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31.
Isocytosine (ICH) exists in solution as two major tautomers, the keto form with N1 carrying a proton (1a) and the keto form with N3 being protonated (1b). In water, 1a and 1b exist in equilibrium with almost equal amounts of both forms present. Reactions with a series of Pd(II) and Pt(II) am(m)ine species such as (dien)Pd(II), (dien)Pt(II), and trans-(NH(3))(2)Pt(II) reveal, however, a distinct preference of these metals for the N3 site, as determined by (1)H NMR spectroscopy. Individual species have been identified by the pD dependence of the ICH resonances. pK(a) values (calculated for H(2)O) for deprotonation of the individual tautomers complexes are 6.5 and 6.4 for the N3 linkage isomers of dienPd(II) and dienPt(II), respectively, as well as 6.2 and 6.0 for the N1 linkage isomers. The dimetalated species [(dienM)(2)(IC-N1,N3)](3+) (M = Pd(II) or Pt(II)) are insensitive over a wide range of pD. The crystal structure analysis of [(dien)Pd(ICH-N3)](NO(3))(2) is reported. Ab initio calculations have been performed for tautomer compounds of composition [(NH(3))(3)Pt(ICH)](2+), cis- and trans-[(NH(3))(2)PtCl(ICH)](+), as well as trans-[(NH(3))(2)Pt(ICH)(2)](2+). Without exception, N3 linkage isomers are more stable, in agreement with experimental findings. As to the reasons for this binding preference, an NBO (natural bond orbital) analysis for [(NH(3))(3)Pt(ICH-N3)](2+)strongly suggests that intramolecular hydrogen bonding between trans-positioned NH(3) ligands and the two exocyclic groups of the ICH is of prime importance. The calculations furthermore show a marked pyramidalization of the NH(2) group of ICH in the complex once the heterocyclic ligand forms a dihedral angle <90 degrees with the Pt coordination plane. 相似文献
32.
Rolf Meyer Zu Kcker Gerlinde Frenzen Bernhard Neumüller Kurt Dehnicke Jrg Magull 《无机化学与普通化学杂志》1994,620(3):431-437
Syntheses and Crystal Structures of the Phosphaneimine Complexes MCl2(Me3SiNPMe3)2 with M = Zn and Co, and CoCl2(HNPMe3)2 The molecular complexes MCl2(Me3SiNPMe3)2 (M = Zn, Co) have been prepared by the reaction of the dichlorides of zinc and cobalt with Me3SiNPMe3 in CH3CN and CH2Cl2, respectively, whereas the complex CoCl2(HNPMe3)2 has been prepared by the reaction of CoCl2 with NaF in boiling acetonitrile in the presence of Me3SiNPMe3. All complexes were characterized by IR spectroscopy and by crystal structure determinations. The complexes MCl2(Me3SiNPMe3)2 crystallize isotypically. ZnCl2(Me3SiNPMe3)2: Space group P212121, Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at ?70°C: a = 1243.6; b = 1319.0; c = 1464.7 pm. CoCl2(Me3SiNPMe3)2: Space group P212121, Z = 4, 3963 observed unique reflections, R = 0,071. Lattice dimensions at ?80°C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoCl2(HNPMe3)2 · CH2Cl2: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at ?80°C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in which the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneimine molecules. 相似文献
33.
The enzymatic elongation of acyl-CoA esters by malonyl-CoA, respectively de novo synthesis of fatty acids from malonyl-CoA by liver microsomes and non particulate fraction of α-tocopherol deficient rats is diminished versus controls. However, liver microsomes of vitamin E deficient rats synthesize more eicosatetraenic acid from γ-linolenic acid and more γ-linolenic acid from linolic acid than do those of tocopherol supplemented animals. It has often been shown that the liver phosphatides of tocopherol deficient rats contain more arachidonic acid than those of controls, a fact which can be explained now by increased activity of the enzymes involved in the biosynthesis of arachidonic acid. Certain polyenic fatty acids are more rapidly synthesized in the absence of naturally occuring antioxidants. Some enzymes of the respiratory chain have also been examined. No vitamin E deficiency effect has been found on enzymes such as gluconate-6-P-dehydrogenase, isocitrate-dehydrogenase, malate-dehydrogenase and lactate dehydrogenase contained in the non particulate fraction. Sonicated mitochondria of tocopherol deficient rats show a greater activity towards cytochrome, oxydase and β-hydroxy-acetyl-CoA-dehydrogenase than controls, possibly due to ultrastractural alteration of this particle. 相似文献
34.
Reinhard Schubert Achim Ansmann Paul Bleckmann Bernhard Schrader 《Journal of Molecular Structure》1975,26(2):429-438
By using the values of the vibrational frequencies of normal and deuterated cyclopropenone (II-d0 , II-d2 ) and 16 O-and 18 O-substituted dimethylcyclopropenone (III) as -well as the infrared and Raman intensities of II a consistent set of force constants has been derived for the cyclopropenone skeleton. The derived values show that the zwitterionic form makes a substantial contribution to the electronic ground state of the molecule. The combined frequency and intensity calculation - simulation of the infrared and the Raman spectrum - is shown to be a good method for making a proper assignment of calculated and observed vibrations and deriving realistic sets of force constants. 相似文献
35.
Boisguerin P Leben R Ay B Radziwill G Moelling K Dong L Volkmer-Engert R 《Chemistry & biology》2004,11(4):449-459
SPOT synthesis permits parallel synthesis and screening of thousands of cellulose membrane-bound peptides to study protein-protein interactions in a proteomic context. Recognition of C-terminal residues is one of the most common binding features of PDZ domains. Unfortunately, most solid support-bound peptide libraries lack a free C terminus due to C-terminal fixation on the solid support. To overcome this restriction, we developed a robust methodology based on our previous strategy for generating peptides with authentic C termini. To validate this improved method, we screened a human peptide library of 6223 C termini with the syntrophin PDZ domain. Furthermore, using the same library, new peptide ligands derived from membrane proteins and receptors were found for the ERBIN PDZ domain. Finally, we identified the protein kinase breakpoint cluster region, which is known as a negative regulator of cell proliferation and oncogenic transformation, as an ERBIN ligand. 相似文献
36.
Reaction of tBuPLi2 with Carbodiimides The reaction of bis(cyclohexyl)carbodiimide with tBuPLi2 in THF at 20 °C leads to the tetranuclear Li‐complex [Li4(THF)2{tBuP([cHexN]2C)2}2] ( 1 ). No addition on the carbodiimide but a silyl transfer was observed under similar conditions during the treatment of bis(trimethylsilyl)carbodiimide with tBuPLi2 to give the lithium salts tBuP(SiMe3)Li and [Li(THF)(Me3SiN‐C≡N)]n ( 2 ). 1 was characterized by NMR, IR and RE spectroscopy, mass spectrometry and X‐ray analyses. Theoretical calculations were performed for 1 . According to the structural investigations 1 consists ofa central centrosymmetrical twelve‐membered Li2N4C4P2 ring adjacent by two six‐membered LiN2C2P rings. The peripheric Li+ cations posssess coordination number (cn) 3 buildt‐up by two N atoms and a THF ligand, while the two central Li+ cations possess only cn 2. However, the theoretical calculations have shown no relevant bonding Li···Li or Li···P interaction. 相似文献
37.
The values of ΔG, ΔH and ΔS for the formation of the mixed 1:1:1 lanthanide EDTA complexes with the anions of 8-hydroxyquinoline-5-sulfonic acid, iminodiacetic acid and nitrilotriacetic acid were determined by pH-titrations and a direct calorimetric method. These thermodynamic data are discussed and compared with those for the formation of the Ln(III)EDTA complexes. Contrary to current opinion it is concluded that all trivalent lanthanide aquoions have the same coordination number in dilute solution. However, in the series of the lanthanide EDTA complexes the coordination number changes between Sm and Tb. In this region, equilibria occur between two types of EDTA complexes with different numbers of coordinated water molecules: The corresponding equilibrium constants could be evaluated. The coordination number changes also in many other Ln complexes along the lanthanide series, and similar equilibria occur. 相似文献
38.
Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical .CHMeCO2(t‐Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain. 相似文献
39.
Wolfgang Reischl Harald Bernhard Christoph Kratky Erich Zbiral 《Monatshefte für Chemie / Chemical Monthly》1985,116(6-7):831-839
Epoxidation of vitamin D3 with benzonitrile ¦H2O2¦ KHCO3 (Payne's reagent) yields exclusively the 5,6-mono-oxirane2. Further epoxidation with the same reagent gives the 5,6-7,8-bisepoxide3 a. Its stereochemistry and therefore the stereochemistry of2 was established by single crystal X-ray analysis of thep-Brbenzoate3b. Thereby for the first time a directive effect of a homoallylic hydroxyl group during thePayne-epoxidation was established.
Herrn Prof.Mihailovic (Universität Belgrad) mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
40.
Diorganogallium Fluorides. The Crystal Structure of the Mixed Crystal [B(CH2Ph)3]0.92[Ga(CH2Ph)3]0.08 · NCMe The reaction of GaR3 with BF3 · OEt2 in diethylether leads to the diorganogallium fluorides R2GaF [R = i-Pr ( 1 ), CH2Ph ( 2 ), Mes ( 3 )]. Compound 1 is also available by the reaction of i-Pr2GaBr ( 6 ) with KF at ?20°C in acetonitrile. The by-product B(CH2Ph)3, formed together with 2 during the first reaction, crystallizes with ca. 8% Ga(CH2Ph)3 in acetonitrile as [B(CH2Ph)3]0.92[Ga(CH2Ph)3]0.08 · NCMe ( 4 ) in the space group P21/n with a = 1050.32(7) pm, b = 1159.5(2) pm, c = 1591.6(1) pm and β = 96.931(6)°. 相似文献