全文获取类型
收费全文 | 1223篇 |
免费 | 35篇 |
国内免费 | 7篇 |
专业分类
化学 | 1084篇 |
晶体学 | 10篇 |
力学 | 6篇 |
综合类 | 1篇 |
数学 | 43篇 |
物理学 | 121篇 |
出版年
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 10篇 |
2017年 | 14篇 |
2016年 | 22篇 |
2015年 | 17篇 |
2014年 | 27篇 |
2013年 | 55篇 |
2012年 | 69篇 |
2011年 | 78篇 |
2010年 | 47篇 |
2009年 | 38篇 |
2008年 | 90篇 |
2007年 | 88篇 |
2006年 | 81篇 |
2005年 | 81篇 |
2004年 | 90篇 |
2003年 | 56篇 |
2002年 | 62篇 |
2001年 | 16篇 |
2000年 | 7篇 |
1999年 | 18篇 |
1998年 | 9篇 |
1997年 | 19篇 |
1996年 | 8篇 |
1995年 | 13篇 |
1994年 | 10篇 |
1993年 | 20篇 |
1992年 | 8篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 11篇 |
1987年 | 7篇 |
1986年 | 9篇 |
1985年 | 14篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 23篇 |
1980年 | 8篇 |
1979年 | 10篇 |
1978年 | 6篇 |
1977年 | 9篇 |
1976年 | 12篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 4篇 |
排序方式: 共有1265条查询结果,搜索用时 15 毫秒
71.
The anthracene–9, 10–bisketene compound 9, 10-dicarbonyl-9, 10–dihydroanthracene (1) was found to react spontaneously with a variety of benzoquinones and benzoquinone diimines to give aromatic polyesters and polyamides, respectively. These addition reactions are regarded as a novel preparative route to polyarylate and polyaramide. 相似文献
72.
Makoto Suzuki Tetsuya Tateishi Masahiko Matsuzawa Masakatsu Saito 《Macromolecular Symposia》1996,109(1):55-66
Amphoteric PVA hydrogels were made from mixed aqueous solutions of poly(acrylic acid), poly(allylamine) hydrochloride and poly(vinyl alcohol) by repetitive freezing and thawing. The hydrogen bond induced gelation produced an elastic and tough microporous hydrogel which generated tension as high as 0.3MPa corresponding to the solvent exchange from water to acetone. In this paper we show the microscopic structure of hydrogels determined by means of cryo-SEM technique and X-ray analysis. 相似文献
73.
74.
Kaname Tsutsumiuchi Keigo Aoi Masahiko Okada 《Macromolecular rapid communications》1995,16(10):749-755
A novel glycopeptide-containing block copolymer, poly[O-(tetra-O-acetyl-β-D -glucopyranosyl)-L -serine]-block-poly(2-methyl-2-oxazoline) ( 5 ), was synthesized by mutual termination of living polymerizations of a sugar-substituted α-amino acid N-carboxyanhydride (NCA) ( 1 ) and 2-methyl-2-oxazoline ( 3 ). 5 was deacetylated to provide the glycopeptide-polyoxazoline block copolymer, poly[O-(β-D -glucopyranosyl)-L -serine]-block-poly(2-methyl-2-oxazoline) ( 6 ). 相似文献
75.
Masahiko Minoda Katsushi Yamaoka Kenji Yamada Akira Takaragi Takeaki Miyamoto 《Macromolecular Symposia》1995,99(1):169-177
The present paper focuses on (i) a new synthetic methodology to prepare vinyl ether-based synthetic glycoconjugates (glycopolymers) with well-controlled structure, and on (ii) the application of glycopolymers bearing modified disaccharide residue as thermotropic liquid crystalline (LC) materials. Two vinyl ethers (VEs) having pendant glucose residues with their hydroxyl functions protected by acetyl and isopropylidene groups, respectively, were found to undergo living cationic polymerization initiated by a HI/ZnI2-initiating system. Deprotection of the resultant monodisperse polymers led to water-soluble polymers bearing a pendant glucose residue. Sequential living block copolymerization of glucose-containing VE and alkyl VE, and subsequent deprotection afforded an amphiphilic block copolymer of well-controlled structure. Transmission electron microscopic observation of its cast thin film revealed microphase-separated surface morphologies that varied with varying segment composition ratio. A VE substituted with a heptadecanoated cellobiose pendant was independently prepared, and was cationically polymerized to give a thermotropic LC polymer. From X-ray analysis, the mesophase was assigned to a discotic columnar in type, in which each main chain, extended due to the steric repulsion between the neighboring bulky pendants, was surrounded by three discotic columns. 相似文献
76.
水滑石类化合物 (LDH) 的层板金属阳离子组成具有可调变性,通过将具有变价特性的过渡金属定量引入 LDH 层板,经热处理后可以得到具有高比表面积和层板金属原子级分散的混合金属氧化物,后者可广泛用作催化剂载体.如三元Mg-Al-Fe 类水滑石材料在光催化、H2S 选择性氧化和乙苯脱氢等反应中表现出较好的活性.Ir 催化剂在α,β-不饱和醛加氢反应中具有较好的活性,Fe 修饰 Ir 催化剂可提高不饱和醇选择性,但有关 Fe 的作用以及 Fe 与活性组分 Ir 间的相互作用本质还不是很清楚.本文以类水滑石材料 Mg3Al1–xFex为载体,采用等体积浸渍法制备了 Ir 催化剂,并用于肉桂醛加氢反应,通过考察 Fe的加入对 Ir 电子和几何结构的影响揭示了 Fe 的加入对活性和选择性的影响规律.结果表明,当 x 从 0 (Ir/Mg3Al) 增加到 1 (Ir/Mg3Fe) 时,肉桂醛加氢的反应速率在 x = 0.25 时达到最大值,肉桂醇选择性从 44.9% 增加到 80.3%,且不随肉桂醛转化率的增加而改变.透射电镜结果表明,Ir 纳米粒子的粒径随着 x 的增加未发生明显变化,均为 1.7±0.2 nm.H2程序升温还原结果发现 Ir 可以促进 Fe3+的还原且两者之间存在相互作用.X射线光电子能谱结果表明,Fe 的掺杂没有改变催化剂表面Ir0和 Ir4+含量的比值,但当 Fe 含量增加时,Fe2+2p3/2向高结合能方向偏移,且 Ir04f7/2向低结合能方向偏移,说明电子从 Fe2+转移到 Ir,形成了富电子的 Ir 物种和缺电子的 Fe 物种.富电子的 Ir 物种有利于肉桂醛分子中的 C=O 键在其表面吸附,并且和 Ir 相邻的 Fen+物种可以作为亲电位点吸附肉桂醛分子中氧,从而极化和活化 C=O 键,因而催化剂活性和选择性增大.采用吸附 CO 红外光谱表征了催化剂表面的几何结构,2058–2069 cm-1处出现了 CO 吸附峰,归属于 Ir0表面 CO 的线性吸附,高波数 2069 cm-1的吸附峰归属于 CO 在高配位 Ir 位点 (平台) 的吸附,低波数 2058 cm-1的吸附峰归属于 CO 在低配位Ir 位点 (台阶、角、楞) 的吸附.随着 Fe 含量的增加,CO 吸附峰蓝移 11 cm-1,表明 Fe 的加入改变了催化剂表面 Ir 的几何结构,低配位 Ir 位点减少,高配位 Ir 位点增多.高配位 Ir 位点 (平台) 有利于肉桂醛分子中 C=O 键的吸附,从而提高了肉桂醇的选择性.总之,Fe 的加入虽然没有明显改变 Ir 纳米粒子的粒径,但却改变了其电子和几何结构,从而提高了催化剂活性和选择性. 相似文献
77.
Masahiko Isaka Somporn Palasarn Wilunda Choowong Suchada Mongkolsamrit 《Tetrahedron letters》2019,60(2):154-156
Conoideoxime A (1), a prenyl-tryptophan dimer possessing bis-oxime functionality, was isolated from cultures of the whitefly pathogenic fungus Conoideocrella luteorostrata BCC 76664. The structure was elucidated by spectroscopic analyses. It displayed antibacterial activity against Gram-positive bacteria, Bacillus cereus, Enterococcus faecium, and Staphylococcus aureus, with MIC values of 3.13, 6.25, and 6.25?μg/mL, respectively. 相似文献
78.
Masahiko Taniguchi 《Tetrahedron》2010,66(30):5549-5565
A series of (p-phenylene)n-linked meso-mesityl-substituted porphyrin dyads (n=2-4) was prepared via Suzuki coupling of zinc(II) and free base porphyrin building blocks. The resulting zinc(II)/free base porphyrin dyads were demetalated. The series of free base porphyrin dimers (n=1-4), four other porphyrin dimers (with p-phenylene, diphenylethyne or diphenylbutadiyne linkers; and aryl or tridec-7-yl meso substituents), and several benchmark monomers were converted to the thallium(III)chloride complexes under mild conditions. The collection of eight Tl(III)Cl/Tl(III)Cl dimers is designed for studies of ground-state hole-transfer processes and comparison with the excited-state energy- and hole-transfer processes of the corresponding Zn(II)/free base dyads. Altogether, 18 new porphyrin arrays and benchmark monomers have been prepared. 相似文献
79.
80.
We reconstructed an animation made from computer-generated holograms with a reflective LCD panel that had a pixel pitch of 10 mumx10 mum and resolution of 1400x1050 . Using a LED as the reference light, we could clearly observe three-dimensional images whose size was approximately 30 mmx10 mm x30 mm . Moreover, we reconstructed a color holograph by use of a simple system with a set of red, green, and blue LEDs as the reference light. 相似文献