全文获取类型
收费全文 | 434篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 331篇 |
晶体学 | 9篇 |
力学 | 9篇 |
数学 | 39篇 |
物理学 | 62篇 |
出版年
2023年 | 5篇 |
2022年 | 14篇 |
2021年 | 13篇 |
2020年 | 11篇 |
2019年 | 9篇 |
2018年 | 9篇 |
2017年 | 16篇 |
2016年 | 13篇 |
2015年 | 3篇 |
2014年 | 10篇 |
2013年 | 37篇 |
2012年 | 14篇 |
2011年 | 43篇 |
2010年 | 14篇 |
2009年 | 10篇 |
2008年 | 26篇 |
2007年 | 19篇 |
2006年 | 17篇 |
2005年 | 16篇 |
2004年 | 17篇 |
2003年 | 12篇 |
2002年 | 10篇 |
2001年 | 4篇 |
2000年 | 7篇 |
1999年 | 8篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1992年 | 8篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1980年 | 4篇 |
1979年 | 7篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1969年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
排序方式: 共有450条查询结果,搜索用时 906 毫秒
71.
The free surface of a soft elastic film becomes unstable and forms an isotropic labyrinth pattern when a rigid flat plate is brought into adhesive contact with the film. These patterns have a characteristic wavelength, lambda approximately 3H, where H is the film thickness. We show that these random structures can be ordered, modulated, and aligned by depositing the elastic film (cross-linked polydimethylsiloxane) on a patterned substrate and by bringing the free surface of the film in increasing adhesive contact with a flat stamp. Interestingly, the influence of the substrate "bleeds" through the film to its free surface. It becomes possible to generate complex two-dimensional ordered structures such as an array of femtoliter beakers even by using a simple one-dimensional stripe patterned substrate when the instability wavelength, lambda approximately 3H, nearly matches the substrate pattern periodicity. The free surface morphology is modulated in situ by merely varying the stamp-surface separation distance. The free surface structures originating from the elastic contact instability can also be made permanent by the UV-ozone induced oxidation and stiffening. 相似文献
72.
Tangirala R Revanur R Russell TP Emrick T 《Langmuir : the ACS journal of surfaces and colloids》2007,23(3):965-969
Interfacial segregation of nanoparticles on droplets, such as water droplets in oil, is achieved by mixing or shaking organic solutions of the nanoparticles with water. This typically results in the formation of droplets with a large distribution of sizes, ranging from 10 microm to greater than 200 microm in diameter. Here we describe the application of track-etch membranes to control the size of these nanoparticle-coated droplets. Passing nanoparticle-coated droplets through the membranes substantially reduces their size by breaking up the droplets during the extrusion process and reforming droplets of comparable size to the membrane pore diameter. When the nanoparticles used in these sizing procedures are covered with functional ligands, stabilization of the post-extrusion diameter is achieved by polymerization/cross-linking of the ligand periphery. 相似文献
73.
In the present paper, an equation of state has been obtained in case of liquid alkali metals like Na, K, Rb and Cs from sound
velocity measurements. The theory developed gives very good agreement for both the sound velocity and the volume as a function
of pressure at different temperatures in these liquid alkali metals. Further, the variation of non-linear parameter,B / A, as a function of pressure and temperature is also studied. 相似文献
74.
Injection moulded copolymer specimens containing between 6 to 11% ethylene were impacted using the drop weight method at 23°C and −20°C. Their response to the impact event was analysed in terms of failure mechanisms by considering their initiation and propagation energies at the respective temperatures. At −20°C, the results indicated that the multiple shear yielding toughening mechanism is predominant whereas room temperature tests show evidence of multiple crazing behaviour. The peak force sustained by the specimens decreased with the testing temperature. 相似文献
75.
G. V. Ravindra 《Mathematische Annalen》2009,345(3):731-748
We prove that any arithmetically Gorenstein curve on a smooth, general hypersurface of degree at least 6, is a complete intersection. This gives a characterisation of complete intersection curves on general
type hypersurfaces in . We also verify that certain 1-cycles on a general quintic hypersurface are non-trivial elements of the Griffiths group. 相似文献
76.
Rosenfeld A Morgan J Goswami LN Ohulchanskyy T Zheng X Prasad PN Oseroff A Pandey RK 《Photochemistry and photobiology》2006,82(3):626-634
The effects of an additional keto group on absorption wavelength and the corresponding metal complexes Zn(II), Cu(II) In(III) on singlet oxygen production and photodynamic efficacy were examined among the alkyl ether analogs of pyropheophorbide-a. For the preparation of the desired photosensitizers, the methyl 13(2)-oxo-pyropheophorbide-a obtained by reacting methyl pyropheophorbide-a with aqueous LiOH-THF was converted into a series of alkyl ether analogs. These compounds were evaluated for photophysical properties and in vitro (by means of the MTT assay and intracellular localization in RIF cells) and in vivo (in C3H mice implanted with RIF tumors) photosensitizing efficacy. Among the alkyl ether derivatives, the methyl 3-decyloxyethyl-3-devinyl-13(2)-oxo-pyropheophorbide-a was found to be most effective and the insertion of In(III) into this analog further enhanced its in vitro and in vivo photosensitizing efficacy. Fluorescence microscopy showed that, in contrast to the hexyl and dodecyl ether derivatives of HPPH (which localize in mitochondria and lysosomes, respectively), the diketo-analogs and their In(III) complexes localized in Golgi bodies. The preliminary in vitro and in vivo results suggest that, in both free-base and metalated analogs, the introduction of an additional keto group at the five-member exocyclic ring in pyropheophorbide-a diminishes its photosensitizing efficacy. This may be due to a shift in subcellular localization from mitochondria to the Golgi bodies. The further introduction of In(III) enhances photoactivity, but not by shifting the localization of the photosensitizer. 相似文献
77.
Kozyrev AN Chen Y Goswami LN Tabaczynski WA Pandey RK 《The Journal of organic chemistry》2006,71(5):1949-1960
Allomerization of bacteriochlorophyll a (Bchl a) was studied under various reaction conditions. Bchl a on stirring with KOH/propanol produced an "unstable bacteriochlorin", which decomposed in acidic conditions to give a complex mixture containing bacteriopurpurin a as a principal component. The yields of other compounds varied and were found to be dependent on reaction condition. The structures of the isolated porphyrins, chlorins, and bacteriochlorins, related to Bchl a, were assigned on the basis of 1D, 2D NMR (ROESY), and mass spectroscopy analyses. The presence of fused anhydride rings in porphyrin, chlorin, and bacterichlorin systems showed a significant influence on their optical properties. Compared to bacteriochlorophyll a and bacteriopheophytin, the related structurally modified analogues, e.g., the bacteriopurpurin a, 13(1)/15(1)-N-alkyl isoimide, and the imide analogues were found to be more stable with a significant difference in spectroscopic properties. Bacteriochlorins containing anhydride, imide, or isoimide cyclic rings demonstrated a significant bathochromic shift of their Q bands in their electronic absorption spectra. Under basic conditions the formation of the 12-hydroxymethyl, 12-formyl, and 12-methylene analogues as byproducts from the 12-methyl-bacteriopurpurin-N-hexylimide could be due to subsequent oxidation of the vinylogous enolate intermediates. To investigate the effect of the central metal in the electronic spectra, the stable bacteriopurpurin-18-N-hexylimide was converted to a series of metal complexes [Zn(II), Cd(II), and Pd(II)] by following the direct or transmetalation approaches. Compared to the free-base analogue, these complexes showed a remarkable shift in their electronic absorption spectra. 相似文献
78.
79.
Swetha Parsha Y. Ravindra Kumar M. Ravichander L. Prakash B. Sudharani 《液相色谱法及相关技术杂志》2016,39(4):178-194
A rapid, precise, and reliable liquid chromatography tandem mass spectrometry (LC–MS/MS) method has been developed for the characterization of stressed degradation products of mirabegron. It is used in the treatment of overactive bladder and administered to treat urinary symptoms such as urgency or frequency and incontinence. It also works by relaxing the muscles around bladder.Mirabegron was subjected to hydrolysis (acidic, alkaline, and neutral) and peroxidation, as per ICH-specified conditions. The drug showed degradation under stress conditions. However, it was stable to neutral conditions. A total of seven degradation products were observed and the chromatographic separation of the drug and its degradation products was achieved on X-TerraRP-8 (250 mm × 4.6 mm, i.d., 5 µm) column using 0.01 M ammonium acetate as mobile phase-A and 60:40 ratio of acetonitrile (ACN):water as mobile phase-B. The degradation products were characterized by LC–MS/MS and its fragmentation pathways were proposed. Probable possible structures were drawn based on parent and daughter molecular ions. One peroxide degradant impurity was isolated using preparative LC and characterized using liquid chromatography–mass spectrometry and NMR data. 相似文献
80.
The stability and electronic properties of carbon in α-Al2O3 are investigated using density functional theory. In the host lattice, the substitutional C prefers the Al site under the O-rich conditions, whereas the O site is preferred by carbon under the Al-rich conditions. The calculated results predict a direct relationship between the thermodynamic and optical transition levels with the degree of the local distortion induced by C in the alumina lattice. We also find C at the O site acts as a charge compensator to stabilize the F+ center, thereby enhancing the TL signal at 465 K. Also, C at Al site can serve as electron traps for TL emission process in α-Al2O3. 相似文献