全文获取类型
收费全文 | 2771篇 |
免费 | 152篇 |
国内免费 | 19篇 |
专业分类
化学 | 2055篇 |
晶体学 | 44篇 |
力学 | 69篇 |
数学 | 175篇 |
物理学 | 599篇 |
出版年
2024年 | 4篇 |
2023年 | 28篇 |
2022年 | 72篇 |
2021年 | 76篇 |
2020年 | 63篇 |
2019年 | 77篇 |
2018年 | 58篇 |
2017年 | 48篇 |
2016年 | 100篇 |
2015年 | 104篇 |
2014年 | 122篇 |
2013年 | 182篇 |
2012年 | 221篇 |
2011年 | 277篇 |
2010年 | 147篇 |
2009年 | 148篇 |
2008年 | 199篇 |
2007年 | 164篇 |
2006年 | 163篇 |
2005年 | 151篇 |
2004年 | 110篇 |
2003年 | 87篇 |
2002年 | 87篇 |
2001年 | 39篇 |
2000年 | 47篇 |
1999年 | 26篇 |
1998年 | 22篇 |
1997年 | 15篇 |
1996年 | 15篇 |
1995年 | 15篇 |
1994年 | 14篇 |
1993年 | 11篇 |
1992年 | 8篇 |
1991年 | 12篇 |
1990年 | 12篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1982年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有2942条查询结果,搜索用时 7 毫秒
141.
142.
Electrophilic pincer-ligated Pt(II)-dications are efficient catalysts for the cycloisomerization of 1,6-dienes, initiated by alkene activation. The tridentate ligands inhibit beta-hydride elimination and thus enable cationic mechanisms that turnover by Pt(II) extrusion. PPP ligands lead to cyclopropane products, while PNP ligands provide cyclohexene products; mechanistic issues are also discussed. 相似文献
143.
Choi WJ Moon HR Kim HO Yoo BN Lee JA Shin DH Jeong LS 《The Journal of organic chemistry》2004,69(7):2634-2636
The preparative and stereoselective synthesis (45-50% overall yields) of the target compound 17 has been accomplished from D-ribose. The bulky protecting groups such as TBDPS and Trityl enforced the facial selectivity during Grignard reaction to give the tertiary beta-allylic alcohol 16 as the sole product, which was oxidatively rearranged to the key molecule 17 in excellent yield. 相似文献
144.
The thermoreversible fcc-bcc transition in concentrated block copolymer micellar solutions is shown to be driven by decreases in the aggregation number as the solvent penetrates the core, leading to a softer intermicelle potential. Small-angle neutron scattering measurements in a dilute solution are used to quantify the temperature-dependent micellar characteristics. The observed phase boundary is in excellent agreement with recent simulations of highly branched star polymers. 相似文献
145.
We propose the remote multiplexing of holograms with random patterns from a multimode fiber bundle used as the reference beams. The random pattern reference beam is characterized by the superposition and concatenation of propagation modes of multimode fiber and free space. For angle, shift, and wavelength remote multiplexing we compare two methods of laser coupling to the fiber bundle, i.e., direct coupling and lens coupling. A theoretical discussion that uses mode orthogonality is provided to describe multiplexing characteristics, and the theory is verified by experimental results. These remote-multiplexing methods can be applied to general multimode waveguide arrays for construction of compact and integrated optical systems in which multiplexing can be controlled remotely. 相似文献
146.
Lee KJ Kim HA Kim PH Lee HS Ma KR Park JH Kim DJ Hahn JH 《Experimental & molecular medicine》2004,36(6):534-544
During chronic inflammatory response, mono- cytes/macrophages produce 92-kDa matrix metalloproteinase-9 (MMP-9), which may contribute to their extravasation, migration and tissue remodeling. Activation of peroxisome proliferator- activated factor receptor-g (PPAR-g) has been shown to inhibit MMP-9 activity. To evaluate whether ox-LDL, a PPAR-g activator, inhibits PMA-induced MMP-9 expression and activity, and if so, whether CD36 and PPAR-g are involved in this process, we investigated the effect of ox-LDL on MMP-9 expression and activity in PMA-activated human monocytic cell line U937. PMA-induced MMP-9 expression and activity were suppressed by the treatment with ox-LDL (50 mg/ml) or PPAR-g activators such as troglitazone (5 mM), ciglitazone (5 mM), and 15d- PGJ2 (1 mM) for 24 h. This ox-LDL or PPAR-g activator-mediated inhibition of MMP-9 activity was diminished by the pre-treatment of cells with a blocking antibody to CD36, or PGF2a (0.3 mM), which is a PPAR-g inhibitor, as well as overexpression of a dominant-negative form of CD36. Taken together, these results suggest that ox-LDL suppresses PMA-induced MMP-9 expression and activity through CD36-mediated activation of PPAR-g. 相似文献
147.
The objective of this paper is to develop a nondestructive method for estimating the fracture toughness (K(IC)) of CrMoV steels used as the rotor material of steam turbines in power plants. To achieve this objective, a number of CrMoV steel samples were heat-treated, and the fracture appearance transition temperature (FATT) was determined as a function of aging time. Nonlinear ultrasonics was employed as the theoretical basis to explain the harmonic generation in a damaged material, and the nonlinearity parameter of the second harmonic wave was the experimental measure used to be correlated to the fracture toughness of the rotor steel. The nondestructive procedure for estimating the K(IC) consists of two steps. First, the correlations between the nonlinearity parameter and the FATT are sought. The FATT values are then used to estimate K(IC) using the K(IC) versus excess temperature (i.e., T-FATT) correlation that is available in the literature for CrMoV rotor steel. 相似文献
148.
Four mononuclear metallomacrocycles with identical cavities but different transition metals (Os(VI), Pd(II), Pt(II), and Re(I)) were prepared. With these metallomacrocycles, the corresponding rotaxanes 2-Os, 2-Pd, 2-Pt, and 2-Re were self-assembled by hydrogen-bonding interactions. The kinetic stabilities of the rotaxanes were determined quantitatively and compared with each other by (1)H NMR spectroscopic techniques, including two-dimensional exchange spectroscopy (2D-EXSY) experiments. The activation free energies (DeltaG( not equal )) for the exchange between the rotaxanes 2-Os, 2-Pd and 2-Pt and their free components were determined to be 15.5, 16.0, and 16.4 kcal mol(-1), respectively. These magnitudes imply that the rotaxanes 2-Os, 2-Pd and 2-Pt are kinetically labile at room temperature and exist only as equilibrium mixtures with free components in solution. In contrast, the rotaxane 2-Re is kinetically stable enough to be isolated in pure form by silica gel chromatography under ordinary laboratory conditions. However, at higher temperatures (>60 degrees C) 2-Re was slowly disassembled into its components until the equilibrium was established. The rate constants were measured at three different temperatures, and the Eyring plot yielded the activation enthalpy DeltaH(not equal)=35 kcal mol(-1) and the activation entropy DeltaS(not equal)=27 eu for the disassembly of the rotaxane 2-Re in Cl(2)CDCDCl(2). These thermodynamic parameters gave the activation free energy DeltaG(not equal)(off)=27.1 kcal mol(-1) at 25 degrees C. Consequently, 2-Re is one example of a novel metallomacrocycle-based rotaxane that contains a coordination bond with enough strength to allow both for isolation in pure form around room temperature and for self-assembly at higher temperatures. 相似文献
149.
Song HY Joo JM Kang JW Kim DS Jung CK Kwak HS Park JH Lee E Hong CY Jeong S Jeon K Park JH 《The Journal of organic chemistry》2003,68(21):8080-8087
The proposed structure of lasonolide A was synthesized employing radical cyclization reactions of beta-alkoxyacrylates for preparation of the tetrahydropyranyl units A and B, but the spectroscopic data did not match those of the natural product. Both enantiomers of a revised structure featuring 17E,25Z double bonds were synthesized, and the (-)-isomer was found to be the biologically active enantiomer. 相似文献