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71.
Ewald Sattler Harald Krautscheid Eberhard Matern Gerhard Fritz Ilona Kovcs 《无机化学与普通化学杂志》2001,627(2):186-193
Formation and Reactions of the CH2Li‐Derivatives of tBu2P–P=P(CH3)tBu2 and (Me3Si)tBuP–P=P(CH3)tBu2 With nBuLi, (Me3Si)tBuP–P=P(CH3)tBu2 ( 1 ) and tBu2P–P=P(CH3)tBu2 ( 2 ) yield (Me3Si)tBuP–P=P(CH2Li)tBu2 ( 3 ) and tBu2P–P=P(CH2Li)tBu2 ( 4 ), wich react with Me3SiCl to give (Me3Si)tBuP–P=P(CH2–SiMe3)tBu2 ( 5 ) and tBu2P–P=P(CH2–SiMe3)tBu2 ( 6 ), respectively. With tBu2P–P(SiMe3)–PtBuCl ( 7 ), compound 3 forms 5 as well as the cyclic products [H2C–P(tBu)2=P–P(tBu)–PtBu] ( 8 ) and [H2C–P(tBu)2=P–P(PtBu2)–P(tBu)] ( 9 ). Also 3 forms 8 with tBuPCl2. The cleavage of the Me3Si–P‐bond in 1 by means of C2Cl6 or N‐bromo‐succinimide yields (Cl)tBuP–P=P(CH3)tBu2 ( 10 ) or (Br)tBuP–P=P(CH3)tBu2 ( 11 ), resp. With LiP(SiMe3)2, 10 forms (Me3Si)2P–P(tBu)–P=P(CH3)tBu2 ( 12 ), and Et2P–P(tBu)–P=P(CH3)tBu2 ( 13 ) with LiPEt2. All compounds are characterized by 31P NMR Data and mass spectra; the ylide 5 and the THF adduct of 4 additionally by X‐ray structure analyses. 相似文献
72.
Reaction of the chiral lithium stannate [HC{SiMe2N[(S)–CH(Me)Ph]}3SnLi(thf)] ( 1 ) with Me3SnCl gave the corresponding distannane [HC{SiMe2N[(S)–CH(Me)Ph]}3Sn–SnMe3] ( 2 ) in good yield. Its [2,2,2]bicyclooctane‐related cage structure, comprising the trisilylsilane unit and the triamido‐tin fragment, as well as the Sn–Sn bond (2.7978(15)–2.8020(15) Å in the three crystallographically independent molecules) were established by a single crystal X‐ray structure analysis: Space proup P3, Z = 3, lattice dimensions at 293(2) K: a = 17.724(3), c = 10.597(2) Å, R = 0.0374. 相似文献
73.
Jrg Schrder Herbert Wenzel Hans‐Georg Stammler Anja Stammler Beate Neumann Harald Tschesche 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(5):593-596
The title compounds, (2S)‐N‐[5‐(4‐chlorophenyl)‐2,3‐dihydro‐6H‐1,3,4‐thiadiazin‐2‐ylidene]‐2‐[(phenylsulfonyl)amino]propanamide, C18H17ClN4O3S2, (I), (2R)‐N‐[5‐(4‐fluorophenyl)‐6H‐1,3,4‐thiadiazin‐2‐yl]‐2‐[(phenylsulfonyl)amino]propanamide, C18H17FN4O3S2, (II), and (2S)‐N‐[5‐(5‐chloro‐2‐thienyl)‐6H‐1,3,4‐thiadiazin‐2‐yl]‐2‐[(phenylsulfonyl)amino]propanamide, C16H15ClN4O3S3, (III), are potent inhibitors of matrix metalloproteinases. In all three compounds, the thiadiazine ring adopts a screw‐boat conformation. The molecules of compound (I) show a short intramolecular NAla—H?Nexo hydrogen bond [N?N 2.661 (3) Å] and are linked into a chain along the c axis by Nendo—H?Sendo and Nendo—H?OAla hydrogen bonds [N?S 3.236 (3) and N?O 3.375 (3) Å] between neighbouring molecules. In compound (II), the molecules are connected antiparallel into a chain along the a axis by Nexo—H?OAla and NAla—H?Nendo hydrogen bonds [N?O 2.907 (6) and N?N 2.911 (6) Å]. The molecules of compound (III) are dimerized antiparallel through Nexo—H?Nendo hydrogen bonds [N?N 2.956 (7) and 2.983 (7) Å]. The different hydrogen‐bonding patterns can be explained by an amido–imino tautomerism (prototropic shift) shown by different bond lengths within the 6H‐1,3,4‐thiadiazine moiety. 相似文献
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76.
Oxidefluorides of Niobium and Tantalum The reaction of NbF5 with SiO2 (silica glass ampules) at 310°C or with SiO2 (Aerosil) at 180°C always leads to NbO2F. To the contrary the reaction with laboratory glass (Jenaer Geräteglas) at 130°C leads to NbOF3. TaF5 reacts in silica glass ampules at 400°C by formation of TaO2F, however at 300°C or 260°C by formation of TaOF3. Silica glass did not react with NbF5 at 130°C, however Nb2O5 and NbF5 gave at 130°C in silica glass ampoules NbOF3. Similarly, TaF5 and Ta2O5 or TaO2F formed at 260°C in nickel ampoules TaOF3. The chemical and the thermochemical behaviour of oxidefluorides have been investigated. The compounds NbOF3 and TaOF3 are isomorphic. Lattice constants are mentioned. 相似文献
77.
Towards a Sustainable Synthesis of Oxymethylene Dimethyl Ether by Homogeneous Catalysis and Uptake of Molecular Formaldehyde 下载免费PDF全文
Andreas Peter Samuel M. Fehr Valentin Dybbert Dr. Daniel Himmel Ines Lindner Dr. Eberhard Jacob Mohamed Ouda Dr. Achim Schaadt Dr. Robin J. White Dr. Harald Scherer Prof. Dr. Ingo Krossing 《Angewandte Chemie (International ed. in English)》2018,57(30):9461-9464
Oxymethylene dimethyl ethers (OMEn; CH3(‐OCH2‐)nO‐CH3, n=3–5) are a novel class of sustainable synthetic fuels, which are of increasing interest due to their soot‐free combustion. Herein a novel anhydrous OMEn synthesis route is presented. Catalyzed by trimethyloxonium salts, dimethoxymethane takes up monomeric gaseous formaldehyde instantaneously and forms high purity OMEn at temperatures of 25–30 °C. This new anhydrous approach using molecular formaldehyde and catalytic amounts of highly active trimethyloxonium salts represents a promising new step towards a sustainable formation of OMEn emanating from CO2 and H2. 相似文献
78.
Peptide-based molecular probes identified by bacteriophage (phage) display technology expand the peptide repertoire for in vivo diagnosis and therapy of cancer. Numerous peptides that bind cancer-associated antigens have been discovered by panning phage libraries. However, until now only few of the peptides selected by phage display have entered clinical applications. The success of phage derived peptides essentially depends on the quality of the library screened. This review summarizes the methods to achieve highly homogenous libraries that cover a maximal sequence space. Biochemical and chemical strategies for the synthesis of DNA libraries and the techniques for their integration into the viral genome are discussed in detail. A focus is set on the methods that enable the exclusion of disturbing sequences. In addition, the parameters that define the variability, the minimal numbers of copies per library and the use of alternating panning cycles to avoid the loss of selected hits are evaluated. 相似文献
79.
Dr. Jindong Ren Dr. Henning Klaasen Melanie C. Witteler Lena Viergutz Prof. Dr. Johannes Neugebauer Dr. Hong-Ying Gao Prof. Dr. Armido Studer Prof. Dr. Harald Fuchs 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16727-16732
The reactivity of aryl triflates in on-surface C−C coupling is reported. It is shown that the triflate group in aryl triflates enables regioselective homo coupling with preceding or concomitant hydrodetriflation on Cu(111). Three different symmetrical π-systems with two and three triflate functionalities were used as monomers leading to oligomeric conjugated π-systems. The cascade, comprising different intermediates at different reaction temperatures as observed for one of the molecules, proceeds via initial removal of the trifluoromethyl sulfonyl group to give an aryloxy radical which in turn is deoxygenated to the corresponding aryl radical. Thermodynamically driven regioselective 1,2-hydrogen atom transfer leads to a translocated aryl radical which in turn undergoes coupling. For a sterically more hindered bistriflate, where one ortho position was blocked, dehydrogenative coupling occurred at remote position with good regioselectivity. Starting materials, intermediates as well as products were analyzed by scanning tunneling microscopy. Structures and suggested mechanism were further supported by DFT calculations. 相似文献
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