全文获取类型
收费全文 | 28618篇 |
免费 | 2632篇 |
国内免费 | 1834篇 |
专业分类
化学 | 23717篇 |
晶体学 | 214篇 |
力学 | 402篇 |
综合类 | 111篇 |
数学 | 471篇 |
物理学 | 8169篇 |
出版年
2024年 | 73篇 |
2023年 | 360篇 |
2022年 | 810篇 |
2021年 | 742篇 |
2020年 | 945篇 |
2019年 | 945篇 |
2018年 | 838篇 |
2017年 | 1093篇 |
2016年 | 1293篇 |
2015年 | 1185篇 |
2014年 | 1242篇 |
2013年 | 2107篇 |
2012年 | 1935篇 |
2011年 | 1771篇 |
2010年 | 1385篇 |
2009年 | 1773篇 |
2008年 | 1536篇 |
2007年 | 1877篇 |
2006年 | 1566篇 |
2005年 | 1437篇 |
2004年 | 1284篇 |
2003年 | 1064篇 |
2002年 | 850篇 |
2001年 | 607篇 |
2000年 | 572篇 |
1999年 | 557篇 |
1998年 | 458篇 |
1997年 | 435篇 |
1996年 | 407篇 |
1995年 | 329篇 |
1994年 | 288篇 |
1993年 | 244篇 |
1992年 | 207篇 |
1991年 | 223篇 |
1990年 | 126篇 |
1989年 | 100篇 |
1988年 | 78篇 |
1987年 | 53篇 |
1986年 | 50篇 |
1985年 | 45篇 |
1984年 | 41篇 |
1983年 | 18篇 |
1982年 | 30篇 |
1981年 | 20篇 |
1980年 | 14篇 |
1979年 | 13篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1974年 | 9篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
《Magnetic resonance in chemistry : MRC》2003,41(2):139-142
Bioassay‐guided fractionation of the methanol extract of Odontadenia macrantha afforded a new limonoid, odontadenin A (1) and two known triterpenoids, lupeol (2) and α‐amyrin (3). The structure of 1 was established on the basis of 1D and 2D NMR and high‐resolution fast atom bombardment mass spectrometric data. The new compound was found to possess moderate cytotoxicity against A2780, the ovarian cancer cell line. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
22.
Mohamed Haouas Amine Harrane Mohamed Belbachir Francis Taulelle 《Journal of Polymer Science.Polymer Physics》2007,45(22):3060-3068
Results of multinuclear MAS NMR spectroscopy are reported for poly (ε‐caprolactone)/maghnite nanocomposite formation, with ε‐caprolactone in situ polymerized in the presence of maghnite, a proton exchanged montmorillonite clay. Exfoliated and intercalated materials with different maghnite loading in the range 3–15 wt % were investigated. 1H NMR evidences Brønsted acid hydroxyl groups in the silicate layers and shows that their broad signal at 7.6 ppm present in the parent clay disappears in the nanocomposite material. 27Al MAS NMR results show that beside the hexacoordinated aluminum signal, two additional peaks corresponding to two different tetrahedral Al sites are present in the clay framework. The NMR signal intensity of only one of them was found to be affected in the nanocomposites compared with the parent maghnite, suggesting that these specific aluminum sites are the reactive ones at the initial stages of the polymerization. However almost no changes occurred in the 29Si NMR spectra, confirming that the polymer grafting, as indicated earlier by atomic force microscopy, took place on the aluminum tetracoordinated sites rather than on the silicon sites. A mechanism of maghnite surface catalyzed polymerization of ε‐caprolactone was proposed, involving Brønsted and Lewis acid sites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3060–3068, 2007 相似文献
23.
Sankar Prasad Bhuniya Safikur Rahman Anshul J. Satyanand Mahendrasinh M. Gharia Ashok M. Dave 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1650-1658
Maize starch was modified by allyl chloride adopting an interfacial reaction technique with cetyltrimethyl ammonium bromide as a phase‐transfer catalyst and pyridine as an acid acceptor. The degree of substitution was determined from an increasing carbon content of the modified starch. The percentage of carbon and hydrogen of the allyl‐modified starch was estimated by elemental analysis (C, H, and N), and the product characterization was done through 1H NMR and 13C NMR analyses. The allyl‐modified starch was then copolymerized with methacrylic acid and a combination of methacrylic acid and acrylamide at 50 and 70 °C with potassium persulfate as an initiator. The copolymer thus formed swelled in distilled water after neutralization with sodium carbonate. The percentage of absorption capacity of the hydrogels was determined with distilled water and 0.9% NaCl solution. The highest percentage of absorption, 6500%, was achieved for the developed hydrogel containing allyl starch and acrylic monomer in a 1.7:1 w/w ratio and acrylic monomer, namely, methacrylic acid and acrylamide in a 3.2:1 w/w ratio. The study on biodegradability of the developed hydrogel showed that the hydrogel is degradable in the presence of diastase (amylase). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1650–1658, 2003 相似文献
24.
Shigeru Katayama Mika Horiike Kazuyuki Hirao Naoto Tsutsumi 《Journal of Polymer Science.Polymer Physics》2002,40(24):2800-2806
We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002 相似文献
25.
Stefanie M. Walz Thomas E. Malner Ulrich Mueller Rolf Muelhaupt 《Journal of Polymer Science.Polymer Physics》2003,41(4):360-367
We explored phase separation and self‐assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser‐induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film‐forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine‐free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine‐free or low‐fluorine polymers, self‐assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 360–367, 2003 相似文献
26.
The crystal structure of a novel ferrocene derivative with potential flame-retardant/smoke-suppressant activity, 1,4,5,6,7,7-hexachloro-2-endo-ferrocenyl-hydroxymethyl-3-endo-hydroxymethyl-5-norbornene, has been determined. Some of the carbon–carbon bonds within the chlorendic residue are unusually long, and there is no interaction between the hydroxyl groups and the iron atom. There is evidence of intramolecular hydrogen bonding between the two hydroxyl groups. 相似文献
27.
G. Lligadas J. C. Ronda M. Gali V. Cdiz 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5630-5644
A new phosphorous‐containing fatty acid diepoxide was obtained from 10‐undecenoyl chloride and 10‐(2′,5′‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and crosslinked with 4,4′‐diaminodiphenylmethane and bis(m‐aminophenyl)methylphosphine oxide. The properties of the thermosetting materials were evaluated by differential scanning calorimetry, dynamic mechanical thermal analysis, thermogravimetric analysis, and limiting oxygen index (LOI). Thermal and thermooxidative degradation was studied by gas chromatography/mass spectrometry, FTIR, 31P magic angle spinning NMR spectroscopy, and scanning electron microscopy. LOI values indicate good flame‐retardant properties that are related to the formation of a protective phosphorous‐rich layer that slowed down the degradation and prevented it from being total. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5630–5644, 2006 相似文献
28.
Ken‐ichi Shinohara Tasuku Suzuki Takeshi Kitami Shingo Yamaguchi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(2):801-809
We fabricated a micrometer‐long supramolecular chain in which π‐conjugated polyrotaxane was coupled. A new experimental setup was designed and constructed, and the simultaneous direct imaging of the structure and fluorescent function was achieved. Furthermore, we identified the formation of a polymer intertwined network and observed novel fluorescence due to a long‐range interaction via this intertwined network over a distance of 5 μm or more without quenching over 15 min in the near field. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 801–809, 2006 相似文献
29.
30.
Aspects of the mechanism of the overall reaction between CaCO3/CaO and SO2/SO3 under oxidizing conditions are discussed. The limestone and lime sulphation processes were carried out in a thermobalance
under conditions relevant to atmospheric fluidized bed combustion. Sulphated samples, prepared in the form of cross-section
particles, were examined in a scanning electron microscope by energy-dispersive X-ray and back-scattered electron imaging.
Photomicrographs are presented. The reaction proceeded from the outer surface of the particles and along the pores. Surface
textural changes during the reaction were considered. The layer of products was identified as controlling both the rate and
extent of limestone/lime sulphation. In the products, two sulphur-bearing solids (CaSO4 and CaS) were identified. The presence of CaS, which may cause difficulties in practice, is attributed to CaSO3 disproportionation.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献