全文获取类型
收费全文 | 3787篇 |
免费 | 147篇 |
国内免费 | 11篇 |
专业分类
化学 | 2836篇 |
晶体学 | 53篇 |
力学 | 32篇 |
数学 | 168篇 |
物理学 | 856篇 |
出版年
2023年 | 22篇 |
2022年 | 28篇 |
2021年 | 40篇 |
2020年 | 78篇 |
2019年 | 63篇 |
2018年 | 59篇 |
2017年 | 40篇 |
2016年 | 104篇 |
2015年 | 75篇 |
2014年 | 104篇 |
2013年 | 170篇 |
2012年 | 250篇 |
2011年 | 310篇 |
2010年 | 153篇 |
2009年 | 145篇 |
2008年 | 246篇 |
2007年 | 243篇 |
2006年 | 246篇 |
2005年 | 237篇 |
2004年 | 200篇 |
2003年 | 163篇 |
2002年 | 153篇 |
2001年 | 66篇 |
2000年 | 56篇 |
1999年 | 39篇 |
1998年 | 41篇 |
1997年 | 39篇 |
1996年 | 40篇 |
1995年 | 23篇 |
1994年 | 30篇 |
1993年 | 20篇 |
1992年 | 35篇 |
1991年 | 19篇 |
1990年 | 19篇 |
1989年 | 21篇 |
1988年 | 18篇 |
1987年 | 15篇 |
1986年 | 11篇 |
1985年 | 22篇 |
1984年 | 34篇 |
1983年 | 25篇 |
1982年 | 28篇 |
1981年 | 17篇 |
1980年 | 35篇 |
1979年 | 24篇 |
1978年 | 24篇 |
1977年 | 23篇 |
1976年 | 16篇 |
1975年 | 18篇 |
1973年 | 9篇 |
排序方式: 共有3945条查询结果,搜索用时 15 毫秒
51.
Satoshi Ito Kazuya Koizumi Katsuhiko Fukuda Naohiro Kameta Tsukasa Ikeda Toru Oba Kazuhisa Hiratani 《Tetrahedron letters》2006,47(48):8563-8566
A new series of BINOL-based macrocycles with two phenolic protons have been synthesized via oxidative coupling reaction using CuCl(OH)-TMEDA. 相似文献
52.
Chihiro Kachi‐Terajima Dr. Takamasa Akatsuka Masa‐aki Kohbara Satoshi Takamizawa Dr. 《化学:亚洲杂志》2007,2(1):40-50
The crystalline one‐dimensional compound, [RhII2(bza)4(pyz)]n ( 1 ) (bza=benzoate, pyz=pyrazine) demonstrates gas adsorbency for N2, NO, NO2, and SO2. These gas‐inclusion crystal structures were characterized by single‐crystal X‐ray crystallography as 1 ?1.5 N2 (298 K), 1 ?2.5 N2 (90 K), and 1 ?1.95 NO (90 K) under forcible adsorption conditions and 1 ?2 NO2 (90 K) and 1 ?3 SO2 (90 K) under ambient pressure. Crystal‐phase transition to the P space group that correlates with gas adsorption was observed under N2, NO, and SO2 conditions. The C2/c space group was observed under NO2 conditions without phase transition. All adsorbed gases were stabilized by the host lattice. In the N2, NO, and SO2 inclusion crystals at 90 K, short interatomic distances within van der Waals contacts were found among the neighboring guest molecules along the channel. The adsorbed NO molecules generated the trans‐NO???NO associated dimer with short intermolecular contacts but without the conventional chemical bond. The magnetic susceptibility of the NO inclusion crystal indicated antiferromagnetic interaction between the NO molecules and paramagnetism arising from the NO monomer. The NO2 inclusion crystal structure revealed that the gas molecules were adsorbed in the crystal in dimeric form, N2O4. 相似文献
53.
Stability of porphyrin-calix[4]arene complexes analyzed by electrospray ionization mass spectrometry
Arai S Ishihara S Takeoka S Ohkawa H Shibue T Nishide H 《Rapid communications in mass spectrometry : RCM》2004,18(18):2065-2068
The stability of some porphyrin-calix[4]arene sodium-ion complexes were determined by a collision-activated decomposition (CAD) method utilizing electrospray ionization mass spectrometry (ESI-MS). Comparing the values of E(1/2), the collision energy at which the relative intensity of the complex ion is 0.5, we found that the porphyrin-calix[4]arene complex with the higher value of E(1/2) corresponded to that with the larger association constant (Kass), as measured by 1H-NMR in CDCl3. Both our ESI-MS and NMR studies proved that the number of hydrogen bonds and the rigidity of the calix[4]arene stabilized the complex. The ESI-MS technique could be successful in screening the binding affinity in host-guest systems with a small amount of sample. 相似文献
54.
The title compound shows dual fluorescence depending on polarity of the solvent used. The fluorescence in the nonpolar solvent, cyclohexane, has a maximuni at 370 nm, while the fluorescence in the polar solvent, methanol, has a maximum at 400nm. The short and long wavelength fluorescences were assigned to the syn and anti conformers, respectively. From these observations one is allowed to conclude that a novel solvent dipole-induced rotational isomerism takes place in the excited singlet state. 相似文献
55.
Tatsuro Ouchi Hirotoshi Fujie Satoshi Jokei Yoshiomi Sakamoto Hidenori Chikashita Takeshi Inoi Otto Vogl 《Journal of polymer science. Part A, Polymer chemistry》1986,24(9):2059-2074
Acryloyl-type polymer fixing 1-β-carbonylethyl-5-fluorouracil residues through D -glucofuranoses via ester bonds was synthesized by means of polymerization of the corresponding monomer and polymer reaction. In order to provide the water-soluble objective polymer, the copolymerization of the acryloyl-type monomer with acrylamide was carried out. The extent of release of 5-FU residues from the copolymer was investigated in the enzyme or nonenzyme system in vitro. Furthermore, the antitumor activities of the water-insoluble homopolymer and water-soluble copolymer obtained were tested in vivo. 相似文献
56.
T Nishi F Saito H Nagahori M Kataoka Y Morisawa Y Yabe M Sakurai S Higashida M Shoji Y Matsushita 《Chemical & pharmaceutical bulletin》1990,38(1):103-109
Syntheses and biological activities of dipeptide renin inhibitors that contain statine analogues are described. The key steps of the synthetic approach to dipeptide renin inhibitors are the asymmetric synthesis of 2(R)-substituted-3-aminocarbonylpropionic acids and the diastereoselective syntheses of (3S,4S)-statine analogues. These inhibitors (2,14-40) inhibited human renin in the 3-140 nM range. Inhibitor ES 6864 (2) was found to be a highly potent inhibitor of human renin (IC50: 4.6 x 10(-9) M) and showed high enzyme specificity. Oral administration of ES 6864 at 3 mg/kg to conscious, sodium-depleted marmosets inhibited plasma renin activity (PRA) more than 80% after 1 h. 相似文献
57.
Bromomagnesium ureide-carbon dioxide adducts, models of the carboxylated biotin complex, undergo caboxylation of a variety of carbonyl compounds in good yield. 相似文献
58.
Chemiluminescence from the reaction of calcium and aluminum with various hydrogen containing compounds in a flowing gas system and in a heat pipe oven are described. Red chemiluminescence of CaH was observed in the reaction of calcium, and weak chemiluminescence of AlH was seen in the reaction of aluminum with formaldehyde (H2CO). It is proposed that a reaction between metal atoms and formaldehyde may be used as a source of diatomic metallic hydrides. 相似文献
59.
Keivan Esfarjani Yuichi Hashi Satoshi Itoh Sigeo Ihara Yoshiyuki Kawazoe 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,41(1):73-76
To study the thermodynamic and mechanical stability of toroidal isomers of C 240, we use a semi-empirical tight-binding theory and calculate their electronic structure, cohesive energy and vibrational spectra within the harmonic approximation. From these, we deduce their free energy at temperatures up to 1500K. The results are also compared to the isomer with icosahedral symmetry. Finally, we discuss within this approach, their stability and abundance. 相似文献
60.
Shimazaki Y Tashiro M Motoyama T Iwatsuki S Yajima T Nakabayashi Y Naruta Y Yamauchi O 《Inorganic chemistry》2005,44(17):6044-6051
Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and 1H NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pKa value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4. 相似文献