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81.
The development of the first highly active enantioselective catalyst for the aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates generating valuable almost enantiopure protected allylic amines is described. Usually Z-configured allylic imidates react significantly slower than their E-configured counterparts, but in the present study the opposite effect was observed. Z-Configured olefins have the principal practical advantage that a geometrically pure C=C double bond can be readily obtained, for example, by semihydrogenations of alkynes. Our catalyst, a C(2)-symmetric planar chiral bispalladacycle complex, is rapidly prepared from ferrocene in four simple steps. Key step of this protocol is an unprecedented highly diastereoselective biscyclopalladation providing dimeric macrocyclic complexes of fascinating structure. In the present study as little as 0.1 mol % of catalyst precursor were sufficient for most of the alkyl substituted substrates to give in general almost quantitative yields. NMR investigations revealed a monomeric structure for the active catalyst species. The bispalladacycle can also be used for the formation of almost enantiomerically pure allylic amines (ee > or =96 %) substituted with important functional groups such as ester, ketone, ether, silyl ether, acetal or protected amino moieties providing high-added-value allylic amine building blocks in excellent yield (> or =94 %). The preparative advantages should render this methodology highly appealing as a practical and valuable tool for the formation of allylic amines in target oriented synthesis. 相似文献
82.
Baumann S Schoof S Harkal SD Arndt HD 《Journal of the American Chemical Society》2008,130(17):5664-5666
Proximity-induced covalent capture (PICC) has been established for the investigation of ligand binding to composite protein/oligonucleotide target complexes. The RNA-induced attachment of the thiopeptides Thiostrepton and Nosiheptide to engineered Cys mutants of the ribosomal protein L11 was highly position selective and allowed mapping of their binding site at amino acid resolution. 相似文献
83.
Dr. Nicolas D'Imperio Dr. Valentina Pelliccioli Dr. Sara Grecchi Dr. Alberto Bossi Prof. Francesca Vasile Prof. Silvia Cauteruccio Dr. Anna I. Arkhypchuk Dr. Arvind Kumar Gupta Prof. Dr. Andreas Orthaber Prof. Dr. Sascha Ott Prof. Emanuela Licandro 《European journal of organic chemistry》2023,26(4):e202201209
The first examples of a π-conjugated benzo[b]phosphole P-oxide in which two phosphole P-oxide units are connected by a carbon-carbon double bond are described. The molecules are synthesized as E isomers with respect to the carbon-carbon double bond and exist as stable cis and trans isomers (chiral and meso one respectively) relatively to the two stereogenic P atoms. The optical and electrochemical properties of both isomers have been investigated by experiment and computations. 相似文献
84.
M. Sc. Markus Warnke Tobias Jung Dr. Juri Dermer Karin Hipp Dr. Nico Jehmlich Prof. Dr. Martin von Bergen Sascha Ferlaino Dr. Alexander Fries Prof. Dr. Michael Müller Prof. Dr. Matthias Boll 《Angewandte Chemie (International ed. in English)》2016,55(5):1881-1884
The hydroxylation of vitamin D3 (VD3, cholecalciferol) side chains to give 25‐hydroxyvitamin D3 (25OHVD3) is a crucial reaction in the formation of the circulating and biologically active forms of VD3. It is usually catalyzed by cytochrome P450 monooxygenases that depend on complex electron donor systems. Cell‐free extracts and a purified Mo enzyme from a bacterium anaerobically grown with cholesterol were employed for the regioselective, ferricyanide‐dependent hydroxylation of VD3 and proVD3 (7‐dehydrocholesterol) into the corresponding tertiary alcohols with greater than 99 % yield. Hydroxylation of VD3 strictly depends on a cyclodextrin‐assisted isomerization of VD3 into preVD3, the actual enzymatic substrate. This facile and robust method developed for 25OHVD3 synthesis is a novel example for the concept of substrate‐engineered catalysis and offers an attractive alternative to chemical or O2 /electron‐donor‐dependent enzymatic procedures. 相似文献
85.
Sascha Eichmann 《Journal of Geometric Analysis》2016,26(4):2563-2590
In this note Willmore surfaces of revolution with Dirichlet boundary conditions are considered. We show two nonuniqueness results by reformulating the problem in the hyperbolic half plane and solving a suitable initial value problem for the corresponding elastic curves. The behavior of such elastic curves is examined by a method provided by Langer and Singer to reduce the order of the underlying ordinary differential equation. This ensures that these solutions differ from solutions already obtained by Dall’Acqua, Deckelnick and Grunau. We will additionally provide a Bernstein-type result concerning the profile curve of a Willmore surface of revolution. If this curve is a graph on the whole real numbers it has to be a Möbius transformed catenary. We show this by a corollary of the above-mentioned method by Langer and Singer. 相似文献
86.
Frontispiece: Judicious Ligand Design in Ruthenium Polypyridyl CO2 Reduction Catalysts to Enhance Reactivity by Steric and Electronic Effects
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87.
In this study the temperature stability of several normal phase and RP columns was investigated using a water-only mobile phase. The temperature was adjusted to 120 degrees C for the bare silica stationary phases and to 185 degrees C for the metal oxide and carbon stationary phases. It could be shown that metal oxide stationary phases exhibited excellent thermal stability over the duration of the test period and are therefore suitable for high temperature LC applications. 相似文献
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90.
Ali AA Benson RE Blumentritt S Cameron TS Linden A Wolstenholme D Thompson A 《The Journal of organic chemistry》2007,72(13):4947-4952
The diastereoselective syntheses of Zn(II) bis(dipyrrinato) helicates is reported, involving ligands templated by the incorporation of homochiral binol within the linker joining the two dipyrrinato units. The most diastereoselective formation of dinuclear bis(dipyrrinato) helicates to date is reported. The formation of either mononuclear or dinuclear helicates can be tuned by varying the length of the linker between the dipyrrinato units and by varying the complexation procedure. The neutral dipyrrinato helicates were readily analyzed by HPLC to ascertain diastereoselectivity, and circular dichroism studies revealed the helical nature of the complexes. The molar ellipticities of the helicates produced by diastereoselective complexation are very large in the visible region and typically correspond to binol moieties in the UV region. Extensive X-ray crystallographic investigations further confirmed the helicity of the mononuclear Zn(II) helicates and identified significant interlayer displacement and bending within crystals. 相似文献