全文获取类型
收费全文 | 26157篇 |
免费 | 513篇 |
国内免费 | 160篇 |
专业分类
化学 | 17518篇 |
晶体学 | 214篇 |
力学 | 655篇 |
综合类 | 1篇 |
数学 | 4401篇 |
物理学 | 4041篇 |
出版年
2021年 | 176篇 |
2020年 | 213篇 |
2019年 | 284篇 |
2018年 | 232篇 |
2017年 | 207篇 |
2016年 | 444篇 |
2015年 | 344篇 |
2014年 | 455篇 |
2013年 | 1322篇 |
2012年 | 1191篇 |
2011年 | 1508篇 |
2010年 | 780篇 |
2009年 | 625篇 |
2008年 | 1365篇 |
2007年 | 1417篇 |
2006年 | 1409篇 |
2005年 | 1411篇 |
2004年 | 1240篇 |
2003年 | 1042篇 |
2002年 | 1016篇 |
2001年 | 368篇 |
2000年 | 296篇 |
1999年 | 244篇 |
1998年 | 285篇 |
1997年 | 312篇 |
1996年 | 393篇 |
1995年 | 298篇 |
1994年 | 282篇 |
1993年 | 287篇 |
1992年 | 273篇 |
1991年 | 238篇 |
1990年 | 224篇 |
1989年 | 240篇 |
1988年 | 268篇 |
1987年 | 250篇 |
1986年 | 245篇 |
1985年 | 386篇 |
1984年 | 436篇 |
1983年 | 323篇 |
1982年 | 427篇 |
1981年 | 402篇 |
1980年 | 341篇 |
1979年 | 331篇 |
1978年 | 347篇 |
1977年 | 331篇 |
1976年 | 274篇 |
1975年 | 270篇 |
1974年 | 260篇 |
1973年 | 240篇 |
1972年 | 143篇 |
排序方式: 共有10000条查询结果,搜索用时 18 毫秒
971.
In connection with our synthetic approach to pentacyclic triterpenes,1 we have required substantial amounts of 2,5,5-trimethyl-1,3-cyclohexanedione (methyldimedone, 2), which is available by methylation of dimedone (1).2 However, methylation may also afford the 2,2-dimethyl product 3, the methyl ether 4, and the C, O-dimethyl product 5. 相似文献
972.
经Opuntia dilenii haw植物提取液绿色合成制备的纳米铝酸锌的催化性质(英文) 总被引:1,自引:0,他引:1
C.Ragupathi J.Judith Vijaya S.Narayanan L.John Kennedy Seeram Ramakrishna 《催化学报》2013,34(10):1951-1958
Various nanosized zinc aluminate(ZnAl2O4) samples were prepared by a conventional and a mi- crowave method both with and without using Opuntia dilenii haw plant extract,and were charac- terized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),high resolution scanning electron microscopy(HRSEM),energy dispersion scanning(EDX),temperature dependent conductance measurements, thermoelectric power measurements, ultraviolet-visible (UV-Vis) diffuse reflectance spectroscopy,and photoluminescence spectroscopy.The formation of a pure ZnAl2O4 phase was confirmed by XRD and FT-IR.A change in morphology from nanosized plates to nanosized sheets with,respectively,the conventional and microwave heating methods was clearly shown by HRSEM.UV-Vis diffusion reflectance spectroscopy measured the band gaps of ZnAl2O4 nanosized plates and nanosized sheets as 3.5 and 3.9 eV,respectively.The synthesized ZnAl2O4 was single crystalline and has three photoluminescence emissions at 482,528,and 540 nm.ZnAl2O4 nanosized sheets prepared by the microwave method showed higher catalytic activity for the oxida- tion of benzyl alcohol(85% conversion) than ZnAl2O4 nanosized plates prepared by the convention- al method(60% conversion). 相似文献
973.
974.
John Bethke Jürgen Kopf Paul Margaretha Bernard Pignon Léon Dupont Léon E. Christiaens 《Helvetica chimica acta》1997,80(6):1865-1868
Irradiation (λ = 350 nm) of 1H-[2]benzothiopyran-1-one ( 2 ) in the solid state affords selectively and in good yield 6aα, 6bα, 12bα, 12cα -tetrahydrocyclobuta[1, 2-c:4, 3-c′]bis([2]benzothiopyran)-5, 8-dione ( 3 ), the head-to-head (HH) cis-cisoid-cis-cyclodimer of 2 , X-Ray analysis of 2 confirms that this reaction proceeds according to the well-established topochemical principles. The same dimer 3 is obtained in low yields on irradiation of 10−1 M solutions of 2 in either MeOH or MeCN, while no conversion at all is observed in benzene. On irradiation of 2 in MeCN in the presence of tetrachloroethene, the [2 + 2] photocycloadduct 4 is formed in good yield, the conversion 2 → 4 being efficiently quenched by naphthalene. In contrast, no reaction is observed -on irradiation of 2 in the presence of 2, 3-dimethylbut-2-ene, neither in polar nor in apolar solvents. 相似文献
975.
Schwizer D Patton JT Cutting B Smieško M Wagner B Kato A Weckerle C Binder FP Rabbani S Schwardt O Magnani JL Ernst B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(5):1342-1351
A new class of N-acetyl-D-glucosamine (GlcNAc) mimics for E-selectin antagonists was designed and synthesized. The mimic consists of a cyclohexane ring substituted with alkyl substituents adjacent to the linking position of the fucose moiety. Incorporation into E-selectin antagonists led to the test compounds 8 and the 2'-benzoylated analogues 21, which exhibit affinities in the low micromolar range. By using saturation transfer difference (STD)-NMR it could be shown that the increase in affinity does not result from an additional hydrophobic contact of the alkyl substituent with the target protein E-selectin, but rather from a steric effect stabilizing the antagonist in its bioactive conformation. The loss of affinity found for antagonists 10 and 35 containing a methyl substituent in a remote position (and therefore unable to support to the stabilization of the core) further supports this hypothesis. Finally, when a GlcNAc mimetic containing two methyl substituents (52 and 53) was used, in which one methyl was positioned adjacent to the fucose linking position and the other was in a remote position, the affinity was regained. 相似文献
976.
Impellizzeri S McCaughan B Callan JF Raymo FM 《Journal of the American Chemical Society》2012,134(4):2276-2283
In search of strategies to photoactivate the luminescence of semiconductor quantum dots, we devised a synthetic approach to attach photocleavable 2-nitrobenzyl groups to CdSe-ZnS core-shell quantum dots coated with hydrophilic polymeric ligands. The emission intensity of the resulting nanostructured constructs increases by more than 60% with the photolysis of the 2-nitrobenzyl appendages. Indeed, the photoinduced separation of the organic chromophores from the inorganic nanoparticles suppresses an electron-transfer pathway from the latter to the former and is mostly responsible for the luminescence enhancement. However, the thiol groups anchoring the polymeric envelope to the ZnS shell also contribute to the photoinduced emission increase. Presumably, their photooxidation eliminates defects on the nanoparticle surface and promotes the radiative deactivation of the excited quantum dots. This effect is fully reversible but its magnitude is only a fraction of the change caused by the photocleavage of the 2-nitrobenzyl groups. In addition, these particular quantum dots can cross the membrane of model cells and their luminescence increases by ~80% after the intracellular photocleavage of the 2-nitrobenzyl quenchers. Thus, photoswitchable luminescent constructs with biocompatible character can be assembled combining the established photochemistry of the 2-nitrobenzyl photocage with the outstanding photophysical properties of semiconductor quantum dots and the hydrophilic character of appropriate polymeric ligands. 相似文献
977.
The treatment of cutaneous vascular lesions (port wine stains etc.) using lasers has been guided by theories based on the “cold” or room‐temperature optical properties of the hemoglobin target chromophore. We have recently presented evidence showing that under the influence of laser irradiation, the optical properties of blood in vitro are time and temperature dependent. Such complications are not currently subsumed into the in vivo theory. Here, we study the time‐domain optical properties of blood undergoing photocoagulation in vitro using two newly developed time‐resolved techniques. We also study the asymptotic effect of laser photocoagulation on the chemical and structural properties of the components of the blood matrix. We present evidence showing that the photocoagulation process involves significant changes in the optical absorption and scattering properties of blood, coupled with photothermally induced chemical and structural changes. We demonstrate the first use of a laser to deliberately generate magnetic resonance imaging contrast in vitro. We show that this technique offers significant potential advantages to in vivo intravenous chemical contrast agent injection. 相似文献
978.
Carlos E. M. Carvalho Solange M. S. V. Wardell James L. Wardell Janet M. S. Skakle John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(1):o28-o32
Molecules of the title compounds N2‐(benzoyloxy)benzamidine, C14H12N2O2, (I), N2‐(2‐hydroxybenzoyloxy)benzamidine, C14H12N2O3, (II), and N2‐benzoyloxy‐2‐hydroxybenzamidine, C14H12N2O3, (III), all have extended chain conformations, with the aryl groups remote from one another. In (I), the molecules are linked into chains by a single N—H⋯N hydrogen bond [H⋯N = 2.15 Å, N⋯N = 3.029 (2) Å and N—H⋯N = 153°] and these chains are linked into sheets by means of aromatic π–π stacking interactions. There is one intramolecular O—H⋯O hydrogen bond in (II), and a combination of one three‐centre N—H⋯(N,O) hydrogen bond [H⋯N = 2.46 Å, H⋯O = 2.31 Å, N⋯N = 3.190 (2) Å, N⋯O = 3.146 (2) Å, N—H⋯N = 138° and N—H⋯O = 154°] and one two‐centre C—H⋯O hydrogen bond [H⋯O = 2.46 Å, C⋯O = 3.405 (2) Å and C—H⋯O = 173°] links the molecules into sheets. In (III), an intramolecular O—H⋯N hydrogen bond and two N—H⋯O hydrogen bonds [H⋯O = 2.26 and 2.10 Å, N⋯O = 2.975 (2) and 2.954 (2) Å, and N—H⋯O = 138 and 163°] link the molecules into sheets. 相似文献
979.
Laurel Ng Alan J. Grodzinsky John Sandy Anna Plaas Christine Ortiz 《Macromolecular Symposia》2004,214(1):1-4
Tapping mode atomic force microscopy (TMAFM) was employed to directly calculate the persistence length of individual fetal bovine epiphyseal and mature nasal cartilage aggrecan monomers, as well as their constituent chondroitin sulfate glycosaminoglycan chains. 相似文献
980.
By combining nonhydrolytic reaction with seed-mediated growth, high-quality and monodisperse spinel cobalt ferrite, CoFe(2)O(4), nanocrystals can be synthesized with a highly controllable shape of nearly spherical or almost perfectly cubic. The shape of the nanocrystals can also be reversibly interchanged between spherical and cubic morphology through controlling nanocrystal growth rate. Furthermore, the magnetic studies show that the blocking temperature, saturation, and remanent magnetization of nanocrystals are solely determined by the size regardless the spherical or cubic shape. However, the shape of the nanocrystals is a dominating factor for the coercivity of nanocrystals due to the effect of surface anisotropy. Such magnetic nanocrystals with distinct shapes possess tremendous potentials in fundamental understanding of magnetism and in technological applications of magnetic nanocrystals for high-density information storage. 相似文献