全文获取类型
收费全文 | 1378篇 |
免费 | 56篇 |
国内免费 | 4篇 |
专业分类
化学 | 949篇 |
晶体学 | 16篇 |
力学 | 6篇 |
数学 | 144篇 |
物理学 | 323篇 |
出版年
2023年 | 15篇 |
2022年 | 5篇 |
2021年 | 26篇 |
2020年 | 36篇 |
2019年 | 38篇 |
2018年 | 16篇 |
2017年 | 12篇 |
2016年 | 38篇 |
2015年 | 30篇 |
2014年 | 31篇 |
2013年 | 81篇 |
2012年 | 98篇 |
2011年 | 121篇 |
2010年 | 42篇 |
2009年 | 38篇 |
2008年 | 80篇 |
2007年 | 100篇 |
2006年 | 105篇 |
2005年 | 75篇 |
2004年 | 61篇 |
2003年 | 45篇 |
2002年 | 44篇 |
2001年 | 15篇 |
2000年 | 15篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 13篇 |
1996年 | 14篇 |
1995年 | 11篇 |
1994年 | 18篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 14篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1983年 | 8篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 9篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 11篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1971年 | 4篇 |
1968年 | 4篇 |
排序方式: 共有1438条查询结果,搜索用时 46 毫秒
31.
In this report, first use of size-selected gold nanoparticles (AuNPs) as matrixes for matrix assisted laser desorption/ionization (MALDI) is described for peptides and proteins. In comparison with conventional organic acid MALDI matrixes, the optimum matrix-to-analyte ratio with AuNP matrixes is reduced by 10-14 orders of magnitude. Significant differences in the relative abundances of the ions observed in positive and negative mode MALDI-time-of-flight mass spectrometry (TOFMS) are revealed as the AuNP size distribution is decreased from 10 to 2 nm, whereby 2-nm AuNPs exhibit quantum confinement effects prevalent in quantum dots. AuNP matrixes allow for selective analyte ionization, as demonstrated in the selective MALDI-TOFMS of phosphotyrosine in a background of phosphoserine and phosphothreonine peptides. 相似文献
32.
Katherine E. BashfordMatthew B. Burton Stuart CameronAnthony L. Cooper Rebecca D. HoggPeter D. Kane David A. MacManusChristopher A. Matrunola Christopher J. Moody Avril A.B. Robertson Mark R. Warne 《Tetrahedron letters》2003,44(8):1627-1629
The Bohlmann-Rahtz reaction has been used to prepare 2,3,6-trisubstituted pyridines suitable for use in library synthesis. The synthesis of piperidine substituted nicotinic acid derivative 9 has been optimised and carried out on a large scale to give ca. 500 g of scaffold which was used in the generation of the pyridine library 11. 相似文献
33.
Katherine Yu. Bezsoudnova Anatoly K. Yatsimirsky 《Reaction Kinetics and Catalysis Letters》1997,62(1):63-69
α- and β-Cyclodextrins accelerate the Smiles rearrangement of 4-nitrophenyl salicylate which proceeds through the mechanism
of intramolecular aromatic nucleophilic substitution. The binding and catalytic rate constants were calculated from the dependences
of the observed pseudo-first-order rate constants of the rearrangement reaction on cyclodextrin concentration obtained at
various pH values. The catalysis was interpreted in terms of a tighter binding of the anionic, highly delocalized δ-complex
intermediate than that of the substrate to cyclodextrins. 相似文献
34.
35.
We report the gas-phase preparation of negatively charged glycine as well as the Gly(H(2)O)(1,2) (-) complexes by entrainment of the neutral precursor into an ionized supersonic expansion tuned to optimize the (H(2)O)(n) (-)Ar(m) clusters. The photoelectron spectrum of Gly(-) displays the signature of a dipole-bound species, with sufficient vibrational fine structure to characterize the core neutral as a higher energy, non-zwitterionic isomer of the amino acid. 相似文献
36.
Vonderheide AP Meija J Tepperman K Puga A Pinhas AR States JC Caruso JA 《Journal of chromatography. A》2004,1024(1-2):129-137
High-performance chelation ion chromatography (HPCIC) was employed to retain cationic Cr(III) on an anion-exchange column and hence allow the separation of the two most prevalent forms of chromium, Cr(II) and Cr(VI). A mobile phase of nitric acid was utilized at pH = 1.5; additionally, 2,6-pyridinedicarboxylic acid was used at a concentration of 6 mM. Additives with different structural characteristics were used in an effort to elucidate retention mechanisms. Inductively-coupled plasma mass spectrometry was used for chromium detection. A collision cell was utilized to reduce chloride-based polyatomic ions that may interfere with the detection of Cr(III), and a detection limit study yielded levels in the low part-per-billion range. The newly developed method was applied to the chromatographic analysis of samples of an incubation medium containing Cr(VI) incubated with cell nuclei. 相似文献
37.
Capillary and microelectrophoretic separations of ligase detection reaction products produced from low-abundant point mutations in genomic DNA 总被引:2,自引:0,他引:2
Thomas G Sinville R Sutton S Farquar H Hammer RP Soper SA Cheng YW Barany F 《Electrophoresis》2004,25(10-11):1668-1677
Capillary gel electrophoresis (CGE) and polymer-based microelectrophoretic platforms were investigated to analyze low-abundant point mutations in certain gene fragments with high diagnostic value for colorectal cancers. The electrophoretic separations were carried out on single-stranded DNA (ssDNA) products generated from an allele-specific ligation assay (ligase detection reaction, LDR), which was used to screen for a single base mutation at codon 12 in the K-ras oncogene. The presence of the mutation generated a ssDNA fragment that was >40 base pairs (bp) in length, while the primers used for the ligation assay were <30 bp in length. Various separation matrices were investigated, with the success of the matrix assessed by its ability to resolve the ligation product from the large molar excess of unligated primers when the mutant allele was lower in copy number compared to the wild-type allele. Using CGE, LDR product models (44 and 51 bp) could be analyzed in a cross-linked polyacrylamide gel with a 1000-fold molar excess of LDR primers (25 bp) in approximately 45 min. However, when using linear polyacrylamide gels, these same fragments could not be detected due to significant electrokinetic biasing during injection. A poly(methylmethacrylate) (PMMA) microchip of 3.5 cm effective column length was used with a 4% linear polyacrylamide gel to analyze the products generated from an LDR. When the reaction contained a 100-fold molar excess of wild-type DNA compared to a G12.2D mutant allele, the 44 bp ligation product could be effectively resolved from unligated primers in under 120 s, nearly 17 times faster than the CGE format. In addition, sample cleanup was simplified using the microchip format by not requiring desalting of the LDR prior to loading. 相似文献
38.
Hiddessen AL Weitz DA Hammer DA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6788-6795
The selectivity and range of energies offered by specific biological interactions serve as valuable tools for engineering the assembly of colloidal particles into novel materials. In this investigation, high affinity biological interactions between biotin-coated "A" particles (RA = 0.475 microm) and streptavidin-coated "B" particles (RB = 2.75 microm) drive the self-assembly of a series of binary colloidal structures, from colloidal micelles (a large B particle coated by smaller A particles) to elongated chain microstructures (alternating A and B particles), as the relative number of small (A) to large (B) particles (2 < or = NA/NB < or = 200) is decreased at a low total volume fraction (10(-4) < or = phiT < or = 10(-3)). At a significantly higher total volume fraction (phiT > or = 10(-1)) and a low number ratio (NA/NB = 2), the rheological behavior of volume-filling particle networks connected by streptavidin-biotin bonds is characterized. The apparent viscosity (eta) as a function of the shear rate gamma, measured for networks at phiT = 0.1 and 0.2, exhibits shear-rate-dependent flow behavior, and both the apparent viscosity and the extent of shear thinning increase upon an increase of a factor of 2 in the total volume fraction. Micrographs taken before and after shearing show a structural breakdown of the flocculated binary particle network into smaller flocs, and ultimately a fluidlike suspension, with increasing shear rate. Rheological measurements provide further proof that suspension microstructure is governed by specific biomolecular interactions, as control experiments in which the streptavidin molecules on particles were blocked displayed Newtonian flow behavior. This investigation represents the first attempt at measuring the rheology of colloidal suspensions where assembly is driven by biomolecular cross-linking. 相似文献
39.
Susan A. Bourne Katherine De Villiers Timothy J. Egan 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(2):o53-o57
The structures of three compounds with potential antimalarial activity are reported. In N,N‐diethyl‐N′‐(7‐iodoquinolin‐4‐yl)ethane‐1,2‐diamine, C15H20IN3, (I), the molecules are linked into ribbons by N—H⋯N and C—H⋯N hydrogen bonds. In N‐(7‐bromoquinolin‐4‐yl)‐N′,N′‐diethylethane‐1,2‐diamine dihydrate, C15H20BrN3·2H2O, (II), two aminoquinoline molecules and four water molecules form an R54(13) hydrogen‐bonded ring which links to its neighbours to form a T5(2) one‐dimensional infinite tape with pendant hydrogen bonds to the aminoquinolines. The phosphate salt 7‐chloro‐4‐[2‐(diethylammonio)ethylamino]quinolinium bis(dihydrogenphosphate) phosphoric acid, C15H22ClN32+·2H2PO4−·H3PO4, (III), was prepared in order to establish the protonation sites of these compounds. The phosphate ions form a two‐dimensional hydrogen‐bonded sheet, while the aminoquinoline cations are linked to the phosphates by N—H⋯O hydrogen bonds from each of their three N atoms. While the conformation of the quinoline region hardly varies between (I), (II) and (III), the amino side chain is much more flexible and adopts a significantly different conformation in each case. Aromatic π–π stacking interactions are the only supramolecular interactions seen in all three structures. 相似文献
40.
Ellipsometry, surface tensiometry, and contact-angle measurement have been used to study the transition between partial wetting and pseudo-partial wetting of surfactant solutions by alkanes. In the partial wetting regime, the air-water surface tension is the same with and without alkane. In the pseudo-partial wetting regime, the air-water surface tension is lowered by the presence of alkane, showing that oil is solubilised into the surfactant monolayer. A discontinuous change in the coefficient of ellipticity with increasing surfactant concentration provides unequivocal evidence for the first-order nature of the wetting transitions. Ellipsometry has been used to explore the generality of wetting transitions of alkanes (dodecane, hexadecane, and squalane) on surfactant solutions [dodecyltrimethylammonium bromide, tetredecyltrimethylammonium bromide, dibucaine hydrochloride, and Aerosol OT (AOT)]. Of the systems studied, only hexadecane on AOT solutions did not show a wetting transition. Excess alkane remains as a lens on the surface of the surfactant solutions at all concentrations, but the contact angle is a minimum at the wetting transition. A semiquantitative model for the variation of the contact angle with surfactant concentration is provided. 相似文献