全文获取类型
收费全文 | 1473篇 |
免费 | 23篇 |
国内免费 | 6篇 |
专业分类
化学 | 920篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 194篇 |
物理学 | 371篇 |
出版年
2019年 | 11篇 |
2016年 | 16篇 |
2015年 | 14篇 |
2014年 | 18篇 |
2013年 | 34篇 |
2012年 | 45篇 |
2011年 | 44篇 |
2010年 | 36篇 |
2009年 | 27篇 |
2008年 | 60篇 |
2007年 | 45篇 |
2006年 | 65篇 |
2005年 | 42篇 |
2004年 | 35篇 |
2003年 | 28篇 |
2002年 | 43篇 |
2001年 | 26篇 |
2000年 | 32篇 |
1999年 | 24篇 |
1998年 | 31篇 |
1997年 | 25篇 |
1996年 | 26篇 |
1995年 | 41篇 |
1994年 | 32篇 |
1993年 | 28篇 |
1992年 | 23篇 |
1991年 | 21篇 |
1990年 | 21篇 |
1989年 | 15篇 |
1988年 | 26篇 |
1987年 | 17篇 |
1986年 | 21篇 |
1985年 | 23篇 |
1984年 | 21篇 |
1983年 | 13篇 |
1982年 | 17篇 |
1981年 | 26篇 |
1980年 | 17篇 |
1979年 | 14篇 |
1978年 | 30篇 |
1977年 | 22篇 |
1976年 | 25篇 |
1975年 | 20篇 |
1974年 | 26篇 |
1973年 | 26篇 |
1970年 | 20篇 |
1968年 | 10篇 |
1967年 | 16篇 |
1966年 | 12篇 |
1965年 | 17篇 |
排序方式: 共有1502条查询结果,搜索用时 91 毫秒
81.
82.
83.
Dietrich Gudat Martin Schrott 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Examples for 2-D shift correlations between 31P and another heteronucleus via nX-detected 2D-INJZPT or 31P-detected HMQC experiments are presented. The former technique is best suited for 31P, 15N correlations and permits the determination of intramolecular connectivities as well as of relative signs of couplings.1 The “inverse” HMQC expenment allows easy recording of the 77Se NMR spectrum of an equilibrium mixture of 2 and 33, disregarding the severe exchange broadening of the 77Se-resonances 相似文献
84.
Dietrich Gudat Asadollah Haghverdi Timo Gans-Eichler Martin Nieger 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1637-1640
The high intrinsic stability of 1,3,2-diazaphospholenium cations enhances ionic polarization of covalent P--X bonds in P -halogeno- and P -hydrido-diazaphospholenes. The physical properties of the latter suggest a hydridic nature of the P--H bond, and their reactivities display an "Umpolung" as compared to known reaction patterns of phosphines. 相似文献
85.
David Gode Christian Schmitt Matthias Engel Dietrich A. Volmer 《Analytical and bioanalytical chemistry》2014,406(12):2841-2852
Enzyme-catalyzed reactions play key roles in disease pathology, thus making them relevant subjects of therapeutic inhibitor screening experiments. Matrix-assisted laser desorption/ionization (MALDI) assays have been demonstrated to be able to replace established screening approaches. They offer increased sample throughput, but care must be taken to avoid instrumental bias from differences in ionization efficiencies. We compared a MALDI-triple-quadrupole (QqQ) method for the Dyrk1A peptide substrate woodtide to LC–MS, liquid chromatography with ultraviolet detection (LC–UV), luminescence, and radiometric assays. MALDI measurements were performed on a MALDI-QqQ instrument in the multiple-reaction monitoring mode. Different MALDI conditions were investigated to address whether matrix type, sample support, and MRM- or SIM-based detection conditions can be used to accommodate the molar responses of substrate peptide and its phosphorylated form. UV detection served as a reference method. The impact of MALDI matrix on IC50 values was small, even considering that matrix preparations were used that are known to alleviate response differences. IC50 values determined by MALDI were ca. 2-fold lower than those determined by LC–UV. Although MALDI generated lower ion yields for the phosphorylated peptide than for the peptide substrate, we found that a correction of compound potencies was readily possible using correction factors based on unbiased LC–UV results. A thorough method development delivered a robust assay with excellent performance (Z′ > 0.91) that was close to that seen for LC–UV. Figure
? 相似文献
86.
Highly Selective Dimerization and Trimerization of Isobutene to Linearly Linked Products by Using Nickel Catalysts 下载免费PDF全文
Prof. Arno Behr Nils Rentmeister Thomas Seidensticker Jonas Vosberg Dr. Stephan Peitz Dr. Dietrich Maschmeyer 《化学:亚洲杂志》2014,9(2):596-601
The unique linear linkage of isobutene to generate highly valuable C8 precursors for plasticizers is feasible by using special nickel catalysts. (4‐Cyclooctene‐1‐yl)(1,1,1,5,5,5‐hexafluoro‐2,4‐acetylacetonato)nickel and aluminum‐alkyl‐activated nickel acetylacetonates produce isobutene dimers with high selectivities of up to 95 %. Moreover, selectivity for the head‐to‐head products (2,5‐dimethylhexenes) is remarkably high at up to 99 %. Additionally, novel C12 isobutene trimers are also formed with a very high selectivity of up to 99 % for the linear linkage. The trimer structure (2,5,8‐trimethylnonenes) reflects the stepwise characteristic of the reaction mechanism. Pathways of insertion and activation and the deactivation processes of the catalyst are discussed in detail. 相似文献
87.
Thomas D. Hettich Richard Rudolf Dr. Christoph M. Feil Nicholas Birchall Dr. Martin Nieger Prof. Dr. Dr. h. c. Dietrich Gudat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(17):5412-5416
Unprecedented metalated phosphonite boranes were prepared from PH-substituted precursors and silyl amides. Although potassium derivatives were thermally stable and could even be isolated and structurally characterised, lithiated analogues proved to be unstable towards self-condensation under cleavage of LiOR at ambient temperature. Reaction studies revealed that the metalated phosphonite boranes exhibit ambiphilic character. Their synthetic potential as nucleophilic building blocks was demonstrated in the synthesis of the first stannylated phosphonite representing a new structural motif in phosphine chemistry. 相似文献
88.
89.
Dennis A. Buschmann Dr. H. Martin Dietrich Dr. David Schneider Dr. Verena M. Birkelbach Dr. Christoph Stuhl Prof. Dr. Karl W. Törnroos Dr. Cäcilia Maichle-Mössmer Prof. Dr. Reiner Anwander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(47):10834-10840
Tetramethylaluminato/halogenido(X) ligand exchange reactions in half-sandwich complexes [CpRLa(AlMe4)2] are feasible in non-coordinating solvents and provide access to large coordination clusters of the type [CpRLaX2]x. Incomplete exchange reactions generate the hexalanthanum clusters [CpR6La6X8(AlMe4)4] (CpR=Cp*=C5Me5, X=I; CpR=Cp′=C5H4SiMe3, X=Br, I). Treatment of [Cp*La(AlMe4)2] with two equivalents Me3SiI gave the nonalanthanum cluster [Cp*LaI2]9, while the exhaustive reaction of [Cp′La(AlMe4)2] with the halogenido transfer reagents Me3GeX and Me3SiX (X=I, Br, Cl) produced a series of monocyclopentadienyl rare-earth-metal clusters with distinct nuclearity. Depending on the halogenido ion size the homometallic clusters [Cp′LaCl2]10 and [Cp′LaX2]12 (X=Br, I) could be isolated, whereas different crystallization techniques led to the aggregation of clusters of distinct structural motifs, including the desilylated cyclopentadienyl-bridged cluster [(μ-Cp)2Cp′8La8I14] and the heteroaluminato derivative [Cp′10La10Br18(AlBr2Me2)2]. The use of the Cp′ ancillary ligand facilitates cluster characterization by means of NMR spectroscopy. 相似文献
90.