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21.
I.J. Galpin F.E. Hancock B.K. Handa A.G. Jackson G.W. Kenner R. Ramage B. Singh 《Tetrahedron》1979,35(23):2791-2794
Combination of the protected peptide fragments 1–16, 17–26 and 27–37 to yield the 1–37 portion of a lysozyme analogue is described. The fragments were combined using DCCI with the addition of HONSu, and the products purified mainly by gel filtration. 相似文献
22.
Apffel A Yin H Hancock WS McManigill D Frenz J Wu SL 《Journal of chromatography. A》1999,832(1-2):149-163
A system is described which allows operation of a range of capillary based liquid phase separations including capillary electrophoresis, isocratic and gradient capillary electrochromatography, isocratic and gradient capillary liquid chromatography and electrically assisted gradient capillary liquid chromatography. The system was coupled to electrospray ionization mass spectrometry in the electrically assisted capillary liquid chromatography mode to investigate the effect of applied voltage on the selectivity in peptide mapping separations. Analyses were performed on tryptic digests of recombinant human growth hormone and tissue plasminogen activator. The results show a small but useful effect on selectivity that can be used to fine tune specific separations. 相似文献
23.
A differential pulse voltammetric study of complexes of Cd(II) and Pb(II) with crown ethers is reported. Measured log K(1) values for Cd(II) with 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane), and 12-crown-4 (1,4,7,10-tetraoxacyclododecane) are respectively 2.53 (+/-0.06), 1.97 (+/-0.07), and 1.72 (+/-0.08) and for Pb(II) with 18-crown-6 is 4.17 (+/-0.03), all at 25 degrees C in 0.1 M LiNO(3). Cd(II) is smaller than is usually associated with strong bonding with crown ethers. The high log K(1) values for Cd(2+) with crown ethers found here are discussed in terms of distortion of Cd(II) by relativistic effects. The resulting plasticity of the coordination geometry of the Cd(II) ion allows it to meet the metal ion size requirements of all the crown ethers, allowing high log K(1) values to occur. Crystal structures for [Cd(bz-18-crown-6)(SCN)(2)] (1) (bz-18-crown-6 = benzo-1,4,7,10,13,16-hexaoxacyclooctadecane) and [K(18-crown-6)][Cd(SCN)(3)] (2) are reported. 1 was triclinic, space group P1, a = 8.5413(2), b = 10.0389(2), and c = 13.4644(2) A, alpha = 94.424(1), beta = 102.286(1), and gamma = 93.236(1) degrees, Z = 2, and final R = 0.023. 2 was orthorhombic, space group Cmc2(1), a = 14.7309(3), b = 15.1647(3), and c = 10.6154(2) A, Z = 4, and final R = 0.020. In 1, the Cd occupies the cavity of the bz-18-crown-6 with long average Cd-O bond lengths of 2.65 A and is N-bonded to the thiocyanates with short average Cd-N bonds of 2.12 A. In [Cd(bz-18-crown-6)(SCN)(2)], the linear coordination involving the Cd and the two N-bonded thiocyanate groups in 1 is discussed in terms of the role of relativistic effects in the tendency to linear coordination geometry in group 12 metal ions. In 2 Cd forms a polymeric structure involving thiocyanate bridges between Cd atoms and K(+) occupies the cavity of the crown ether. 2 highlights the fact that cadmium is almost never S-bonded to thiocyanate except in bridging thiocyanates. 相似文献
24.
Mark D. Ogden Serguei I. Sinkov Mikael Nilson Gregg J. Lumetta Robert D. Hancock Kenneth L. Nash 《Journal of solution chemistry》2013,42(1):211-225
The complexant 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) is a planar tetradentate ligand that is more preorganized for metal complexation than its unconstrained analogue ethylendiiminodiacetic acid (EDDA). Furthermore, the backbone nitrogen atoms of PDA are aromatic, hence are softer than the aliphatic amines of EDDA. It has been hypothesized that PDA will selectively bond to trivalent actinides over lanthanides. In this report, the results of spectrophotometric studies of the complexation of Nd(III) and Am(III) by PDA are reported. Because the complexes are moderately stable, it was necessary to conduct these titrations using competitive equilibrium methods, competitive cation complexing between PDA and diethylenetriaminepentaacetic acid, and competition between ligand protonation and complex formation. Stability constants and ligand protonation constants were determined at 0.1 mol·L?1 ionic strength and at 0.5 mol·L?1 ionic strength nitrate media at 21 ± 1 °C. The stability constants are lower than those predicted from first principles and speciation calculations indicate that Am3+ selectivity over Nd3+ is less than that exhibited by 1,10-phenanthroline. 相似文献
25.
Dr. Erin N. Hancock Prof. M. Kevin Brown 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):565-576
The ladderane family of natural products are well known for their linearly concatenated cyclobutane skeletal structure. Owing to their unique carbocyclic framework, several chemical syntheses have been reported since their discovery in 2002. The focus of this review is to showcase the novel tactics that have been used to generate the ladderane core and the challenges that are associated with the synthesis of these unusual and complex natural products. 相似文献
26.
I.J. Galpin F.E. Hancock B.K. Handa A.G. Jackson G.W. Kenner R. Ramage B. Singh R.G. Tyson 《Tetrahedron》1979,35(23):2779-2783
The fully protected 17–26 fragment of a lysozyme analogue has been synthesised. A fragment condensation approach has been employed using the protected subfragments 17–19, 20–22 and 23–26. In the synthesis of the subfragments the use of the diphenylphosphinyl mixed anhydride method has been demonstrated. 相似文献
27.
Richard A. Hancock Raymond Walder Helmut Weigel 《Journal of mass spectrometry : JMS》1979,14(9):507-511
Consequential upon determinations of kinetic rate constants of ion/molecule reactions in methane and isobutane, simple equations are presented from which the pressures of methane and isobutane in the ion source of chemical ionization mass spectrometers can be calculated. Account is taken of the design of the ion source and it is only necessary to determine two ion currents for each gas. 相似文献
28.
Using plane strain and axisymmetric notched tensile specimens in combination with finite deformation stress analysis, the strain to initiate failure in a range of structural steels is shown to be co-related by the state of stress for both axisymmetric and plane states of strain. The implications of this result for ductile failure terminated by flow localisation is discussed in the light of the theoretical work on localised flow. 相似文献
29.
Rate constants for collisional removal of ã1A1 and b?1B1 CH2 and CD2 have been directly measured, using IR laser induced multiple photon dissociation to prepare the radicals, and time resolved laser induced fluorescence to observe them. For CH2(ã1A1) removal by He, Ne, Ar, Kr, Xe, N2, H2, O2, CO and CH4, rate constants of 3.1, 4.2, 6.0, 7.0, 16, 8.8, 130, 30, 56 and 73 × 10?12 cm3 molecule?1 s?1 were found respectively. These represent significant increases over the previously accepted values. Essentially no isotope effect is observed in the removal of CD2(ã1A1) by the rare gases. The rate determining step in removal by the rare gases and N2 is thought to be singlet—triplet intersystem crossing controlled by long range attractive forces, and the results are discussed in terms of both isolated and mixed state theoretical models of these processes. For the other molecular collision partners, bimolecular chemical removal channels are possible, and may account for the relatively fast rates observed. Radiative lifetimes of five Σ vibronic levels of CH2(b?1B1) and three Σ vibronic levels of CD2(b?1B1) have been measured and found to lie in the range 2.5–6.0 μs, and collisional quenching rates for CH2(b?1B1) are found to be of the order of the gas kinetic collisional frequency. 相似文献
30.