. 相似文献
34.
Akhtaruzzaman M Kamata N Nishida J Ando S Tada H Tomura M Yamashita Y 《Chemical communications (Cambridge, England)》2005,(25):3183-3185
Dithiazolylbenzothiadiazoles easily obtained have high electron affinity and the FET device of a trifluoromethylphenyl derivative exhibited a good n-type performance with high electron mobility. 相似文献
35.
Takashi Kajiwara Kensuke Katagiri Shinya Takaishi Masahiro Yamashita Nobuhiko Iki 《化学:亚洲杂志》2006,1(3):349-351
A dodecaholmium wheel of [Ho12(L)6(mal)4(AcO)4(H2O)14] ( 1 ; mal=malonate) was synthesized by using p‐tert‐butylsulfonylcalix[4]arene (H4L) as a cluster‐forming ligand. The wheel consists of three fragments of mononuclear A3? ([Ho(L)(mal)(H2O)]3?), trinuclear B3? ([Ho(H2O)2(mal)(Ho(L)(AcO))2]3?), and C3+ ([Ho(H2O)2]3+), and an alternate arrangement of these fragments (A3?? C3+? B3?? C3+? A3?? C3+? B3?? C3+? ) results in a wheel structure. The longest and shortest diameters of the core were estimated to be 17.7562(16) and 13.6810(13) Å, respectively, and the saddle‐shaped molecule possesses a pocketlike cavity inside. 相似文献
36.
Intercrystalline migration and a migration-assisted chemical reaction of adsorbed aromatic species between zeolite particles in physical contact were visualized by fluorescence microscopy coupled with a particle manipulation technique. The luminescence color characteristics of particular zeolite particles originating from the specific photochemistry of adsorbed species was exploited to follow the migration of the molecules. Two examples are shown that are relevant to the visualization of the time-dependent migration process: A one guest-two sets of zeolite crystals system: chrysene (Chry)-loaded zeolite Na+ -X (the sodium form of zeolite X) crystals were placed in contact with unloaded Tl+ -X (thallium-exchanged X) crystals and allowed to stand at room temperature. Initially, the blue fluorescence of Chry was detected only from the Na+ -X particles, but later, the development of green phosphorescence emission was discernible from the Tl+ -X which suggests that Chry migrated from the Na+ -X to the Tl+ -X crystals. A two guest-species systems: Electron-donating Chry-loaded Na+ -X crystals were placed in contact with electron-accepting 1,2,4,5-tetracyanobenzene (TCNB)-loaded Na+ -X or Na+ -Y crystals. With time, the former system (Chry/Na+ -X and TCNB/Na+ -X) gave rise to the emission of Chry-TCNB charge-transfer complexes resulting mainly from the migration of Chry while the latter system (Chry/Na+ -X and TCNB/Na+ -Y) afforded the same emission resulting largely from the migration of TCNB. The present investigation reveals that there is a certain direction for guest migration depending on the zeolite host and the nature of host-guest or guest-guest interaction. 相似文献
37.
Noritaka Ohtani Makoto Nakaya Kenji Shirahata Tsuyoshi Yamashita 《Journal of polymer science. Part A, Polymer chemistry》1994,32(14):2677-2686
Polystyrene-based crosslinked cationic ionomers containing ammonium or phosphonium chlorides (AxRCI and PxBuCI) were reacted with decyl methanesulfonate. The kinetic data were correlated with the swelling behavior of the ionomers and the solution viscosity of the corresponding linear ionomers. The reactivity of the ionomers was independent of the particle size of the ionomer beads, indicating no diffusion control of the reaction. The solvent and the ion content of the ionomers greatly affect the reactivity. In nonpolar solvents with a low acceptor number, AN, such as toluene, the aggregation of ionic groups with an increasing ion content reduces the reactivity. A solvent with a high value of AN, such as chloroform, led a very low reactivity independent of the ion content. Aprotic polar solvent, such as acetonitrila, promoted the dissociation of the ionic groups and furnished a relatively high reactivity independent of the ion content. Several catalytic substitution reactions were carried out under liquid-solid-solid triphase conditions. The kinetic results were accounted for in terms of slow nucleophile transport and fast chemical reaction within the ionomer particles. © 1994 John Wiley & Sons, Inc. 相似文献
38.
Summary The surface dyeability of the poly(vinyl alcohol) fiber with different degree of formalization was studied by measuring -potential of the fiber in alkaline aqueous solutions (pH 10) of a cationic dye Methylene Blue. With the increase in the dye concentration, the sign of the -potential of the fiber changed from negative to positive and thereafter the positive value approximated to saturated value, and the amount of dye adsorbed (expressed in mol/cm2-fiber) increased also. These results may possibly be attributed to the formation of the electrostatic bond between the fiber and the dye. The linear relations were found between and logC
d
and its slope did not change with rise of temperature. The free energy of dyeing G (negative) calculated from the slope of the -logC
id
curve, etc. increased with increasing the degree of formalization of the fiber. This fact corresponds to the increase in the surface dye adsorption with increasing the degree of formalization. With increasing the degree of formalization, the heat of dyeing H (negative) increased and the entropy of dyeing S (positive) decreased. The positive value of S for each fiber, suggests the formation of hydrophobic bond as a driving force to the dyeing of Methylene blue on the fiber surface in addition to the electrostatic bond.This paper is Part XXVII in a series on Studies on -potentials and Surface Dyeability of Natural and Synthetic Fibers in Dye Solution. Part XXVI: T. Suzawa andK. Kawakami, Nippon Kagaku Kaishi1975, No. 7,1134. 相似文献
39.
Yuhsuke Kawakami Tomiya Sugiura Yutaka Mizutani Yuya Yamashita 《Journal of polymer science. Part A, Polymer chemistry》1980,18(10):3009-3020
Enantiomer-differentiating ester syntheses from acid salts, chlorides, and an anhydride were studied in the presence of optically active polyamines. Enantiomer selection occurred in reactions of a racemic salt with an achiral alkyl bromide and vice versa, which is good evidence of the importance of activation of the carboxylate group by complexation of the counterion and activation of alkyl bromide by the formation of a quaternary salt with polyamine under solid–liquid, phase-transfer reaction conditions. Only small optical activity was observed in the products of acid anhydride or chloride with alcohol. 相似文献
40.
Novel 1,4-elimination reaction of C,N-bis(trimethylsilyl)-C- trimethylsiloxymethylketenimine and retro Diels-Alder reaction of 2-oligosiloxanyl-5-norbornene-2-carbonitrile cleanly gave α-oligosiloxanylacrylonitriles in excellent yield. 相似文献