全文获取类型
收费全文 | 1103篇 |
免费 | 59篇 |
国内免费 | 10篇 |
专业分类
化学 | 835篇 |
晶体学 | 7篇 |
力学 | 14篇 |
数学 | 174篇 |
物理学 | 142篇 |
出版年
2023年 | 12篇 |
2021年 | 19篇 |
2020年 | 21篇 |
2019年 | 31篇 |
2017年 | 10篇 |
2016年 | 40篇 |
2015年 | 25篇 |
2014年 | 37篇 |
2013年 | 34篇 |
2012年 | 49篇 |
2011年 | 54篇 |
2010年 | 23篇 |
2009年 | 33篇 |
2008年 | 50篇 |
2007年 | 58篇 |
2006年 | 47篇 |
2005年 | 51篇 |
2004年 | 31篇 |
2003年 | 35篇 |
2002年 | 36篇 |
2001年 | 31篇 |
2000年 | 17篇 |
1999年 | 28篇 |
1998年 | 16篇 |
1997年 | 25篇 |
1996年 | 23篇 |
1995年 | 10篇 |
1994年 | 21篇 |
1993年 | 11篇 |
1992年 | 10篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1984年 | 7篇 |
1983年 | 11篇 |
1982年 | 7篇 |
1981年 | 13篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1978年 | 10篇 |
1977年 | 7篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1973年 | 10篇 |
1972年 | 8篇 |
1967年 | 7篇 |
1956年 | 9篇 |
1927年 | 8篇 |
排序方式: 共有1172条查询结果,搜索用时 0 毫秒
11.
Beate Hager Bettina Schwarzinger Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》2006,137(2):163-168
Summary. Two model compounds for the green fluorescent protein chromophore were prepared. One of them incorporates the natural 4-hydroxybenzylidene
group of the natural tyrosin derived chromophore, the other one bears a methyl group instead of the hydroxy group. Whereas
the photochemically prepared (E)-diastereomer of the first compound very effectively reverted thermally (room temperature) to the thermodynamically stable
(Z)-diastereomer, the (E)-diastereomer of the second derivative proved to be stable even at elevated temperatures for more than a day. This finding
can be rationalized by constructing the appropriate resonance structures showing that only in the first case an effective
delocalization enables partial single bond character of the benzylidene double bond. From the standpoint of chemical etiology,
only Nature’s choice of the tyrosin derived chromophore of the green fluorescent protein provides an efficient radiationless
thermal relaxation channel for the unwanted photo-diastereomerization product formed after excitation besides the dominating
fluorescence channel of its chromophore. 相似文献
12.
The new compounds YNi2P2 and LnNi2P2 (Ln = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm) were prépared by sintering the elemental components in silica tubes. Well-developed crystals were obtained using tin as a flux. They crystallize with the ThCr2Si2 (CeGa2Al2)-type structure which was refined from single-crystal X-ray data for EuNi2P2 to a conventional R value of 0.049 for 118 unique structure factors. While the P atoms in formally isotypic EuCo2P2 are isolated from each other, they form pairs in EuNi2P2. This results in a different ratio and an entirely different bonding situation. A comparison of cell volumes shows that Eu in EuNi2P2 has an intermediate valence. 相似文献
13.
Sila-analoguesA 2 andB 2 of two drugs from the benzhydryl ether class, chlorphenoxamine and clofenetamine, were synthesized for the first time by the steps shown in scheme 1. They and their precursors I–VI were characterized by their physical (Table 1) and chemical properties and their structures confirmed by n.m.r., mass and infrared spectrocopy (Tables 2–5). Their physiological effects were investigated and compared with those of the carbon analogues (Chapter 5).
1. Mitt.:R. Tacke undU. Wannagat, Mh. Chem.106, 1005 (1975).
Mit Auszügen aus der DissertationR. Tacke, Techn. Univ. Braunschweig 1974. 相似文献
1. Mitt.:R. Tacke undU. Wannagat, Mh. Chem.106, 1005 (1975).
Mit Auszügen aus der DissertationR. Tacke, Techn. Univ. Braunschweig 1974. 相似文献
14.
The synthesis of glycopeptides carrying tumour-associated antigens is of interest for cancer diagnosis and treatment. Here, a very efficient route lo disaccharide threonine building block 8 is presented which allows the introduction of the sialyl-Tn antigen into a peptide. The syntheses of the undecapeptide and the sialyl-Tn-containing glycoundecapeptide, which are a part of the repeating unit of MUC1, were performed by solid-phase synthesis with an allylic anchor cleavable under neutral conditions. After detachment from the resin, the peptide and the glycopeptide arc completely deprotected giving the target compounds 13 and 15 , respectively. 相似文献
15.
Petre BA Youhnovski N Lukkari J Weber R Przybylski M 《European journal of mass spectrometry (Chichester, England)》2005,11(5):513-518
Nitration of tyrosine residues in proteins may occur in cells upon oxidative stress and inflammation processes mediated through generation of reactive nitroxyl from peroxynitrite. Tyrosine nitration from oxidative pathways may generate cytotoxic species that cause protein dysfunction and pathogenesis. A number of protein nitrations in vivo have been reported and some specific Tyrosine nitration sites have been recently identified using mass spectrometric methods. High-resolution Fourier transform ion cyclotron resonance mass spectrometry (MALDI) FT-ICR-MS) is shown here to be a highly efficient method in the determination of protein nitrations. Following the identification of nitration of the catalytic site Tyr-430 residue of bovine prostacyclin synthase, we synthesised several model peptides containing both unmodified tyrosine and 3-nitro-tyrosine residues, using solid-phase peptide synthesis (SPPS). The structures of the nitrotyrosine peptides were characterised both by ESI- and by matrix-assisted laser desorption/ionisation (MALDI)-FT-ICR-MS, using a standard ultraviolet (UV) nitrogen nitrogen laser and a 2.97 microm Nd-YAG infrared laser. Using UV-MALDI-MS, 3-nitrotyrosyl-peptides were found to undergo extensive photochemical fragmentation at the nitrophenyl group, which may hamper or prevent the unequivocal identification of Tyr-nitrations in cellular proteins. In contrast, infrared-MALDI-FT-ICR-MS did not produce fragmentation of molecular ions of Tyr-nitrated peptides. 相似文献
16.
17.
Kurt Günther Reinhold Carle Ilona Fleischhauer Stefan Merget 《Fresenius' Journal of Analytical Chemistry》1993,345(12):787-790
Summary A semi-preparative low-pressure liquid-chromatographic procedure using tribenzoylcellulose has been developed for the separation and isolation of the four -bisabolol stereoisomers. Stereochemical assignments were made by HPLC-polarimeter coupling and by using the authentical isomers. This method can be applied to the quality control of chamomile preparations, as it allows the detection of adulterations resulting from admixtures of synthetic -bisabolol. In addition, the isolation of all four -bisabolol stereoisomers from commercially available synthetic -bisabolol has been made possible. 相似文献
18.
Kammerer D Carle R Schieber A 《Rapid communications in mass spectrometry : RCM》2003,17(21):2407-2412
Anthocyanins of black carrots (Daucus carota ssp. sativus var. atrorubens Alef.) were investigated by high-performance liquid chromatography/electrospray ionization mass spectrometry. Besides the main compounds which have already been characterized in detail as cyanidin glycosides, six anthocyanins with m/z 757, 565, 595, 903, 933 and 903 were detected and unambiguously characterized as peonidin and pelargonidin glycosides, based on their fragmentation patterns. Peonidin and pelargonidin were identified after acid hydrolysis by comparison of the fragmentation patterns and retention times of the released aglycones with those of standard compounds. To the best of our knowledge this is the first report on anthocyanins in black carrots consisting of aglycones other than cyanidin. 相似文献
19.
Pagel K Seeger K Seiwert B Villa A Mark AE Berger S Koksch B 《Organic & biomolecular chemistry》2005,3(7):1189-1194
We report here an advanced approach for the characterization of the folding pattern of a de novo designed antiparallel coiled coil peptide by high-resolution methods. Incorporation of two fluorescence labels at the C- and N-terminus of the peptide chain as well as modification of two hydrophobic core positions by Phe/[15N,13C]Leu enable the study of the folding characteristics and of distinct amino acid side chain interactions by fluorescence resonance energy transfer (FRET) and NMR spectroscopy. Results of both experiments reveal the antiparallel alignment of the helices and thus prove the design concept. This finding is also supported by molecular dynamics simulations. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in combination with NMR experiments was used for verification of the oligomerization equilibria of the coiled coil peptide. 相似文献