全文获取类型
收费全文 | 5607篇 |
免费 | 160篇 |
国内免费 | 31篇 |
专业分类
化学 | 4411篇 |
晶体学 | 49篇 |
力学 | 76篇 |
数学 | 347篇 |
物理学 | 915篇 |
出版年
2023年 | 24篇 |
2022年 | 47篇 |
2021年 | 57篇 |
2020年 | 65篇 |
2019年 | 95篇 |
2018年 | 54篇 |
2017年 | 47篇 |
2016年 | 111篇 |
2015年 | 97篇 |
2014年 | 133篇 |
2013年 | 284篇 |
2012年 | 314篇 |
2011年 | 383篇 |
2010年 | 208篇 |
2009年 | 238篇 |
2008年 | 381篇 |
2007年 | 376篇 |
2006年 | 415篇 |
2005年 | 362篇 |
2004年 | 335篇 |
2003年 | 273篇 |
2002年 | 272篇 |
2001年 | 89篇 |
2000年 | 70篇 |
1999年 | 60篇 |
1998年 | 70篇 |
1997年 | 69篇 |
1996年 | 67篇 |
1995年 | 54篇 |
1994年 | 35篇 |
1993年 | 42篇 |
1992年 | 29篇 |
1991年 | 36篇 |
1990年 | 18篇 |
1989年 | 19篇 |
1988年 | 26篇 |
1987年 | 30篇 |
1986年 | 45篇 |
1985年 | 58篇 |
1984年 | 47篇 |
1983年 | 23篇 |
1982年 | 52篇 |
1981年 | 53篇 |
1980年 | 45篇 |
1979年 | 38篇 |
1978年 | 31篇 |
1977年 | 26篇 |
1976年 | 23篇 |
1974年 | 15篇 |
1973年 | 18篇 |
排序方式: 共有5798条查询结果,搜索用时 15 毫秒
41.
A palladium-fibroin complex (Pd/Fib) was prepared by soaking silk-fibroin in MeOH solution of Pd(OAc)2 for 2 days (under Ar atmosphere)—4 days (under air). Pd(OAc)2 was gradually absorbed by fibroin and the rapid reduction of fibroin conjugated Pd(OAc)2 proceeded with MeOH as a reductant at room temperature to be the Pd(0) complex. Pd/Fib catalyzed chemoselective hydrogenation of acetylenes, olefins and azides in the presence of aromatic ketones and aldehydes, halides, N-Cbz protective groups and benzyl esters which are readily hydrogenated using Pd/C or Pd/C(en) as a catalyst. 相似文献
42.
Takashi Kagayama 《Tetrahedron letters》2005,46(21):3687-3689
A new route to α-hydroxy-γ-butyrolactones through three-component radical coupling of 1,3-dioxoranes, acrylates, and molecular oxygen using N-hydroxyphthalimide (NHPI) as a key catalyst has been developed. For example, the addition of 1,3-dioxarane to methyl acrylate under dioxygen by NHPI followed by catalytic hydrogenation of the resulting adduct on Pd/C afforded α-hydroxy-γ-butyrolactone in good yield. This method provides a facile approach to α-hydroxy-γ-butyrolactones, which are difficult to synthesize by conventional methods. 相似文献
43.
The three-dimensional reference interaction site model (3D-RISM) theory is applied to the analysis of hydration effects on the partial molar volume of proteins. For the native structure of some proteins, the partial molar volume is decomposed into geometric and hydration contributions using the 3D-RISM theory combined with the geometric volume calculation. The hydration contributions are correlated with the surface properties of the protein. The thermal volume, which is the volume of voids around the protein induced by the thermal fluctuation of water molecules, is directly proportional to the accessible surface area of the protein. The interaction volume, which is the contribution of electrostatic interactions between the protein and water molecules, is apparently governed by the charged atomic groups on the protein surface. The polar atomic groups do not make any contribution to the interaction volume. The volume differences between low- and high-pressure structures of lysozyme are also analyzed by the present method. 相似文献
44.
Dehydrroxy-trans-resorcylide () was synthesized by efficient intramolecular alkylation of the protected cyanohydrin. The butadiene telomer obtained by the palladium catalyzed reaction of butadiene with acetic acid was used as a suitable block of the carbocycle. 相似文献
45.
A laser-induced fluorescence microscopic system based on optical parametric oscillation has been constructed as a tunable detector for microchip analysis. The detection limit of sulforhodamine B (Ex. 520 nm, Em. 570 nm) was 0.2 mol, which was approximately eight orders of magnitude better than with a conventional fluorophotometer. The system was applied to the determination of fluorescence-labeled DNA (Ex. 494 nm, Em. 519 nm) in a microchannel and the detection limit reached a single molecule. These results showed the feasibility of this system as a highly sensitive and tunable fluorescence detector for microchip analysis. 相似文献
46.
A method to analyze human plasma proteins without fractionation, directly applying a plasma-matrix mixture on the target plate of a matrix-assisted laser desorption/ionization-time of flight-mass spectrometer (MALDI-TOF-MS), has been described. Peaks of ionized plasma proteins could not be detected applying a mixture of an undiluted plasma sample and a matrix solution, but they appeared when the plasma was diluted before mixing with the matrix. Tenfold diluted plasma provided well-resolved protein peaks in the m/z range from 4000 to 30,000. The addition of a simple post-crystallization washing procedure performed on the target plate further improved the quality of mass spectra. We numbered 58 peaks in the range of 4-160 kDa and 32 out of which were assigned to the plasma protein species which have been reported. Especially high sensitivity and resolution were obtained in the region < 30 kDa, where multiple isoforms of apolipoprotein A-I, apolipoprotein A-II, apolipoprotein C-I, apolipoprotein C-II, apolipoprotein C-III, and transthyretin could be assigned. Various post-translational modifications are involved in the isoforms, e.g., proteolytic cleavage, glycosylation and chemical modifications. This method will become complementary with the present electrophoretic techniques, especially for the analysis of low-molecular-mass proteins. 相似文献
47.
Kawai H Katoono R Fujiwara K Tsuji T Suzuki T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(3):815-824
The molecular recognition of catecholamines by hydrindacene-based receptors 1 and 2, as well as the durene-based receptor 3, and the guest-induced conformational changes are reported. These receptors selectively bind adrenaline and dopamine salts through the guests' ammonium group and 3-hydroxyl group on the aromatic ring. In the case of adrenaline, an additional hydrogen bond with a benzylic hydroxyl group is formed. In 2 % CD3CN/CDCl3, the association constants are of the order of 10(4) M(-1), which is much larger than with guests without the 3-hydroxyl groups (10(3) M(-1)). The two amide groups of receptor 1 can rotate freely around the C(aromatic)--C(amide) bond, whereas the tert-amide in 2 changes between two stable conformations at a slow enough rate to allow detection by (1)H NMR spectroscopy. In the absence of a guest molecule, the syn-conformer is less stable than the anti-conformer. On complex formation with adrenaline, the syn-conformer becomes dominant due to an intramolecular dipole-reversal effect in addition to multipoint hydrogen bonding. 相似文献
48.
The simple removal of excess of co-extracted reagent in the solvent extraction of metal complex anions with a quaternary ammonium salt greatly improves the determination of iron(II) with pyrogallol red and zephiramine. The method with pyrogallol red is suitable for the determination of trace amounts of iron in natural waters. The apparent molar absorptivities of the iron(II) complex in chloroform are 7.5×104 and 10.3×104 1 mol-1 cm-1 at 560 and 298 nm, respectively. A large excess of reagent can be added, and the ternary complex can be completely extracted over the pH range 8.5–10. Masking agents allow most interferences to be suppressed. The method is suitable for the analysis of potable, river and sea waters. 相似文献
49.
The classicalR-matrix structure for then-particle Calogero-Moser models with (type IV) elliptic potentials is investigated. We show there is no momentum independentR-matrix (without spectral parameter) whenn 4. The assumption of momentum independence is sufficient to reproduce the dynamicalR-matrices of Avan and Talon for the type I, II, III degenerations of the elliptic potential. The inclusion of a spectral parameter enables us to findR-matrices for the general elliptic potential. 相似文献
50.
Staudinger/aza-Wittig reaction of 6,6,6-trifluoro-5-oxohexanoyl azide with PPh(3) or PBu(3) was examined. A reactive intermediate acyl imine 1 was trapped by methanol. Without nucleophile, isomerized enamide form 3 was obtained. N-Iodobenzoylation and N-haloalkylation of 3 and following radical cyclization via the 5-exo or 6-exo mode gave benzoindolizidinone, indolizidinone, and quinolizidinone derivatives 10-14, which have a trifluoromethyl group at the bridgehead position adjacent to nitrogen. Although LiAlH(4) reduction of 10 and 11 gave a mixture of saturated benzoindolizidine 15 and amino alcohol 16, reduction with BH(3)/THF selectively gave the desired 15 and indolizidine 17 from 13. 相似文献