全文获取类型
收费全文 | 6012篇 |
免费 | 1057篇 |
国内免费 | 799篇 |
专业分类
化学 | 4373篇 |
晶体学 | 102篇 |
力学 | 383篇 |
综合类 | 44篇 |
数学 | 694篇 |
物理学 | 2272篇 |
出版年
2024年 | 23篇 |
2023年 | 136篇 |
2022年 | 246篇 |
2021年 | 255篇 |
2020年 | 344篇 |
2019年 | 299篇 |
2018年 | 273篇 |
2017年 | 282篇 |
2016年 | 354篇 |
2015年 | 392篇 |
2014年 | 359篇 |
2013年 | 500篇 |
2012年 | 561篇 |
2011年 | 537篇 |
2010年 | 395篇 |
2009年 | 374篇 |
2008年 | 387篇 |
2007年 | 320篇 |
2006年 | 307篇 |
2005年 | 260篇 |
2004年 | 214篇 |
2003年 | 150篇 |
2002年 | 160篇 |
2001年 | 112篇 |
2000年 | 103篇 |
1999年 | 98篇 |
1998年 | 39篇 |
1997年 | 45篇 |
1996年 | 39篇 |
1995年 | 34篇 |
1994年 | 12篇 |
1993年 | 29篇 |
1992年 | 23篇 |
1991年 | 16篇 |
1990年 | 12篇 |
1989年 | 10篇 |
1988年 | 19篇 |
1986年 | 15篇 |
1985年 | 16篇 |
1984年 | 14篇 |
1983年 | 6篇 |
1982年 | 13篇 |
1980年 | 6篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1974年 | 5篇 |
1973年 | 5篇 |
排序方式: 共有7868条查询结果,搜索用时 0 毫秒
11.
T Kai T Isami K Kobata Y Kurosaki T Nakayama T Kimura 《Chemical & pharmaceutical bulletin》1992,40(9):2498-2504
The maximum fluxes (Jmax) of beta-blockers through keratinized membranes were determined in vitro and compared with their physiochemical parameters such as lipophilicity (log k'0) and melting point (mp). Rat abdominal skin and hamster cheek pouch mucosa were used as the model membranes. Propranolol, metoprolol, timolol, pindolol, nadolol and agenolol were used as beta-blockers with a variety of physicochemical characters. Linear relations of Jmax with either log k'0 or mp were observed both in intact rat skin and in intact hamster cheek pouch, suggesting that the lipophilicity and thermodynamic activity of a drug in the crystal state primarily affect the drug's permeation through these membranes. However, the slope, dJmax/d(log k'0), for cheek pouch mucosa was greater than that for rat skin, corresponding to the lack of appendigeal shunt pathways in cheek pouch. Penetration studies using the delipidized membranes and the isolated stratum corneum sheet of hamster cheek pouch mucosa clarified that the primary rate-limiting barrier function might exist in the lipid layer of the stratum corneum. Jmax values for the tape-stripped and delipidized skins correlated with both the solubilities of drugs in the vehicle and with the mp, suggesting the polar porous characteristics of both model membranes. However, a theoretical approach confirmed that the contribution of an intracellular or aqueous pore route in the intact membrane to the permeation of drugs with positive lipophilic indexes is negligible. 相似文献
12.
Kai Kamada Shintaro Udo Shuichi Yamashita Yuko Tsutsumi Yasumichi Matsumoto 《Solid State Ionics》2003,160(3-4):389-394
Quantitative analysis of metal cation doping by solid oxide electrochemical doping (SOED) has been performed under galvanostatic doping conditions. A M–β″-Al2O3 (M=Ag, Na) microelectrode (contact radius: about 10 μm) was used as cation source to attain a homogeneous solid–solid contact between the β″-Al2O3 and doping target. In Ag doping into alkali borate glass, the measured dopant amount closely matched the theoretical value. High Faraday efficiencies of above 90% were obtained. This suggests that the dopant amount can be precisely controlled on a micromole scale by the electric charge during electrolysis. On the other hand, current efficiencies of Na doping into Bi2Sr2CaCu2Oy (BSCCO) ceramics depended on the applied constant current. Efficiencies of above 80% were achieved at a constant current of 10 μA (1.6 A cm−2). The relatively low efficiencies were explained by the saturation of BSCCO grain boundaries with Na. By contrast, excess Na was detected on the anodic surface of ceramics at a constant current of 100 μA (16 A cm−2). In the present study, we demonstrate that SOED enables micromole-scale control over dopant amount. 相似文献
13.
14.
Guey‐Sheng Liou Sheng‐Huei Hsiao Yi‐Kai Fang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(21):6466-6483
Two new phenyl‐ and naphthyl‐substituted rigid‐rod aromatic dicarboxylic acid monomers, 2,2′‐diphenylbiphenyl‐4,4′‐dicarboxylic acid ( 4 ) and 2,2′‐di(1‐naphthyl)biphenyl‐4,4′‐dicarboxylic acid ( 5 ), were synthesized by the Suzuki coupling reaction of 2,2′‐diiodobiphenyl‐4,4′‐dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass transition temperatures in the range of 187–234 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(1,3,4‐oxadiazole)s exhibited Tg's in the range of 252–283 °C, 10% weight‐loss temperature in excess of 470 °C, and char yield at 800 °C in nitrogen higher than 54%. These organo‐soluble polyhydrazides and poly(1,3,4‐oxadiazole)s exhibited UV–Vis absorption maximum at 262–296 and 264–342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414–445 and 404–453 nm, respectively, with quantum yield up to 38%. The electron‐transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4‐oxadiazole) films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited reversible reduction redox with Eonset at ?1.37 to ?1.57 V versus Ag/AgCl in dry N,N‐dimethylformamide solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6466–6483, 2006 相似文献
15.
Teruhiko Kai Yasunori Suma Shuichiro Ono Takeo Yamaguchi Shin‐ichi Nakao 《Journal of polymer science. Part A, Polymer chemistry》2006,44(2):846-856
We have investigated the effect of the surface state and surface treatment of the pores of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes. Shirasu porous glass (SPG) was used as the inorganic substrate, and methyl acrylate was used as the grafting monomer. The grafting rate increased as the density of silanol on the SPG substrate increased. This result suggests that radicals are generated mainly at the silanol groups on the pore surface by plasma irradiation. The SPG substrates were treated with silane coupling agents used to control the mass of organic material bonded to the pore surface. The thickness of the grafted layer became thinner as the mass of organic material bonded to the pore surface of SPG increased. This decrease in the thickness of the grafted layer could be explained by the decrease in the penetration depth of vacuum ultraviolet rays contained in plasma having a wavelength of less than 160 nm that generated radicals in the pores of the substrate. The thickness of the grafted layer inside the SPG substrates could be controlled through the control of the mass of organic material bonded to the pore surface of the SPG substrate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 846–856, 2006 相似文献
16.
Sheng‐Hsiung Yang Hsing‐Chuan Li Chien‐Kai Chen Chain‐Shu Hsu 《Journal of polymer science. Part A, Polymer chemistry》2006,44(23):6738-6749
Two series of poly(2,3‐diphenyl‐1,4‐phenylenevinylene) (DP‐PPV) derivatives containing multiple bulky substituents were synthesized. In the first series, two different groups were incorporated on C‐5,6 positions of the phenylene moiety to increase steric hindrance and to obtain blue‐shifted emissions. In the second series, bulky fluorenyl groups with two hexyl chains on the C‐9 position were introduced on two phenyl pendants to increase the solubility as well as steric hindrance to prevent close packing of the main chain. Polymers with high molecular weights and fine‐tuned electro‐optical properties were obtained by controlling the feed ratio of different monomers during polymerization. The maximum photoluminescent emissions of the thin films are located between 384 and 541 nm. Cyclic voltammetric analysis reveals that the band gaps of these light‐emitting materials are in the range from 2.4 to 3.3 eV. A double‐layer EL device with the configuration of ITO/PEDOT/P4/Ca/Al emitted pure green light with CIE′1931 at (0.24, 0.5). Using copolymer P6 as the emissive layer, the maximum luminescence and current efficiency were both improved when compared with the homopolymer P4. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6738–6749, 2006 相似文献
17.
本文利用X光电子能谱(XPS)及其它技术对过硫酸铵水溶液处理聚乙烯表面改进粘合性的作用机理进行了研究。结果表明,过硫酸铵的氧化作用使聚乙烯表面引入酮、醛、羧基等含氧基团,使其粘合强度显著提高。高密度聚乙烯表面的氧化深度小于40,低密度聚乙烯的均匀氧化深度在40—90之间。处理后的聚乙烯表面未发现明显的交联产物。 相似文献
18.
Jun Fan Wei‐Guang Zhang Min‐Yu Tan Yu Tang Wei‐Sheng Liu Ning Tang Kai‐Bei Yu 《中国化学》2004,22(6):508-511
The La(III) complex with a new amide‐type tripodal ligand,2,2′.2″‐nitrilotris{[(2′‐benzylaminofomyl)‐phenoxylethyl)amine (L), was synthesized and characterized by X‐ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic. space group, P21/n, a= 1.0644(3) nm. b=2.3889(5) nm, c= 2.1917(5) nm, β=90.65°, V=5.573(2) nm3, Z=1, Dc=1.394 g°cm?3, R1=0.0487, wR [1>2s?(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two‐dimensional sheet of 4.82 networks is assembled by metal‐ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three‐connected nodes. 相似文献
19.
硅杂环丁烷在有机硅化学中是一类非常重要的小分子环系化合物。由于硅杂环丁烷和环丁烷的环张力相似,因而显示出较高的反应活性。例如能与某些试剂作用,生成开环产物;在光解或热解条件下,产生具有Si=C结构的高活性中间体,可用以合成多种有机硅化合物。 相似文献
20.