全文获取类型
收费全文 | 2840篇 |
免费 | 114篇 |
国内免费 | 71篇 |
专业分类
化学 | 2073篇 |
晶体学 | 7篇 |
力学 | 36篇 |
综合类 | 2篇 |
数学 | 429篇 |
物理学 | 478篇 |
出版年
2021年 | 21篇 |
2020年 | 43篇 |
2019年 | 47篇 |
2018年 | 23篇 |
2017年 | 19篇 |
2016年 | 66篇 |
2015年 | 68篇 |
2014年 | 87篇 |
2013年 | 109篇 |
2012年 | 132篇 |
2011年 | 152篇 |
2010年 | 103篇 |
2009年 | 79篇 |
2008年 | 114篇 |
2007年 | 138篇 |
2006年 | 147篇 |
2005年 | 133篇 |
2004年 | 100篇 |
2003年 | 87篇 |
2002年 | 91篇 |
2001年 | 70篇 |
2000年 | 58篇 |
1999年 | 58篇 |
1998年 | 46篇 |
1997年 | 41篇 |
1996年 | 31篇 |
1995年 | 36篇 |
1994年 | 41篇 |
1993年 | 31篇 |
1992年 | 46篇 |
1991年 | 27篇 |
1990年 | 26篇 |
1989年 | 31篇 |
1988年 | 36篇 |
1987年 | 45篇 |
1986年 | 31篇 |
1985年 | 44篇 |
1984年 | 32篇 |
1983年 | 21篇 |
1982年 | 22篇 |
1981年 | 32篇 |
1980年 | 35篇 |
1979年 | 23篇 |
1978年 | 33篇 |
1977年 | 23篇 |
1976年 | 31篇 |
1975年 | 34篇 |
1974年 | 35篇 |
1973年 | 33篇 |
1971年 | 19篇 |
排序方式: 共有3025条查询结果,搜索用时 31 毫秒
61.
Vaporization of Silver in a Stream of Oxygen Using a transport equipment the vaporization of silver at 611–721°C in a stream of oxygen has been measured. Experiments with detachable cuffs of silver or with wools of silver in a bulb made from quartzglass or silver lead to the same results. By variation of the O2-pressure and the activity of silver is observed that the vaporization happens as Ag2O,g, see “Inhaltsübersicht”. The solid was at first pure silver. During long lasting experiments, however, it is covered with a thin layer of oxygen or silver oxide, which lowers the concentration of Ag2O,g in the equilibrium gas to a smaller, yet constant value. The following measurements using N2 as carrier gas lead to the decomposition of this layer and ends with the very small vapor pressure of silver. The layer of oxygen or silver oxide on the metal could be shown after Davies [2] using mercury. 相似文献
62.
The change in fluorescence quantum yield for indole as a function of excitation wavelength between 250 and 220 nm is found to vary with the static dielectric constant of various alcohol—water mixtures at 296 K. The supports the intermediacy of a CTTS state in the photoionization process. 相似文献
63.
Harald Rotzsche und Harald Rösler 《Fresenius' Journal of Analytical Chemistry》1961,181(1):407-417
Zusammenfassung Bei der Herstellung von Siliconkautschuk verursachte eine uns nicht bekannte Komponente im Ausgangsmaterial Octamethylcyclotetrasiloxan Schwierigkeiten. Es traten bei der Polymerisation mitunter unerwünschte Vernetzungen auf. Gaschromatographisch wurde festgestellt, daß das Vorprodukt Dimethyldichlorsilan noch Methylhydrodichlorsilan enthielt. In dem aus einem solchen Dimethyldichlorsilan hergestellten Octamethylcyclotetrasiloxan fanden wir ebenfalls gaschromatographisch zwischen 0,02 und 0,2% einer uns nicht bekannten Substanz, die an Silicium gebundenen Wasserstoff aufwies. Die gleiche Substanz konnte durch Cohydrolyse der beiden Chlorsilane neben anderen cyclischen Verbindungen dargestellt und isoliert werden. Ihr Retentionsvolumen wurde unter anderem an der Verteilungsflüssigkeit Siliconöl DC 703 bestimmt. Trug man die Logarithmen der Retentionsvolumina dieser cyclischen Verbindungen als Funktion des Molgewichtes auf, so zeigte sich, daß es sich bei dem störenden Bestandteil um Heptamethylcyclotetrasiloxan handelte. An Modellgemischen wurde festgestellt, daß diese Verbindung die D4-Polymerisation tatsächlich stört.Auf die gleiche Weise konnte eine Reihe anderer, bisher noch nicht beschriebener Cyclosiloxane mit Si-H-Bindungen in dem Cohydrolysat aus (CH3)2SiCl2 und CH3HSiCl2 festgestellt werden. In einer Tabelle sind die effektiven und relativen Retentionsvolumina von 18 Cyclosiloxanen angegeben.Bei mehreren dieser Verbindungen sind diese gaschromatographischen Kennzahlen die ersten gemessenen physikalisch-chemischen Daten, da die Mehrzahl der Methylhydrocyclosiloxane noch nicht in reiner Form isoliert worden ist.50. Mitteilung: Rich. Müller, R. Köhne u. S. Sliwinski, J. prakt. Chem., [4] 11, 336 (1960). 相似文献
64.
George Hohlneicher Harald Pulm Hans-Joachim Freund 《Journal of Electron Spectroscopy and Related Phenomena》1985,37(2):209-224
First, we show that the quantity Δβ(i) = ΔEA(kii) + 2ΔEB(i) — ΔEB(k) is directly related to the final state relaxation contribution ΔER(i) of the binding energy shift ΔEB(i). ΔEA(kii) is the kinetic energy shift of the Auger transition which corresponds to the decay of a hole state with a hole in level k into a final state with two holes in level i. The shift parameter Δβ(i), which is based on information on two binding energies, is conceptually similar to Wagner's Auger parameter. To establish the relation between Δβ(i) and ΔR(i) one needs, however, less drastic approximations than in the case of Auger parameter shifts. The only approximation necessary is the assumption that ΔR(i) is determined by coulomb contributions.Secondly, we use Δβ (i) to analyse the experimental data of eighteen gaseous phosphorus-containing compounds obtained by Sodhi and Cavell1. It is shown that ΔR(P2p) is strongly related to changes in the polarizability of the ligands. The initial state effects derived from our study deviate from those expected on the basis of simple electronegativity considerations. 相似文献
65.
66.
Sagi D Peter-Katalinic J Conradt HS Nimtz M 《Journal of the American Society for Mass Spectrometry》2002,13(9):1138-1148
Application of the negative mode electrospray ionization-quadrupole time-of-flight mass spectrometry (ESI QTOF) tandem MS for determination of substitution patterns by sialic acid and/or fucose and extention by additional LacNAc disaccharide units in single branches of multianternary N-glycans from biological samples is described. Fragmentation patterns which can be obtained by low energy collision-induced dissociation (CID) using the QTOF instrument include cleavage ions, diagnostic for determination of antennarity and for specific structural features of single antennae. Systematic fragmentation studies in the negative ion mode were focussed toward formation of the D diagnostic ion relevant for assignment of 3- and 6-antennae in complex N-glycans carrying three and four antennae in combination with epitope-relevant B- and C-type ions. For validation of this approach ESI QTOF fragmentation of the permethylated analogues was carried out in the positive ion mode. Using this strategy, products of in vitro glycosylation reactions were investigated in order to clarify some general aspects of N-glycan acceptor specificity during biosynthesis. Alpha1-3fucosylation using GDP-fucose along with a soluble form of the recombinant human alpha1-3fucosyltransferase VI was carried out on tri- and tetraantennary precursors to test structural requirements for formation of Le(x) versus sLe(x) motifs. 相似文献
67.
A rigid terpyridine ligand containing chiral alkyl chains has been synthesized, characterized and subsequently complexed with ruthenium(II) ions. The product was characterized by MALDI-TOF-MS, UV-vis and NMR. Circular dichroism showed the appearance of extended helical columnar aggregates. 相似文献
68.
Cyclic α-trimethylsilylketones are synthesized from cyclic vinyltrimethylsilanes via the epoxides , and the alcohols . 相似文献
69.
Formation of CoAl3Cl11 at higher Al2Cl6 Pressures The reaction of CoCl2,f with Al2Cl6,g (≈ 3 atm) is investigated considering every component of the gas phase (Al2Cl6, AlCl3, Al3Cl9, CoAlCl5, CoAl2Cl8, CoAl3Cl11) and the deviation from the ideal behaviour. The conclusion is derived that at 600 K from CoCl2,s and larger pressures of Al2Cl6 besides CoAl2Cl8 a small amount of CoAl3Cl11 is formed. 相似文献
70.
Jianhua WangElo Harald Hansen 《Analytica chimica acta》2002,456(2):283-292
An automated sequential injection (SI) on-line solvent extraction-back extraction separation/preconcentration procedure is described. Demonstrated for the assay of cadmium by electrothermal atomic absorption spectrometry (ETAAS), the analyte is initially complexed with ammonium pyrrolidinedithiocarbamate (APDC) in citrate buffer and the chelate is extracted into isobutyl methyl ketone (IBMK), which is separated from the aqueous phase by means of a newly designed dual-conical gravitational phase separator. A metered amount of the organic eluate is aspirated and stored in the PTFE holding coil (HC) of the SI-system. Afterwards, it is dispensed and mixed with an aqueous back extractant of dilute nitric acid containing Hg(II) ions as stripping agent, thereby facilitating a rapid metal-exchange reaction with the APDC ligand and transfer of the Cd into the aqueous phase. The aqueous phase is separated in a second dual-conical gravitational phase separator, and 30 μl of it is entrapped and metered in a sample loop (SL) and subsequently introduced via air segmentation into the graphite tube for analyte quantification. The ETAAS determination is performed in parallel with the separation/preconcentration process of the ensuing sample. An enrichment factor of 21.4, a detection limit of 2.7 ng l−1, along with a sampling frequency of 13 h−1 were obtained at a sample flow rate of 6.0 ml min−1. The precision (R.S.D.) at the 0.4 μg l−1 level was 1.8% as compared to 3.2% when quantifying the organic extractant directly. The applicability of the procedure is demonstrated for the determination of trace levels of cadmium in three certified reference materials. 相似文献