全文获取类型
收费全文 | 377篇 |
免费 | 14篇 |
国内免费 | 1篇 |
专业分类
化学 | 298篇 |
晶体学 | 11篇 |
力学 | 2篇 |
数学 | 19篇 |
物理学 | 62篇 |
出版年
2023年 | 2篇 |
2022年 | 4篇 |
2021年 | 4篇 |
2020年 | 2篇 |
2019年 | 5篇 |
2018年 | 10篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 5篇 |
2014年 | 14篇 |
2013年 | 20篇 |
2012年 | 35篇 |
2011年 | 28篇 |
2010年 | 17篇 |
2009年 | 19篇 |
2008年 | 34篇 |
2007年 | 24篇 |
2006年 | 20篇 |
2005年 | 19篇 |
2004年 | 19篇 |
2003年 | 16篇 |
2002年 | 13篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 8篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1958年 | 1篇 |
1955年 | 1篇 |
排序方式: 共有392条查询结果,搜索用时 15 毫秒
61.
Ohno H Okano A Kosaka S Tsukamoto K Ohata M Ishihara K Maeda H Tanaka T Fujii N 《Organic letters》2008,10(6):1171-1174
The palladium-catalyzed domino cyclization of propargyl bromides having two nucleophilic functional groups is described. Treatment of 1,7-diamino-5-bromohept-3-yne derivatives with catalytic Pd(PPh3)4 in the presence of NaH in MeOH gives the 2,7-diazabicyclo[4.3.0]non-5-enes in good yields. Interestingly, the regioselectivity of the reaction is completely controlled by the relative reactivity of the amine functional groups, irrespective of the position of the nucleophiles. The malonate derivative also undergoes domino cyclization to produce a hexahydroindole derivative. 相似文献
62.
Okano A Mizutani T Oishi S Tanaka T Ohno H Fujii N 《Chemical communications (Cambridge, England)》2008,(30):3534-3536
Treatment of allenic bromoalkenes bearing a nucleophilic moiety with a catalytic amount of palladium(0) in the presence of TBAF or Cs(2)CO(3) in MeCN affords bicyclic heterocycles in good to high yields, through zipper-mode cascade cyclisation. 相似文献
63.
Li WS Yamamoto Y Fukushima T Saeki A Seki S Tagawa S Masunaga H Sasaki S Takata M Aida T 《Journal of the American Chemical Society》2008,130(28):8886-8887
For tailoring solution-processable optoelectronic thin films, a rational strategy with amphiphilic molecular design is proposed. A donor-acceptor dyad consisting of an oligothiophene and C60, when modified with a hydrophilic wedge on one side and a paraffinic wedge on the other (1Amphi), forms over a wide temperature range a photoconducting smectic A liquid crystal having bicontinuous arrays of densely packed donor and acceptor units. In contrast, when modified with only paraffinic wedges (1Lipo), the dyad forms a smectic A liquid crystalline mesophase, which however is poorly conductive. As indicated by an absorption spectral feature along with a synchrotron radiation small-angle X-ray scattering profile, 1Lipo in the lamellar structure does not adopt a uniform head/tail orientation. Such defective donor and acceptor arrays likely contain a large number of trapping sites, leading to short-lived charge carriers, as observed by a flash photolysis time-resolved microwave conductivity study. 相似文献
64.
Sakurai T Shi K Sato H Tashiro K Osuka A Saeki A Seki S Tagawa S Sasaki S Masunaga H Osaka K Takata M Aida T 《Journal of the American Chemical Society》2008,130(42):13812-13813
A triply fused copper porphyrin dimer, when site-specifically modified on its periphery with hydrophobic and hydrophilic wedges (1C12/TEG), self-assembles into a columnar liquid crystalline (LC) mesophase over a wide-temperature range from -17 to 99 degrees C but gives rise to an amorphous solid when modified with only hydrophobic (1C12/C12) or hydrophilic wedges (1TEG/TEG). A LC film of 1C12/TEG displays at 16 degrees C a top-class one-dimensional electron mobility (0.27 cm2/V x s), as evaluated from its maximum flash-photolysis time-resolved microwave conductivity. 相似文献
65.
Liu Y Kuzuya A Sha R Guillaume J Wang R Canary JW Seeman NC 《Journal of the American Chemical Society》2008,130(33):10882-10883
We describe the synthesis of a hybrid DNA/organic macrocycle that is prepared by formation of an amide linkage across one full turn of DNA. Formation of a catenane proved that the linkage crossed a turn rather than running along the phosphodiester backbone contour. The product, a doubly tailed catenane, contains 5'- and 3'-termini that can be functionalized further or used to incorporate the catenane structure into other DNA assemblies. 相似文献
66.
Mechanistic study of a Pd/C-catalyzed reduction of aryl sulfonates using the Mg-MeOH-NH(4)OAc system
Mori A Mizusaki T Ikawa T Maegawa T Monguchi Y Sajiki H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(5):1432-1441
A method for the deoxygenation of phenolic hydroxy groups via aryl triflates or mesylates has been established by using a combination of Pd/C-Mg-MeOH. The addition of NH(4)OAc to the system markedly accelerated the reaction rate and expanded the scope of the reaction. Mechanistic studies suggested that a single-electron transfer process from the Pd(0) center to the benzene ring is involved in the reduction of aryl sulfonates and that NH(4)OAc works as a solubilization reagent of the Mg salt and as an accelerator of the electron transfer, thus enhancing the reaction process. Our method was also applicable to the regioselective deuteration of benzene derivatives with CH(3)OD as the solvent and deuterium source: the original hydroxy group could be efficiently replaced with a deuterium atom. 相似文献
67.
Ab initio HF and MP2 calculations on prototype model linkages of phosphorothioate DNA backbones illuminate the effects of phosphorothioation on electronic and structural properties of DNA backbone. The replacement of a bridging oxygen atom by sulfur in the phosphodiester linkage is energetically favored over that of replacement of a non-bridging oxygen atom. In phosphorothioate derivatives containing the P(OS)nb moiety, the non-bridging oxygen atom always bears a higher negative charge than the non-bridging sulfur. Additional calculations on protonated (neutral) adducts suggest that phosphorothioation of the phosphodiester linkage lowers its proton affinity. Moreover, protonation of the non-bridging oxygen atom at phosphorous is favored over the protonation of the non-bridging sulfur atom for linkages containing the P(OS)nb moiety. The ab initio calculated structural parameters are compared to the available crystallographic data of small phosphorothioate molecules and phosphorothioate oligodeoxynucleotides. These results have implications upon the biological activity of phosphorothioate DNA analogs. 相似文献
68.
Akinori Nishio Amane Mochizuki Jun‐Ichi Sugiyama Kazuhiko Takeuchi Michihiko Asai Koichiro Yonetake Mitsuru Ueda 《Journal of polymer science. Part A, Polymer chemistry》2000,38(11):2106-2114
An ordered polyurethane with a head‐to‐head (H‐H) or tail‐to‐tail (T‐T) content over 95% was prepared by polyaddition reaction of a nonsymmetric monomer, p‐isocyanatobenzyl isocyanate (1) with a symmetric monomer, ethylene glycol (2). The model reactions were studied in detail to demonstrate the feasibility of polymer formation. The polymerization was conducted in THF in the presence of triethylamine (TEA) at 0 °C by slow addition of a half amount of 2 to 1, followed by removing THF and then adding the rest of 2 in DMF at once at 30 °C in the presence of dibutyltin dilaurate (DBTL). The microstructure of the polymer obtained was investigated by 13C NMR spectroscopy, and it was found that the polymer had the expected structural regularity. The constitutional regularity of polymers influenced their thermal properties. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2106–2114, 2000 相似文献
69.
Masato Tazaki Toshihiko Hieda Hironori Maeda Shizuo Nagahama Akinori Jyo 《Heteroatom Chemistry》1998,9(3):281-287
Lithiated furans have been found to cleave the S–S bond of polymerization-resistant 1,2-dithiolanes to give the ring opened products in good yields. In the case of lithiated benzofuran, the excess reagent reacted with the normal product to give a mixture. Lithiated dihydrofuran and dihydropyran gave the corresponding ring-opened products that rearranged to spiro-1,3-dithianes during acidic workup. The reaction was applied to the selective synthesis of substrates for intramolecular Diels-Alder reactions. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:281–287, 1998 相似文献
70.
Taking advantage of a radical-based methodology, mild and chemoselective phosphination reactions of organic halide and alkyl imidazole-1-carbothioates have been developed. The mild reaction conditions allow labile functional groups to survive during the reaction. 相似文献