全文获取类型
收费全文 | 754篇 |
免费 | 11篇 |
国内免费 | 8篇 |
专业分类
化学 | 662篇 |
晶体学 | 7篇 |
力学 | 5篇 |
数学 | 23篇 |
物理学 | 76篇 |
出版年
2023年 | 4篇 |
2021年 | 2篇 |
2020年 | 5篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 6篇 |
2014年 | 25篇 |
2013年 | 45篇 |
2012年 | 39篇 |
2011年 | 37篇 |
2010年 | 29篇 |
2009年 | 16篇 |
2008年 | 39篇 |
2007年 | 41篇 |
2006年 | 52篇 |
2005年 | 43篇 |
2004年 | 37篇 |
2003年 | 47篇 |
2002年 | 44篇 |
2001年 | 17篇 |
2000年 | 15篇 |
1999年 | 14篇 |
1998年 | 8篇 |
1997年 | 11篇 |
1996年 | 11篇 |
1995年 | 12篇 |
1994年 | 12篇 |
1993年 | 6篇 |
1992年 | 3篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 8篇 |
1986年 | 5篇 |
1985年 | 10篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 12篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 8篇 |
1978年 | 13篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1974年 | 11篇 |
1973年 | 7篇 |
1965年 | 3篇 |
1936年 | 2篇 |
排序方式: 共有773条查询结果,搜索用时 15 毫秒
51.
Hardness and slip systems by an indentation method were investigated on different habit planes of orthorhombic hen egg-white lysozyme (O-HEWL) crystals containing water. A dependence of the hardness on the water-evaporation time exhibits three stages as incubation, transition and saturated ones, as tetragonal (T)-HEWL crystals reported previously. The hardness values of (1 1 0), (0 1 0) and (0 1 1) habit planes of O-HEWL in the incubation stage or wet condition exhibits 6, 8 and 10 MPa, respectively. The hardness depends on indented planes but it is independent of the air-humidity and crystal volumes. These values correspond to the intrinsic hardness for O-HEWL crystals containing water. In the incubation stage, the slip traces are clearly observed around the indentation mark and the corresponding six kinds of slip systems are identified to be {0 1 1}<1 0 0>, {1 1 0}<1 1 0>, {0 1 1}<0 1 1>, {1 1 0}<0 0 1>, {1 0 0}<0 0 1> and {0 1 0}<0 0 1>. 相似文献
52.
The first bisgermylene with an acyclic structure was synthesized for the first time by one-pot, two-step ligand substitution reactions from the 1,4-dioxane complex of germanium dichloride. The reactions of the bisgermylene with organic halides gave corresponding oxidative addition products, and with organic dihalides gave oligomeric polyadditon products. 相似文献
53.
54.
Shiro Kobayashi 《Macromolecular Symposia》1991,47(1):393-399
Divalent group 14 metal species, a germylene(la) and a stannylene(lb), behaved as a comonomer(reductant monomer) in the copolymerization with p-benzoquinone derivatives(oxidant monomer)(“oxidation-reduction copolymerization”) and as an initiator for anionic monomers. The copolymerization took place without initiator at a lower temperature to give an alternating copolymer. N-phenyl-p-quinoneimine also behaved as a reactive oxidant monomer toward la and lb. These species have been shown to induce the polymerization of anionically polymerizable monomers such as methyl methacrylate, methacrylonitrile, and 4-vinylpyridine. Based on the mechanistic examination of the polymerization, a new alternating copolymerization between la and 2-cyclohexene-l-one has been developed to produce a copolymer having a metal-enolate structure, which involves the oxidation-reduction process during the copolymerization. 相似文献
55.
Masahiro Sekiya Takeshi Noro Toshikatsu Koga Shiro L. Saito 《Journal of computational chemistry》2010,31(3):497-499
Developed and reported are compact yet efficient correlating basis sets for the 57La and 89Ac atoms, missing in the literature. Good performance of these correlating sets is exemplified in molecular applications to diatomic oxides and fluorides. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
56.
A comparative study on chemical conversion of cellulose between the batch-type and flow-type systems in supercritical water 总被引:1,自引:0,他引:1
Microcrystalline cellulose (avicel) was treated in supercritical waterusing batch-type and flow-type systems. The flow-type system made it possibletoshorten the heating, treating and cooling times, compared with the batch-typesystem. As a result, the flow-type system was able to liquefy avicel withoutproducing any supercritical water-insoluble residue. Although hydrolyzedproducts such as glucose and fructose, and pyrolyzed products such aslevoglucosan, 5-hydroxymethyl furfural, erythrose, methylglyoxal,glycolaldehydeand dihydroxyacetone were found in common from the water-soluble portiontreatedby both systems, the flow-type system gave a water-soluble portion with morehydrolyzed and less pyrolyzed products, together with water-solubleoligosaccharides consisting of cellobiose to cellododecaose and theirdecomposedproducts at their reducing end of glucose, such as[–glucopyranosyl]1–11 –levoglucosan,[–glucopyranosyl]1–11 –erythrose and[–glucopyranosyl]1–11 –glycolaldehyde. Inaddition, the precipitates of polysaccharides were recovered after 12h setting of the water-soluble portion. These results indicatedthat the flow-type system can hydrolyze cellulose with minimizing pyrolyzedproducts. On the other hand, the batch-type system resulted in a higher yieldof the pyrolyzed products due to the longer treatment, but a higher yield ofglucose due possibly to the higher pressure and concomitantly higher ionicproduct of water. Based on these lines of evidence, the process to increase theyield of the sugar is discussed under supercritical water treatment. 相似文献
57.
Matsumoto T Kominami T Ueda K Sugimoto T Tada T Noguchi S Yoshino H Murata K Shiro M Negishi E Toyota N Endo S Takahashi K 《Inorganic chemistry》2002,41(18):4763-4769
The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1. 相似文献
58.
An insoluble and assembled catalyst of palladium and a non-cross-linked amphiphilic polymer were developed. In the presence of 50-500 ppm mol equiv of catalyst, the Suzuki-Miyaura reaction proceeded efficiently under organic solvent-free conditions. The catalyst was reused 10 times without any decrease in activity and was recycled without any special treatment.[structure: see text] 相似文献
59.
[reaction: see text] D-Mannono-1,4-lactone was efficiently converted into L-ribose in eight steps. A key step of this synthesis is the cyclization of a gamma-hydroxyalkoxamate under Mitsunobu conditions. It is noteworthy that the O-alkylation product was obtained in 94% yield and that none of the N-alkylation product was detected in this cyclization. 相似文献
60.
Kodera M Tachi Y Kita T Kobushi H Sumi Y Kano K Shiro M Koikawa M Tokii T Ohba M Okawa H 《Inorganic chemistry》2000,39(2):226-234
Two sterically hindered tris-pyridyl methane ligands, tris(6-methyl-2-pyridyl)methane (L1) and bis(6-methyl-2-pyridyl)pyridylmethane (L2), are newly synthesized. Under aerobic conditions, Ln (n = 1 or 2) reacts with CuX2 (X = Cl or Br), oxygenated at the methine position to LnOH or LnOMe. The former alcoholate ligand creates trinuclear Cu(II) complexes [Cu3(X)(LnO)3](PF6)2 [(X, n) = (Br, 1) 1, (C1, 1) 2, (Br, 2) 3, or (C1, 2) 4] in which the alkoxide oxygen atoms bridge copper centers. The crystal structures of 1-4 are presented along with their magnetic susceptibility data. The weak antiferromagnetic coupling between the Cu(II) centers in this trinuclear arrangement is due to weak interaction of the magnetic orbitals (dz2) which are oriented along three alternate sides in a hexagon of the Cu3O3 core in 1-4. Under anaerobic conditions, L1 reacts with CuBr2 to form a square pyramidal complex [CuL1Br2] (9) with the ligand facially capping. [Cu(Br)2(L1OMe)] (10) was obtained after the suspension of 9 in MeOH was stirred under air for 48 h. In the presence of cyclohexene, 9 is converted to [Cu(Br)(L1)]m (m = 1 or 2) 5 quantitatively to give trans- 1,2-dibromocyclohexane, indicating that Br2 is generated during the reaction. The FAB MS spectrum of [18O]-1 prepared by the reaction of L1 with CuBr2 under 18O2 shows that the ligand of [18O]-1 is L1(18O-.) L1(18OH), L1OCD3, and bis(6-methyl-2-pyridyl) ketone were obtained from reaction of L1 with CuBr2 in CD3OD under 18O2. These results indicate that the origins of the O atom in L1OH and L1OMe are O2 and MeOH, respectively. On the basis of these results, a mechanism of the oxygenation of L1 in the present system will be proposed. 相似文献