全文获取类型
收费全文 | 605篇 |
免费 | 13篇 |
专业分类
化学 | 389篇 |
晶体学 | 11篇 |
力学 | 25篇 |
数学 | 48篇 |
物理学 | 145篇 |
出版年
2023年 | 5篇 |
2022年 | 7篇 |
2021年 | 14篇 |
2020年 | 8篇 |
2019年 | 7篇 |
2018年 | 9篇 |
2017年 | 6篇 |
2016年 | 20篇 |
2015年 | 21篇 |
2014年 | 14篇 |
2013年 | 31篇 |
2012年 | 48篇 |
2011年 | 30篇 |
2010年 | 32篇 |
2009年 | 17篇 |
2008年 | 31篇 |
2007年 | 32篇 |
2006年 | 20篇 |
2005年 | 16篇 |
2004年 | 16篇 |
2003年 | 18篇 |
2002年 | 18篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1999年 | 12篇 |
1998年 | 10篇 |
1997年 | 8篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 21篇 |
1992年 | 15篇 |
1991年 | 5篇 |
1990年 | 12篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1975年 | 5篇 |
1974年 | 4篇 |
1967年 | 7篇 |
1891年 | 2篇 |
排序方式: 共有618条查询结果,搜索用时 15 毫秒
41.
42.
In this Letter, we derive the dispersion relation of the surface waves at the interfaces between Mott-insulating and superfluid domains for a two-dimensional Bose-Einstein condensate in an optical lattice subjected to a confining potential. We then calculate their contribution to the heat capacity of the system and show how its low-temperature scaling allows an experimental test of the existence and properties of Mott insulator-superfluid domains. 相似文献
43.
Two-dimensional protein map of human vastus lateralis muscle 总被引:4,自引:0,他引:4
Protein samples of human vastus lateralis muscle were analyzed by two-dimensional gel electrophoresis, using immobilized pH gradients encompassing several pH regions in the first dimension and sodium dodecyl sulfate-polyacrylamide gel electrophoresis in the second dimension. More than 500 protein spots on each gel were detected by silver staining, of which 150 were excised, digested in-gel with trypsin and characterized by matrix assisted laser desorptioin/ionization-mass spectrometry and tandem electrospray mass spectrometry. Using these techniques, 124 spots including contractile proteins and metabolic enzymes were identified. This database should provide a valuable resource for the definition of the functional properties of muscle fibres and for assessment of the influence of e.g., hypoxia, ischaemia and ageing on protein level. 相似文献
44.
Summary A comparison of the official EPA method 515.1 for determination of chlorinated acidic pesticides and a modification of it is illustrated. Extraction of the analytes from water and their determination and quantitation is by gas chromatography-electron capture detection (GC-ECD), liquid chromatography-UV detection and liquid chromatography-particle beam mass spectrometry. Although HPLC-PBMS was found to be less sensitive than the GC-ECD method, it was, nevertheless, more sensitive than HPLC-UV. The modified method is simpler, quicker and allows more accurate determination of pesticides in aqueous samples.Deceased July 31, 1996 相似文献
45.
de Souza BM Marques MR Tomazela DM Eberlin MN Mendes MA Palma MS 《Rapid communications in mass spectrometry : RCM》2004,18(10):1095-1102
The social wasp P. paulista is relatively common in southeast Brazil causing many medically important stinging incidents. The seriousness of these incidents is dependent on the amount of venom inoculated by the wasps into the victims, and the characteristic envenomation symptoms are strongly dependent on the types of peptides present in the venom. In order to identify some of these naturally occurring peptides available in very low amounts, an analytical protocol was developed that uses a combination of reversed-phase and normal-phase high-performance liquid chromatography (HPLC) of wasp venom for peptide purification, with matrix-assisted laser desorption/ionization time-of-flight post-source decay mass spectrometry (MALDI-Tof-PSD-MS) and low-energy collision-induced dissociation (CID) in a quadrupole time-of-flight tandem mass spectrometry (QTof-MS/MS) instrument for peptide sequencing at the sub-picomole level. The distinction between Leu and Ile was achieved both by observing d-type fragment ions obtained under CID conditions and by comparison of retention times of the natural peptides and their synthetic counterparts (with different combinations of I and/or L at N- and C-terminal positions). To distinguish the isobaric residues K and Q, acetylation of peptides was followed by Q-Tof-MS analysis. The primary sequences obtained were INWLKLGKMVIDAL-NH(2) (MW 1611.98 Da) and IDWLKLGKMVMDVL-NH(2) (MW 1658.98 Da). Micro-scale bioassay protocols characterized both peptides as presenting potent hemolytic action, mast cell degranulation, and chemotaxis of polymorphonucleated leukocyte (PMNL) cells. The primary sequences and the bioassay results suggest that these toxins constitute members of a new sub-class of mastoparan toxins, directly involved in the occurrence of inflammatory processes after wasp stinging. 相似文献
46.
Pérez CM Rodríguez-Delgado A Palma P Álvarez E Gutiérrez-Puebla E Cámpora J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(46):13834-13842
Manganese alkyl complexes stabilised by 2,6-bis(N,N'-2,6-diisopropyl-phenyl)acetaldiminopyridine ((iPr)BIP) have been selectively prepared by reacting suitable alkylmanganese(II) precursors, such as homoleptic dialkyls [(MnR(2))(n)] or the corresponding THF adducts [{MnR(2)(thf)}(2)] with the mentioned ligand. For R=CH(2)CMe(2)Ph or CH(2)Ph, formally Mn(I) derivatives are produced, in which one of the two R groups migrates to the 4-position of the central pyridine ring in the (iPr)BIP ligand. In contrast, a true dialkyl complex [MnR(2)((iPr)BIP)] can be isolated for R=CH(2)SiMe(3). In solution, this compound slowly evolves to the corresponding Mn(I) monoalkyl derivative. A detailed study of this reaction provides insights on its mechanism, showing that it proceeds through successive alkyl migrations, followed by spontaneous dehydrogenation. Protonation of [Mn(CH(2)SiMe(3))(2)((iPr)BIP)] with the pyridinium salt [H(Py)(2)][BAr'(4)] (Ar'=3,5-C(6)H(3)(CF(3))(2)) leads to the cationic species [Mn(CH(2)SiMe(3))(Py)((iPr)BIP)](+). Alternatively, the same complex can be produced by reaction of the pyridine complex [{Mn(CH(2)SiMe(3))(2)(Py)}(2)] with the protonated ligand salt [H(iPr)BIP](+)[BAr'(4)](-). This last reaction allows the synthesis of analogous cationic alkylmanganese(II) derivatives, when precursors of type [MnR(2)((iPr)BIP)] are not available. Treatment of these neutral and cationic (iPr)BIP alkylmanganese derivatives with a range of typical co-catalysts (modified methylaluminoxane (MMAO), B(C(6)F(5))(3), trimethyl or triisobutylaluminum) does not lead to active ethylene polymerisation catalysts. 相似文献
47.
Antonella De Palma Antonella Roveri Mattia Zaccarin Louise Benazzi Simone Daminelli Giorgia Pantano Mauro Buttarello Fulvio Ursini Massimo Gion Pier Luigi Mauri 《Journal of chromatography. A》2010,1217(33):5328-5336
Since red blood cells (RBCs) lack nuclei and organelles, cell membrane is their main load-bearing component and, according to a dynamic interaction with the cytoskeleton compartment, plays a pivotal role in their functioning. Even if erythrocyte membranes are available in large quantities, the low abundance and the hydrophobic nature of cell membrane proteins complicate their purification and detection by conventional 2D gel-based proteomic approaches. So, in order to increase the efficiency of RBC membrane proteome identification, here we took advantage of a simple and reproducible membrane sub-fractionation method coupled to Multidimensional Protein Identification Technology (MudPIT). In addition, the adoption of a stringent RBC filtration strategy from the whole blood, permitted to remove exhaustively contaminants, such as platelets and white blood cells, and to identify a total of 275 proteins in the three RBC membrane fractions collected and analysed. Finally, by means of software for the elaboration of the great quantity of data obtained and programs for statistical analysis and protein classification, it was possible to determine the validity of the entire system workflow and to assign the proper sub-cellular localization and function for the greatest number of the identified proteins. 相似文献
48.
P.D.S.C. Mariani K. Allganer F.B. Oliveira E.J.B.N. Cardoso L.H. Innocentini-Mei 《Polymer Testing》2009,28(8):824-829
The development of biodegradable polymers is considered to be a good alternative to decrease the volume of the plastic waste disposed into the environment every year. The use of natural polymers as raw materials to develop polymer blends and composites has increased the demand for renewable sources such as starch and soy protein.In this work, the authors prepared and characterized the thermal, mechanical and morphological properties of blends based on poly (-caprolactone) and modified corn starch, with added soy protein isolate (SPI) and sorbitol. All samples were processed by extrusion in a single-screw extruder and hot pressing. It was observed that the addition of modified corn starch and SPI were responsible for the reduction of thermal and mechanical properties of the materials, compared to pristine PCL. However, with increasing amounts of SPI and the reduction of starch incorporated into the samples, their properties tend to recover. The insertion of soy protein isolate in the formulations was done with the aim of balancing the C/N ratio of the blend, which plays a key role in the biodegradation process of these materials. 相似文献
49.
Tonia M. Di Palma Maria V. Prati Antonio Borghese 《Journal of the American Society for Mass Spectrometry》2009,20(12):2192-2198
Here we report on a laser plasma-based tunable VUV photoionization time-of-flight (TOF) mass spectrometer conceived mainly
to study complex gaseous mixtures. Ionizing photons at tunable vacuum UV (VUV) wavelengths are generated by a gas-target laser-produced
plasma, spectrally dispersed in the range 100–160 nm and efficiently focused onto a sample molecular beam. As a test case,
we studied the exhaust gas of a four-stroke moped, a typical example of a complex gaseous mixture. Due to the VUV “soft” ionization,
the mass spectra are less congested and more easily interpretable. Substituted benzene derivatives are found to give the most
intense signals. Several aliphatic hydrocarbons are also detected. The use of tunable VUV radiation allowed the investigation
of the contribution of isomers in the mass spectrum from the onset and shape of the photoionization efficiency spectra. Semiquantitative
analysis was performed using known literature data detailing the photoionization cross sections. Our findings suggest that
using combined data on the mass/photoionization efficiency spectra may be very helpful for a comprehensive analysis of complex
gaseous mixtures. 相似文献
50.
Sandra L. Gmez Carlos M. Sanabria Alirio Palma Ali Bahsas Justo Cobo Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(9):o465-o469
In (2RS,4SR)‐7‐chloro‐2‐exo‐(2‐chloro‐6‐fluorophenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C16H12Cl2FNO, (I), molecules are linked into chains by a single C—H...π(arene) hydrogen bond. (2RS,4SR)‐2‐exo‐(2‐Chloro‐6‐fluorophenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C16H13ClFNO, (II), is isomorphous with compound (I) but not strictly isostructural with it, as the hydrogen‐bonded chains in (II) are linked into sheets by an aromatic π–π stacking interaction. The molecules of (2RS,4SR)‐7‐methyl‐2‐exo‐(4‐methylphenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C18H19NO, (III), are linked into sheets by a combination of C—H...N and C—H...π(arene) hydrogen bonds. (2S,4R)‐2‐exo‐(2‐Chlorophenyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C16H14ClNO, (IV), crystallizes as a single enantiomer and the molecules are linked into a three‐dimensional framework structure by a combination of one C—H...O hydrogen bond and three C—H...π(arene) hydrogen bonds. 相似文献