全文获取类型
收费全文 | 2704篇 |
免费 | 43篇 |
国内免费 | 9篇 |
专业分类
化学 | 1893篇 |
晶体学 | 15篇 |
力学 | 41篇 |
数学 | 569篇 |
物理学 | 238篇 |
出版年
2016年 | 34篇 |
2015年 | 34篇 |
2014年 | 35篇 |
2013年 | 118篇 |
2012年 | 56篇 |
2011年 | 75篇 |
2010年 | 41篇 |
2009年 | 70篇 |
2008年 | 85篇 |
2007年 | 64篇 |
2006年 | 73篇 |
2005年 | 82篇 |
2004年 | 79篇 |
2003年 | 66篇 |
2002年 | 68篇 |
2001年 | 61篇 |
2000年 | 50篇 |
1999年 | 25篇 |
1998年 | 38篇 |
1997年 | 49篇 |
1996年 | 46篇 |
1995年 | 35篇 |
1994年 | 50篇 |
1993年 | 45篇 |
1992年 | 47篇 |
1991年 | 38篇 |
1990年 | 43篇 |
1989年 | 61篇 |
1988年 | 68篇 |
1987年 | 65篇 |
1986年 | 31篇 |
1985年 | 46篇 |
1984年 | 50篇 |
1983年 | 26篇 |
1982年 | 46篇 |
1981年 | 48篇 |
1980年 | 68篇 |
1979年 | 49篇 |
1978年 | 49篇 |
1977年 | 30篇 |
1976年 | 32篇 |
1975年 | 49篇 |
1974年 | 39篇 |
1973年 | 45篇 |
1972年 | 33篇 |
1971年 | 35篇 |
1970年 | 32篇 |
1969年 | 18篇 |
1967年 | 26篇 |
1966年 | 25篇 |
排序方式: 共有2756条查询结果,搜索用时 15 毫秒
51.
Kraus RM Lagoudakis PG Müller J Rogach AL Lupton JM Feldmann J Talapin DV Weller H 《The journal of physical chemistry. B》2005,109(39):18214-18217
We study the interplay between Auger effects and ionization processes in the limit of strong electronic confinement in core/shell CdSe/ZnS semiconductor nanocrystal quantum dots. Spectrally resolved fluorescence decay measurements reveal a monotonic increase of the photoluminescence decay rate on excitation density. Our results suggest that Auger recombination accelerates ionization processes that lead to the occupation of dark, nonemissive nanocrystal states. A model is proposed in the quantized Auger regime describing these experimental observations and providing an estimate of the Auger assisted ionization rates. 相似文献
52.
Larry I. Amstutz Horst Meyer Samuel M. Myers
Robert L. Mills
《Journal of Physics and Chemistry of Solids》1969,30(12):2693-2697Measurements of T1 in the hep phase of H2, over the temperature range 2°–12°K and the ortho concentration range between 0.5 and 0.97 are presented. At temperatures below 10°K, the thermally activated self-diffusion is negligible and the mechanism for nuclear relaxation is that attributed by Moryia and Motizuki and by Harris to intramolecular dipolar interaction, modulated by intennolecular electric quadrupole-quadrupole (EQQ) interaction. The gaussian approximation for the correlation function was used by these authors to predict T1. From the comparison between experiment and theory, we determine the EQQ parameter Γ/kB to be 0.67°K. Above 10°K the effect of diffusion influences T1, and the experimental results for an 88 per cent ortho H2 sample up to the melting point suggest that the relaxation mechanisms resulting from EQQ interaction and diffusion are not independent of one another. 相似文献
53.
In contrast to normal cells, the glycoprotein profile on epithelial tumor cells is distinctly altered. Due to an incomplete formation of the glycan side-chains resulting from a premature sialylation, additional peptide epitopes become accessible to the immune system in mucin-type glycoproteins on tumor cells. These tumor-associated structure alterations constitute the basis for a selective immunological attack on cancer cells. For the construction of immunostimulating antigens, glycopeptide partial structures from the mucins MUC1 and MUC4 carrying the tumor-associated sialyl-T(N), alpha2,6-sialyl-T and alpha2,3-sialyl-T antigens have been synthesized. Employing different linkers such as the allylic HYCRON or the fluoride-sensitive PTMSEL anchor, the antigenic glycopeptide structures were constructed on the solid phase utilizing pre-assembled glycosyl amino acid building blocks prepared in solution by convergent chemical or chemoenzymatic strategies. The proliferation of cytotoxic T cells has been induced applying a construct composed of a sialyl-T(N) MUC1-glycopeptide conjugated with a tetanus toxin T cell peptide epitope. 相似文献
54.
Wolf-Dieter Fessner Gottfried Sedelmeier Lothar Knothe Horst Prinzbach Grety Rihs Zhong-Zhi Yang Branka Kova
Edgar Heilbronner 《Helvetica chimica acta》1987,70(7):1816-1842
‘Face-to-Face’ Benzo-anellated Homologous Hypostrophenes. Syntheses, X-Ray-Structure Analyses and PE Spectra ‘Face-to-face’ Benzo-anellated homologous hypostrophenes (series M ), of interest as substrates for [6 + 6]-photocycloaddition reactions, have been synthesized. From X-ray structural analyses of 13b and 13c shortest C? C distances of 2.80(2.76)/2.71 Å and interorbital angles (ω) of 129° (128°)/130° between the benzene rings have been determined. The PE spectra are discussed in the context of transannular π,π interactions. 相似文献
55.
56.
The crystal structure of the title compound has been determined from single crystal X-ray diffraction data and refined toR=0.125. The unit cell is triclinic, space group P,
(No. 2),a=5.688(1),b=5.701(1),c=8.583(1) Å, =81.32(1), =71.50(1), =67.95(1)° andZ=2. The structure consists of isolated [GeO4] tetrahedra linked together by four- and five-coordinate sodium atoms. Na4GeO4 is isostructural with Na4CoO4 (which has been described to be non-centrosymmetric and for which a centrosymmetric model is presented), K4GeO4, K4SnO4 and K4PbO4. 相似文献
57.
Horst Weitkamp und Friedhelm Korte 《Fresenius' Journal of Analytical Chemistry》1964,204(4):245-263
Zusammenfassung Die Spin-Spin-Kopplungskonstanten der olefinischen Protonen mit dem 31P sowie die Feinstruktur der 1H-NMR-Spektren sind charakteristisch für die Lage der Doppelbindung. Vielfach kann auch die Intensität der
C=C-Schwingung im IR zur Bestimmung der Doppelbindungslage benutzt werden. Massenspektren geben nur in Ausnahmefällen Hinweise, können jedoch zur exakten Bestimmung des Molekulargewichts dienen.
Die Ausführung der Untersuchungen erfolgte unter Mitarbeit von Herrn F. Dlugosch, Herrn H. Au und Fräulein R. Barth.
Herrn Dr. C. A. Reilly, Shell-Development Company, Emeryville, USA, danken wir für die Überlassung getesteter Programmkartensätze zur Berechnung der NMR-Spektren. 相似文献
Summary The spin-spin coupling constants of the olefinic protons with the phosphorus-31 as well as the fine structure of the nmr-spectra are characteristic for the position of the double bond. In the infrared, the intensity of the C=C-frequency may often serve as indication of the position of the double bond. The applicability of mass spectra is limited to a small number of compounds. They may be used, however, for an accurate determination of the molecular weight.
Die Ausführung der Untersuchungen erfolgte unter Mitarbeit von Herrn F. Dlugosch, Herrn H. Au und Fräulein R. Barth.
Herrn Dr. C. A. Reilly, Shell-Development Company, Emeryville, USA, danken wir für die Überlassung getesteter Programmkartensätze zur Berechnung der NMR-Spektren. 相似文献
58.
Friedrich Bossert Horst Meyer Egbert Wehinger 《Angewandte Chemie (International ed. in English)》1981,20(9):762-769
The aryldihydropyridines first prepared by Hantzsch almost 100 years ago have recently been found to be highly effective calcium antagonists with suitable pharmacological profiles. An illustrative example is dimethyl-l,4-dihydro-2,6-dimethyl-4-(o-nitrophenyl)pyridine-3,5-dicarboxylate (Nifedipine) which is already employed therapeutically. This substance lowers the frequency of attack of angina pectoris and reduces blood pressure. The discovery of the therapeutic activity of this class of substances initiated renewed investigation of the Hantzsch condensation and the synthesis of numerous 4-aryldihydropyridines and related compounds. Qualitative and quantitative structure/activity relationships of these substances can be deduced from their biological data. 相似文献
59.
Roswitha Stejskal Ernst Urban Horst Völlenkle 《Monatshefte für Chemie / Chemical Monthly》1991,122(3):145-156
Summary Oxidation of isobenzofuranone1 yielded in a diastereoselective reaction epoxide2. Acidolysis of2 resulted in a mixture oftrans-glycols6 a (88%) and7 a (4%), which were separated by crystallization. The relative configuration of6 a and7 a at the chiral centers 3 a, 5, 6, and 7 a was determined by1H-NMR-spectroscopy and X-ray analysis of O-acetylated and 7 a-methylated derivatives. 相似文献
60.
Eberling J Braun P Kowalczyk D Schultz M Kunz H 《The Journal of organic chemistry》1996,61(8):2638-2646
The selective C-terminal deprotection of O-glycopeptide (methoxyethoxy)ethyl esters is achieved under mild conditions (pH 6.6, 37 degrees C) by enzymatic hydrolysis using papain or lipase M from Mucor javanicus to give building blocks useful for chain-extending glycopeptide synthesis. On the other hand, the selective removal of acetyl protecting groups from the saccharide portion of glycopeptides is accomplished by alternative enzymatic hydrolysis with lipase WG from wheat germ to furnish model substrates for enzymatic glycosyl transfer reactions in order to extend the carbohydrate side chain of these conjugates. 相似文献