全文获取类型
收费全文 | 5556篇 |
免费 | 191篇 |
国内免费 | 30篇 |
专业分类
化学 | 4384篇 |
晶体学 | 49篇 |
力学 | 76篇 |
数学 | 348篇 |
物理学 | 920篇 |
出版年
2023年 | 23篇 |
2022年 | 37篇 |
2021年 | 56篇 |
2020年 | 66篇 |
2019年 | 94篇 |
2018年 | 54篇 |
2017年 | 47篇 |
2016年 | 110篇 |
2015年 | 97篇 |
2014年 | 133篇 |
2013年 | 285篇 |
2012年 | 315篇 |
2011年 | 384篇 |
2010年 | 207篇 |
2009年 | 240篇 |
2008年 | 382篇 |
2007年 | 374篇 |
2006年 | 416篇 |
2005年 | 365篇 |
2004年 | 336篇 |
2003年 | 272篇 |
2002年 | 271篇 |
2001年 | 83篇 |
2000年 | 66篇 |
1999年 | 58篇 |
1998年 | 70篇 |
1997年 | 68篇 |
1996年 | 66篇 |
1995年 | 54篇 |
1994年 | 35篇 |
1993年 | 42篇 |
1992年 | 34篇 |
1991年 | 36篇 |
1990年 | 18篇 |
1989年 | 19篇 |
1988年 | 26篇 |
1987年 | 31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 | 44篇 |
1979年 | 38篇 |
1978年 | 29篇 |
1977年 | 26篇 |
1976年 | 23篇 |
1975年 | 15篇 |
1973年 | 18篇 |
排序方式: 共有5777条查询结果,搜索用时 15 毫秒
211.
Ruslim C Hashimoto M Matsunaga D Tamaki T Ichimura K 《Langmuir : the ACS journal of surfaces and colloids》2004,20(1):95-100
The inherent chromonic lyotropic liquid crystalline properties of a dye have been manipulated to fabricate multi-axial micropolarizing thin films by means of the photoalignment technique. The dye aqueous solution is deposited on a photopatterned polymer film to result in the macroscopic alignment of the dye molecules, followed by drying at ambient temperature. The solid polarizing dye layers thus produced exhibit very a high contrast ratio and degree of polarization in the region of visible light. Addition of a small amount of surfactant to the dye solution is a prerequisite for the generation of a nematic chromonic phase and for the formation of homogeneous thin dye layers on the polymer film. The correlation between the optical and surface morphological properties of the dye layers is discussed. 相似文献
212.
Kakei H Tsuji R Ohshima T Shibasaki M 《Journal of the American Chemical Society》2005,127(25):8962-8963
We succeeded in a catalytic asymmetric epoxidation reaction of alpha,beta-unsaturated esters via a conjugate addition of an oxidant using 2-10 mol % of the yttirium-chiral biphenyldiol catalyst. A variety of substrates with beta-aryl and beta-alkyl substituents were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy esters in up to 97% yield and 99% ee. 相似文献
213.
A mononuclear five-coordinate molybdenum(IV) monosulfide complex, (Et4N)2[MoS(L)2] (L = cyclohexene-1,2-dithiolate) (1), was obtained and characterized by IR, UV-vis spectroscopic methods, and X-ray crystallography. 1 was oxidized by an equivalent ferrocenium cation to give the corresponding mononuclear molybdenum(V) complex, (Et4N)[MoS(L)2] (2), which was stable for a few minutes under a lower concentration than 0.3 mM and then further dimerized to (Et4N)2[Mo(L)2]2(mu-S)2 (3). 相似文献
214.
[reaction: see text] We describe a catalytic asymmetric synthesis of both syn- and anti-3,5-dihydroxy esters. The method relies upon catalytic asymmetric epoxidation of alpha,beta-unsaturated imidazolides and amides, using lanthanide-BINOL complexes, and diastereoselective reduction of ketones. The method was applied to the enantioselective syntheses of 1,3-polyol/alpha-pyrone natural products 9a, 9b, and strictifolione (10). The absolute stereochemistry of 9a and 9b was also determined. 相似文献
215.
Matsuo T Dejima H Hirota S Murata D Sato H Ikegami T Hori H Hisaeda Y Hayashi T 《Journal of the American Chemical Society》2004,126(49):16007-16017
Sperm whale myoglobin, an oxygen storage hemoprotein, was successfully reconstituted with the iron porphycene having two propionates, 2,7-diethyl-3,6,12,17-tetramethyl-13,16-bis(carboxyethyl)porphycenatoiron. The physicochemical properties and ligand bindings of the reconstituted myoglobin were investigated. The ferric reconstituted myoglobin shows the remarkable stability against acid denaturation and only a low-spin characteristic in its EPR spectrum. The Fe(III)/Fe(II) redox potential (-190 mV vs NHE) determined by the spectroelectrochemical measurements was much lower than that of the wild-type. These results can be attributed to the strong coordination of His93 to the porphycene iron, which is induced by the nature of the porphycene ring symmetry. The O2 affinity of the ferrous reconstituted myoglobin is 2600-fold higher than that of the wild-type, mainly due to the decrease in the O2 dissociation rate, whereas the CO affinity is not so significantly enhanced. As a result, the O2 affinity of the reconstituted myoglobin exceeds its CO affinity (M' = K(CO)/K(O2) < 1). The ligand binding studies on H64A mutants support the fact that the slow O2 dissociation of the reconstituted myoglobin is primarily caused by the stabilization of the Fe-O2 sigma-bonding. The IR spectra for the carbon monoxide (CO) complex of the reconstituted myoglobin suggest several structural and/or electrostatic conformations of the Fe-C-O bond, but this is not directly correlated with the CO dissociation rate. The high O2 affinity and the unique characteristics of the myoglobin with the iron porphycene indicate that reconstitution with a synthesized heme is a useful method not only to understand the physiological function of myoglobin but also to create a tailor-made function on the protein. 相似文献
216.
Enami S Yamanaka T Hashimoto S Kawasaki M Tonokura K 《The journal of physical chemistry. A》2005,109(27):6066-6070
The reactions of Cl atoms with RI (R = n-C3H7, n-C4H9, cyclo-C6H11, C6H5, C6F5, and p-CH3C6H4) have been studied using cavity ring-down spectroscopy at a temperature range of 233-313 K and at 100 Torr total pressure of N2 diluent. Visible absorption spectra of the RI-Cl adducts were recorded at 440-520 nm at 263 K. The yields of the adducts were temperature-dependent. There was no discernible reaction of the adducts in the presence of 100 Torr of O2 at 263 K. Theoretical calculations were performed for C4H9I-Cl and C6H5I-Cl for quantitative explanation of the absorption spectra and the strength of the I-Cl bonds in the charge-transfer complexes. Evidence for the adduct formation following the reaction of Cl with C6H5Br was sought but not found at 440 and 520 nm. 相似文献
217.
Ayae Sugawara Akira Oichi Hiroko Suzuki Yuzo Shigesato Toshihiro Kogure Takashi Kato 《Journal of polymer science. Part A, Polymer chemistry》2006,44(17):5153-5160
Assembled structures of calcium carbonate (CaCO3) nanocrystals have been examined for polymer/CaCO3 thin-film composites synthesized through a self-organization process inspired by biomineralization. For the crystallization of CaCO3, a thin-film matrix of chitosan has been used as a polymeric substrate. When the matrix is immersed into a supersaturated aqueous solution of CaCO3 containing 1.4 × 10−3 wt % poly(aspartate) (PAsp), thin-film crystals of CaCO3 are formed spontaneously. Three kinds of disklike films have been observed under a polarizing optical microscope. Electron diffraction analyses of each film have revealed that one is aragonite, displaying radial orientation of the c axes, and the others are vaterite, exhibiting different orientations. Detailed observation by scanning electron microscopy has clarified that these films are assemblies of crystalline particles 10–20 nm in size. The thin-film composites have been obtained over a PAsp concentration range of 4.4 × 10−4 to 1.0 × 10−2 wt %. Vaterite formation becomes dominant when the concentration of PAsp is increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5153–5160, 2006 相似文献
218.
Three new metabolites, kunzeanones A (1), B (2), and C (3), along with three known compounds, cryptostrobin (4), (+)-spathulenol (5), and (−)-globulol (6), were isolated from the non-polar fraction of the dried leaves of Kunzea ambigua (Myrtaceae), which shows ichthyotoxicity toward a small fish, medaka. The structures of these new compounds were elucidated as condensates of alkylated phloroglucinol with methylflavanone and germacrane-type sesquiterpene, respectively, on the basis of spectral analyses including 1-D and 2-D NMR spectra. The stereochemistries of kunzeanones A and B were determined by X-ray crystallographic analysis. A sesquiterpene, (+)-spathulenol (5), among the isolates was characterized as the ichthyotoxic principle of the extract. 相似文献
219.
Hiroshi Tanaka Tsuyoshi Hasegawa Narumi Kita Hiroko Nakahara Takahiro Shibata Sho Oe Makoto Ojika Koji Uchida Takashi Takahashi 《化学:亚洲杂志》2006,1(5):669-677
An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ12,14‐PGJ2 (15dPGJ2) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ2 derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ2 derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ2 derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ2 derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ2. 相似文献
220.
Hiroyuki Nakazumi Takashi Endo Toshiyuki Nakaue Teijiro Kitao 《Journal of heterocyclic chemistry》1985,22(1):89-92
3-Amino-4H-1-benzothiopyran-4-one (3-aminothiochromone) was easily prepared by reaction of 3-bromo-thiochromen-4-one with sodium azide in methanol-water. Condensation of 3-aminothiochromone with diethyl ethoxymethylenemalonate and with dimethyl acetylenedicarboxylate gave intermediates, which were thermally cyclized to give 4,10-dihydro-4,10-dioxo-1H[1]benzothiopyrano[3,2-b]pyridinecarboxylates. 3-Formyl-thiochromone was condensed with o-phenylenediamine to give 7-oxo-7,13-dihydro[1]benzothiopyrano[2,3-b]-1,5-benzodiazepine. 相似文献