全文获取类型
收费全文 | 1641篇 |
免费 | 73篇 |
国内免费 | 9篇 |
专业分类
化学 | 1366篇 |
晶体学 | 11篇 |
力学 | 15篇 |
数学 | 82篇 |
物理学 | 249篇 |
出版年
2024年 | 3篇 |
2023年 | 22篇 |
2022年 | 18篇 |
2021年 | 20篇 |
2020年 | 34篇 |
2019年 | 46篇 |
2018年 | 41篇 |
2017年 | 16篇 |
2016年 | 34篇 |
2015年 | 57篇 |
2014年 | 55篇 |
2013年 | 89篇 |
2012年 | 109篇 |
2011年 | 107篇 |
2010年 | 72篇 |
2009年 | 67篇 |
2008年 | 119篇 |
2007年 | 85篇 |
2006年 | 121篇 |
2005年 | 121篇 |
2004年 | 108篇 |
2003年 | 75篇 |
2002年 | 63篇 |
2001年 | 26篇 |
2000年 | 24篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 13篇 |
1984年 | 9篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1980年 | 9篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1967年 | 2篇 |
排序方式: 共有1723条查询结果,搜索用时 15 毫秒
41.
Hiroki FurutaToyohisa Takase Hisafumi HayashiRyoji Noyori Yuji Mori 《Tetrahedron》2003,59(49):9767-9777
An efficient method has been developed for the synthesis of trans-fused tetrahydropyrans with angular methyl groups adjacent to the ring oxygen. The procedure involves the coupling reaction of a sulfonyl-stabilized oxiranyl anion with an appropriate triflate followed by 6-endo cyclization, and is effective for the construction of 6/6- and 6/7/6-cyclic ether ring systems with sterically congested 1,3-diaxial methyl groups. 相似文献
42.
Hiroyuki?OhshimaEmail author Hiroko?Sato Hiroki?Matsubara Atsushi?Hyono Masayoshi?Okubo 《Colloid and polymer science》2004,282(10):1174-1178
A theory of adsorption kinetics with time delay [Ohshima et al. (1992) Colloid Polym. Sci. 270:707] is developed and applied to the surface tension of a polymer solution. It is found that the general appearance of the overshoot and oscillation in the time course of the surface tension of aqueous gelatin solution observed by Sato and Ueberreiter [(1979) Makromol. Chem. 180:829, 1107; (1979) Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 20:907) can be explained by the present theory. 相似文献
43.
A series of samples with the composition Ca(1)(-)(x)Na(2)(x)Al(2)B(2)O(7) (0 < x < or = 1) was investigated and a hexagonal structure with unusually large range of homogeneity (at least from x = 0.01 to 0.95) was revealed. The hexagonal phase consists of [Al(2)B(2)O(7)](infinity)(2)(-) lamellae stacked along the c axis, as in CaAl(2)B(2)O(7) and Na(2)Al(2)B(2)O(7). Nevertheless, the configuration and stacking sequence of the [Al(2)B(2)O(7)](infinity)(2)(-) lamellae are different in these three structures. In the hexagonal structure of Ca(1)(-)(x)()Na(2)(x)()Al(2)B(2)O(7), Ca and half Na cations (Na1) statistically occupy the same crystallographic site which is located between the [Al(2)B(2)O(7)](infinity)(2)(-) lamellae, the other half Na cations (Na2) distribute in the planes bisecting the [Al(2)B(2)O(7)](infinity)(2)(-) lamellae. Depending on the composition, the site occupation factor of Na2 site can vary in the same range as x, leading to a tunable density of Na(+) vacancies in the structure. The AlO(4) tetrahedra and BO(3) triangles in the structure tilt in appropriate ways to improve the bond valence sum of Na2 cations which are not sufficiently bonded to the anions. 相似文献
44.
Paul Grocki Mark Woollam Luqi Wang Shengzhi Liu Maitri Kalra Amanda P. Siegel Bai-Yan Li Hiroki Yokota Mangilal Agarwal 《Molecules (Basel, Switzerland)》2022,27(13)
Volatile organic compounds (VOCs) in urine are potential biomarkers of breast cancer. Previously, our group has investigated breast cancer through analysis of VOCs in mouse urine and identified a panel of VOCs with the ability to monitor tumor progression. However, an unanswered question is whether VOCs can be exploited similarly to monitor the efficacy of antitumor treatments over time. Herein, subsets of tumor-bearing mice were treated with pitavastatin at high (8 mg/kg) and low (4 mg/kg) concentrations, and urine was analyzed through solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS). Previous investigations using X-ray and micro-CT analysis indicated pitavastatin administered at 8 mg/kg had a protective effect against mammary tumors, whereas 4 mg/kg treatments did not inhibit tumor-induced damage. VOCs from mice treated with pitavastatin were compared to the previously analyzed healthy controls and tumor-bearing mice using chemometric analyses, which revealed that mice treated with pitavastatin at high concentrations were significantly different than tumor-bearing untreated mice in the direction of healthy controls. Mice treated with low concentrations demonstrated significant differences relative to healthy controls and were reflective of tumor-bearing untreated mice. These results show that urinary VOCs can accurately and noninvasively predict the efficacy of pitavastatin treatments over time. 相似文献
45.
Ionic liquids (ILs) are salts with an extremely low melting point. Substantial efforts have been made to address their low melting point from the enthalpic standpoint (i.e. interionic interactions). However, this question is still open. In this study, we report our findings that entropic (large fusion entropy), rather than enthalpic, contributions are primarily responsible for lowering the melting point in many cases, based on a large thermodynamic dataset. We have established a computational protocol using molecular dynamics simulations to decompose fusion entropy into kinetic (translational, rotational, and intramolecular vibrational) and structural (conformational and configurational) terms and successfully applied this approach for two representatives of ILs and NaCl. It is revealed that large structural contribution, particularly configurational entropy in the liquid state, plays a deterministic role in the large fusion entropy and consequently the low melting point of the ILs.Large structural entropy makes salts liquid at room temperature. 相似文献
46.
Shigekazu Ito Hiroki Sugiyama Masaaki Yoshifuji 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):785-788
1-(2,4,6-Tri-tert-butylphenyl)-2-phosphaethyne (1) was allowed to react with 0.5 equiv of an alkyllithium and subsequently with an alcohol to afford a bulky 1,3-diphosphacyclobutene, and its structure and coordination properties on transition metals were investigated. On the other hand, 1 was allowed to react with an alkyllithium and iodomethane to form a stable biradical, 1,3-diphosphacyclobutane-2,4-diyl. 相似文献
47.
Precipitation temperature-total polymer concentration diagrams for toluene solutions of two styrene-acrylonitrile copolymers different in chemical composition and their mixtures were determined and then triangular phase diagrams of this system were constructed from these diagrams. It is speculated from the triangular phase diagrams and experimentally shown that the copolymer may be effectively fractionated by chemical composition in this system. 相似文献
48.
49.
Two kinds of polyelectrolytes containing maleic acid component (MA copolymers), i.e., poly(styrene-alt-maleic acid) (PSMA) and poly(vinyl methyl ether-alt-maleic acid) (PVMEMA), were investigated on their polymer chain dimensional changes in solution, and also in gel phase for the latter, as a function of the polymer charge density or pH of the (immersing) solution. Being different from common poly(carboxylic acid)s such as poly(acrylic acid), both of the MA copolymers showed maximum in the reduced viscosity or the gel size with increasing the charge density or the solution pH. The maximum in the reduced viscosity was much more significant for PSMA than PVMEMA. To see if intramolecular hydrogen bond between a pair of dissociated and undissociated carboxyl groups in an MA residue contributes to the emergence of the peak or not, similar measurements were performed also in the presence of concentrated urea (5 M). Almost the same values were obtained up to the peak position for the reduced viscosity and the gel swelling degree with increasing pH of the (immersing) solutions, which strongly suggested that the supposed effect is negligible, if any. All the results including those for PVMEMA system were interpreted in terms of the ionomer-like conformational change (ion cluster formation) of polyelectrolytes that has been often observed when the polymer charges are in rather less polar circumstances. 相似文献
50.
Tohru TakeiTakumi Ohki Yosuke HaradaNaoto Kumagai Hiroki FukumotoTake-aki Koizumi Akihiro MaedaTakahiro Kojima Yoshihisa SeiKohei Shiramizu Masahiro AbeMasashi Oota Takakazu Yamamoto 《Tetrahedron letters》2012,53(44):5907-5910
Dibromopyridines or dibromopyridone with -(CH2)m-SO3Na group(s) has been prepared via the reactions of the corresponding dibromopyridines with -OH and -NH2 groups with sultone. These compounds were converted into polymers with the -(CH2)m-SO3H groups via organometallic polycondensation. The polymer showed proton conducting properties and high stability toward oxidation. 相似文献