全文获取类型
收费全文 | 638篇 |
免费 | 18篇 |
国内免费 | 3篇 |
专业分类
化学 | 450篇 |
晶体学 | 10篇 |
力学 | 5篇 |
数学 | 72篇 |
物理学 | 122篇 |
出版年
2022年 | 5篇 |
2021年 | 9篇 |
2020年 | 11篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2017年 | 6篇 |
2016年 | 9篇 |
2015年 | 15篇 |
2014年 | 12篇 |
2013年 | 22篇 |
2012年 | 42篇 |
2011年 | 40篇 |
2010年 | 22篇 |
2009年 | 21篇 |
2008年 | 35篇 |
2007年 | 27篇 |
2006年 | 28篇 |
2005年 | 27篇 |
2004年 | 31篇 |
2003年 | 23篇 |
2002年 | 25篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 11篇 |
1996年 | 7篇 |
1995年 | 7篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 10篇 |
1991年 | 10篇 |
1990年 | 12篇 |
1989年 | 14篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 13篇 |
1984年 | 9篇 |
1983年 | 10篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1972年 | 3篇 |
1968年 | 5篇 |
1965年 | 4篇 |
排序方式: 共有659条查询结果,搜索用时 0 毫秒
31.
The partial molar free energy, enthalpy, and entropy of oxygen in niobium oxides with ratios from 2.47 to 2.50 were measured with a galvanic cell in the temperature range from 1084 to 1325 K. The partial molar enthalpies of oxygen of the Nb2O5?x and V phases were observed to be nearly independent of composition, indicating the presence of only weak interactions between defects. The value of the slope for the plots of log x in Nb2O5?x against log PO2 was observed to be which is interpreted in terms of a defect structure involving both singly ionized and doubly ionized oxygen vacancies. The previously proposed phase diagram in the vicinity of Nb2O5?x was confirmed by the present emf measurements. 相似文献
32.
Yohei Saito Atsushi Mizokami Kouji Izumi Renato Naito Masuo Goto Kyoko Nakagawa-Goto 《Molecules (Basel, Switzerland)》2021,26(9)
α-Trifluoromethyl chalcones were prepared and evaluated for their antiproliferative activities against androgen-independent prostate cancer cell lines as well as five additional types of human tumor cell lines. The most potent chalcone 5 showed superior antitumor activity in vivo with both oral and intraperitoneal administration at 3 mg/kg. Cell-based mechanism of action studies demonstrated that 5 induced cell accumulation at sub-G1 and G2/M phases without interfering with microtubule polymerization. Furthermore, several cancer cell growth-related proteins were identified by using chalcone 5 as a bait for the affinity purification of binding proteins. 相似文献
33.
Allylation reaction of electron-deficient imines with allylic alcohol derivatives in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide was studied. The reversibility of allylation was observed in the reaction of glyoxylic oxime ether having camphorsultam. As the important effect of water on regioselectivity, the gamma-adducts were kinetically formed from monosubstituted allylic reagents in the presence of water. The selective formation of thermodynamically stable alpha-adducts was observed in anhydrous THF. In contrast, the allylation of N-sulfonylimine gave the gamma-adducts with high regioselectivities even under anhydrous reaction conditions. 相似文献
34.
Miftakhul Huda Keigo Minamisawa Takamasa Tsukamoto Makoto Tanabe Kimihisa Yamamoto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(4):1014-1018
Subnanocatalysts (SNCs) containing various noble metals (Cu, Ru, Rh, Pd, or Pt) with sizes of approximately 1 nm were synthesized using dendritic poly(phenylazomethine)s as a macromolecular template. These materials exhibit high catalytic performance during toluene oxidation without the use of harmful solvents or explosive oxidants, resulting in the formation of valuable organic products, including benzoic acid as the major product. In particular, Pt19 SNC with a narrow particle size distribution exhibits extraordinary catalytic activity, with a turnover frequency of 3238 atom?1 h?1, which is 1700 times greater than that obtained by commercial Pt/C catalysts. 相似文献
35.
36.
Daisuke Asai Tadashi Fukuda Kazunori Morokuma Daiki Funamoto Yuko Yamaguchi Takeshi Mori Yoshiki Katayama Keigo Shibayama Hideki Nakashima 《Macromolecular bioscience》2019,19(10)
Vaccines typically contain an antigen, delivery system (vehicle), and adjuvant, all of which contribute to inducing a potent immune response. Consequently, design of new vaccines is difficult, because the contributions and interactions of these components are difficult to distinguish. Here, it is aimed to develop an easy‐to‐use, non‐immunogenic, injectable depot system for sustained antigen release that will be suitable for assessing the efficacy of prolonged antigen exposure per se for inducing an immune response. This should mimic real‐life infections. Recombinant elastin‐like polypeptides with periodic cysteine residues (cELPs) are selected, which reportedly show little or no immunogenicity, as carriers and tetanus toxoid (Ttd) as an antigen. After subcutaneous injection of the mixture, cELP rapidly forms a disulfide cross‐linked hydrogel in situ, within which Ttd is physically incorporated, affording a biodegradable antigen depot. A series of Ttd‐containing hydrogels is examined. A single injection induces high levels of tetanus antibody with high avidity for at least 20 weeks in mice. The chain length of cELP proves critical, whereas differences in hydrophobicity has little effect, although hydrophilic cELPs are more rapidly biodegraded. This system's ability to distinguish the contribution of sustained antigen release to antibody induction should be helpful for rational design of next‐generation vaccines. 相似文献
37.
The total synthesis of 6,7-dideoxysqualestatin H5 (3) has been completed by a concise approach that features the stereoselective intramolecular vinylogous aldol reaction of the furoic ester 25a to give 30 or its trimethylsilyl ether derivative 34, which possess the requisite absolute stereochemistry at C(3)-C(5) of 3. Compound 34 was reduced to the saturated bislactone 39, and the C(1) side chain subunit 47 was introduced leading to a mixture of the hemiacetals 48 and the corresponding ketone 49. When this mixture was stirred with methanolic acid, transketalization occurred to give a mixture of 50 and the spirocyclic methyl acetals 51a,b. Oxidation of the primary alcohol group in 50 followed by saponification of the two remaining ester groups gave 3. The longest linear sequence in the synthesis commences with commercially available erythronolactone (26) and requires 17 chemical steps with only 10 isolated intermediates. 相似文献
38.
Stereoselective polymerization of racemic lactide (rac-LA) was examined using Al-achiral ligand complexes. By introduction of substituents in aromatic rings of Schiff base ligands, a higher selectivity was obtained without any chiral auxiliaries in the catalyst via a chain-end control mechanism. The T(m) values (T(m) 170-192 degrees C) were comparable to or higher than that of homochiral polymer, poly(L-LA) (T(m) 162 degrees C), and a thermally more stable polylactide than poly(L-LA) was prepared from rac-LA. 相似文献
39.
Kondo M Irie Y Shimizu Y Miyazawa M Kawaguchi H Nakamura A Naito T Maeda K Uchida F 《Inorganic chemistry》2004,43(20):6139-6141
Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1. 相似文献
40.
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