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81.
The binding constants with the host cyclobis(paraquat-p-phenylene), 1(4+), have been determined in CH(3)CN by UV-vis spectrophotometry for a series of p-phenylene guests, symmetrically substituted with side arms of varying length and functionality. Semiempirical molecular orbital theory was employed to provide a detailed structural and energetic interpretation of the experimental binding data. In particular, the length of the side arms and the type and position of the heteroatoms on the side arms were systematically varied in order to understand the effects of external interactions on the association constants of the guests with host 1(4+). A large chelate effect involving the ethyleneoxy side arm oxygen atoms and a cooperative effect between the guest aromatic core and the side arms are significant factors which determine the binding with this host. Sequential ethyleneoxy linkages along the side arms markedly increase the binding constant with respect to a compound in which the same number of oxygens along the side arms are separated by longer aliphatic linkages. In addition, a multiplicative rather than additive effect on the binding constant is observed which demonstrates that the oxygen atoms exhibit a strong chelate effect. It was also discovered that while the side arms of these guests contribute most of the driving force for complexation, an aromatic core is necessary for the guest to reside in the cavity of the host. The binding of these guests then is dependent upon cooperation between the arms and the aromatic core. Furthermore, elongation of the central aromatic core with aliphatic side arms containing no heteroatoms leaves the association constant relatively unchanged and replacement of the oxygen atoms with sulfur markedly decreases the observed binding. These effects have been used to rationalize several observations regarding this system in the literature and may serve to improve the design of new supramolecular systems and to better understand the host/guest interaction process. 相似文献
82.
Peter B. Hitchcock John F. Nixon Robson M. Matos 《Journal of organometallic chemistry》1995,490(1-2):155-162
Synthesis and structural studies of the ruthenium(II) ‘sandwich’ complexes [Ru(η5-P3C2tBu2)2], [Ru(η5-P3C2C2tBu2)(η5-P2C3tBu3)], [Ru(η5-C5R5)(η5-P3C2tBu2)] (R=H, Me) are described. The results of a single crystal X-ray structural study of [Ru(η5-P3C2tBu2)2] are discussed. 相似文献
83.
Taboada P Velasquez G Barbosa S Castelletto V Nixon SK Yang Z Heatley F Hamley IW Ashford M Mosquera V Attwood D Booth C 《Langmuir : the ACS journal of surfaces and colloids》2005,21(12):5263-5271
Three triblock copolymers of ethylene oxide and phenyl glycidyl ether, type E(m)G(n)E(m), where G = OCH2CH(CH2OC6H5) and E = OCH2CH2, were synthesized and characterized by gel-permeation chromatography, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, and NMR spectroscopy. Their association properties in aqueous solution were investigated by surface tensiometry and light scattering, yielding values of the critical micelle concentration (cmc), the hydrodynamic radius, and the association number. Gel boundaries in concentrated micellar solution were investigated by tube inversion, and for one copolymer, the temperature and frequency dependence of the dynamic moduli served to confirm and extend the phase diagram and to highlight gel properties. Small-angle X-ray scattering was used to investigate gel structure. The overall aim of the work was to define a block copolymer micellar system with better solubilization capacity for poorly soluble aromatic drugs than had been achieved so far by use of block copoly(oxyalkylene)s. Judged by the solubilization of griseofulvin in aqueous solutions of the E(m)G(n)E(m) copolymers, this aim was achieved. 相似文献
84.
The syntheses of Co(π-all)(PF3)2(PPh3) complexes (π-all = π-allyl, anti-1-Me-π-allyl, syn-1-Me-π-allyl, 1,1-dimethyl-π-allyl, anti-1,2-diMe-π-allyl, syn,syn-1,3-diMe-π-allyl, 2Et-π-allyl, π-cyclooctenyl, h3-π-cycloheptadienyl) are described. 1H and 19F NMR data are presented and discussed in relation to the structures of the complexes. The compound Co(π-C5H9)(PF3)(PPh3)2 is also reported. Several of the π-allylic complexes are found to be active catalysts for the isomerisation of 1-octene to 2-octene under a hydrogen atmosphere. 相似文献
85.
Alan Nixon Ronald F. Childs 《Journal of polymer science. Part A, Polymer chemistry》1980,18(5):1499-1509
The reactions of crotonaldehyde (CA) with ethyl aluminum chlorides have been examined using a titration technique at low temperature. The titrations were followed by 1H-NMR spectroscopy. Evidence for complexes of the type (Et2AlCl)2CA and (Et2AlCl-CA)2 has been obtained. Ethyl aluminum sesquichloride undergoes sequential addition of CA to the EtAlCl2 moiety, to the Et2AlCl moiety, and again to the EtAlCl2 moiety. Ethyl aluminum dichloride undergoes ligand redistribution, alternately disproportionating and reproportionating, the ultimate product being EtAlCl2-CA2. 相似文献
86.
Harrison WJ Aboulgasem GJ Elathrem FA Nixon SK Attwood D Price C Booth C 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6170-6178
The micellization in dilute aqueous solution of a 50/50 wt% mixture of two triblock copolymers, E45B14E45 and E62P39E62, and the gelation of concentrated micellar solutions have been investigated over a range of temperatures. Here E, B, and P denote oxyethylene, oxubutylene, and oxypropylene chain units. Comparison is made with aqueous solutions of the individual copolymers. The results of light scattering measurements are consistent with effectively separate micellization of the two copolymers in the mixture. Hard gel formed when the extent of micellization was high for both copolymers. Because of the relatively high critical micellization temperatures of copolymer E62P39E62, the low-temperature boundary of the hard gel was high for this copolymer and for the mixture. The minimum concentration for hard-gel formation was higher for the mixture than for either of the individual copolymers, as would be expected for packing of two distributions of micelles of different average size. 相似文献
87.
J.F. Nixon 《Journal of fluorine chemistry》1973,3(2):179-185
The 19F NMR spectra of π-allyl-tris(trifluorophosphine)rhodium(I), [A], benzene-tris(trifluorophosphine)chromium(0), [B], and nitrosyl-tris(trifluorophosphine) rhodium(-I), [C], are presented. These are examples of [AX3]3 nuclear spin systems (A = phosphorus, X = fluorine). The spectra of [A] and [B] have been completely analysed to afford values of 1J(PF), 2J(PP′), 3J(PF′) and 4J(FF′). 相似文献
88.
A series of reactions between SF5CF2CF2I and SF5(CF2)4I with F2CCF2 was carried out in an effort to find the most effective methods for chain-extension. Also, for the first time, SF5(CF2)8I and SF5(CF2)10I have been prepared and isolated. The reaction conditions for the addition of H2CCH2 were also investigated. A determination of the crystal structure of the SF5(CF2)4CH2CH2I has been carried out: the crystal system is monoclinic, with space group P2(1)/n and a=23.465(5) Å; b=6.0971(12) Å; c=44.892(9) Å; α=90°; β=99.38(3)°; γ=90°; Z=20. 相似文献
89.
Continuous families of solitons in the nonlinear Schrödinger equation with non‐‐symmetric complex potentials and general forms of nonlinearity are studied analytically. Under a weak assumption, it is shown that stationary equations for solitons admit a constant of motion if and only if the complex potential is of a special form , where is an arbitrary real function. Using this constant of motion, the second‐order complex soliton equation is reduced to a new second‐order real equation for the amplitude of the soliton. From this real soliton equation, a novel perturbation technique is employed to show that continuous families of solitons bifurcate out from linear discrete modes in these non‐‐symmetric complex potentials. All analytical results are corroborated by numerical examples. 相似文献
90.
Jason M. Lynam Tracy D. Nixon Adrian C. Whitwood 《Journal of organometallic chemistry》2008,693(19):3103-3110
Reaction of cis-[RuCl2(dppm)2] (dppm = 1,2-bis(diphenylphosphino)methane) with PhCCH and NaPF6 utilising methanol as solvent results in the formation of the η3-butenynyl complex [Ru(η3-PhCCCCHPh)(dppm)2][PF6] in good yield. Similar reactions with ButCCH and PrnCCH resulted in the corresponding alkyl-substituted complexes and all three of these compounds have been characterised by NMR spectroscopy and X-ray crystallography. The mechanism of this reaction has been probed by employing labelling experiments with both PhCCD and PhC13CH allowing the identity of possible intermediates in the reaction to be determined. Furthermore, [Ru(η3-PhCCCCHPh)(dppm)2][PF6] has been shown to be an effective regio- and stereo-selective catalyst for the dimerisation of PhCCH to Z-PhCCCHCHPh in the absence of solvent. In contrast, no evidence for the formation of alkyne coupling was obtained from the reaction of cis-[RuCl2(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) with PhCCH and NaPF6. 相似文献