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1.
2.
Keikichi Uno Mutsuko Ohara Harold G. Cassidy 《Journal of polymer science. Part A, Polymer chemistry》1968,6(10):2729-2740
Ten vinylhydroquinone and one vinyl resorcinol derivatives are compared, particularly with respect to NMR spectra and copolymerizability with styrene. They are vinylhydroquinone dimethyl ether (I), vinyl-O,O′-bis(1-ethoxyethyl)hydroquinone (II), vinylhydroquinone di(2-pentyl)ether (III), 4-vinyl resorcinol bismethoxymethyl ether (IV), 2-vinyl-5-methylhydroquinone dimethyl ether (V), 2-vinyl-5-methyl-O,O′-bis(1-ethoxyethyl)hydroquinone (VI), 2-vinyl-6-methylhydroquinone dimethyl ether (VII), 2-vinyl-5-tert-butylhydroquinone dimethyl ether (VIII), 2-vinyl-5-chlorohydroquinone dimethyl ether (IX), 2-vinyl-3,6-dimethylhydroquinone dimethyl ether (X), and 2-vinyl-3,5,6-trimethylhydroquinone dimethyl ether (XI). All the vinyl protons have almost the same coupling constants. Though subtle distinctions are found among all the spectra, they can in general be put into two groups on the basis of the chemical shifts. Let the hydrogen on carbon-1 of the vinyl group be A, the hydrogen cis to A be B the hydrogen trans to A be C, then in the first group, (I) through (IX), the chemical shifts (τ) are (A) 3.02 ± 0.08, (C) 4.41 ± 0.05, and (B) 4.87 ± 0.07, and in the second group, (X) and (XI), they are (A) 3.30 ± 0.03, (C) 4.49 ± 0.01, and (B) 4.59 ± 0.03. It is supposed that in (X) and (XI) the vinyl group is out of the plane of the ring, because of the two ortho substituents, and this conformation is reflected in the NMR data. Ultraviolet spectra are consonant with this interpretation, since the λmax of (X) and (XI) correspond closely with those of nonvinyl reference compounds, while those of (II), (V), and (VIII) are shifted to longer wavelengths. When these compounds are copolymerized separately with styrene, the behaviors are classifiable into the following three groups, where r1 and r2 are monomer reactivity ratios with styrene as the first monomer: (i) r1 < 1 and r2 < 1 for compounds (II) and (III) and the reference compound O,O′-dibenzoylvinylhydroquinone, (ii) r1 < 1 and r2 > 1 for compounds (I), (V), (VII), (VIII), (IX), and (iii) r1 > 1 and r2 = 0 for compounds (X) and (XI). These behaviors are correlated with the effect of electronegativity of groups on the stability of the radical at the growing end of the chain and with the simultaneous effects of steric hindrance. 相似文献
3.
4.
Gerhard Wegner Nobuo Nakabayashi Harold G. Cassidy 《Journal of polymer science. Part A, Polymer chemistry》1968,6(11):3151-3156
It is possible to prepare polyurethanes from p-benzoquinone-diols and diisocyanates by using dibutyltin diacetate catalyst at room temperature or below, since the benzoquinone group does not react with isocyanate under these conditions. This permits preparation of new redox polymers. In preparing the polyurethanes excess isocyanate groups must be destroyed at the end of the reaction time in order to prevent crosslinking during work-up. These polymers are readily reduced by aqueous hydrosulfite. Good viscosity numbers are obtained; and, in general, upon reduction the viscosity increases over that of the oxidized form. There is no evidence of crosslinking. When oxidized and reduced forms of these polymers are mixed there is no evidence of charge transfer. 相似文献
5.
A number of experimental parameters have been optimized for the separation of 26 metal ions, including alkali, alkaline earth, transition and lanthanide metal ions. Experimental parameters that were evaluated included nature of indirect-detection reagent, pH of electrolyte, concentration of complexing agent and nature of the surface of the capillary; unbonded and C1 and C18 bonded phases were studied. In addition the effect of internal diameter on linearity and signal-to-noise ratio was examined, and separation efficiency was determined for a variety of experimental conditions. Detection limits (signal-to-noise RATIO = 3) were ca. 1 μg/ml for the lanthanides, ca. 0.6 μg/ml for transition and alkaline earth ions and ca. 0.1–0.8 μg/ml for alkali metal ions. The average relative standard deviations of were 3.7, 5.1 and 2.5% on unbonded, C1 and C18 capillaries, respectively. Whereas conventional regression analysis suggested that the calibration curves were linear over the range of 1·10−5 to 4·10−4 mol/l, sensitivity plots showed that the results were actually linear to within 6% only over the range of 2.5·10−5 to 4·10−4 mol/l. 相似文献
6.
Ivan Bernal D. C. Levendis Richard Fuchs G. M. Reisner Juanita M. Cassidy 《Structural chemistry》1997,8(4):275-285
The crystal structure of 4-cyclopropylacetanilide was investigated at room temperature (21C) and at –100C in order to determine the orientation of the phenyl ring with respect to the cyclopropane moiety and the effect of this substituent on the stereochemistry of the three-membered ring. The compound was chosen because it is one of the few species containing a simple phenyl ring as the sole cyclopropane ring substituent and whose crystals are suitable for X-ray diffraction at room temperature. The substance crystallizes in space groupP2l/c at either temperature (no phase transitions) with cell constants: (at 21C)a=9.725(2),b=10.934(3), andc=9.636(2) å,=106.13(1);V=984.21 å3 andd(calc;z=4)=1.182 g cm–3. The relevant parameters for the –100C structure area=9.557(4),b=10.980(2), andc=9.641(2) å,=106.34(3);V=970.76 å3 and d(calc;z=4)=1.199 g cm–3. Final values wereR(F)=0.042, Rw=0.035, using unit weights, and its nonhydrogen atoms were used to phase the low-temperature data, whose final discrepancy indices wereR(F)=0.051,R
w
=0.061. The phenyl substituent is almost exactly in the bisecting conformation with respect to the C-C-C angle at the point of attachment to cyclopropane and conjugative effects are clearly evident in the lengths of the cyclopropane ring [1.494(3), 1.498(3), and 1.474(4) å, the later being the distal bond]. If one omits the terminal methylene fragments at C10 and C11, the atoms comprising the acetanilide fragment and the substituted carbon of the cyclopropane ring lie in a nearly perfect plane. Molecular mechanics as well as semiempirical (AM1) calculations were carried out in order to determine the structure of the energy-minimized configurations in the two computational environments. The molecular conformations thus obtained are close to that experimentally observed from the X-ray diffraction experiment. In both theoretical models, the lowest energy conformation is that in which the plane of the phenyl ring bisects the cyclopropane C-C-C angle as was experimentally observed. Finally, the shape of the conformational barrier as a function of the orientation of the plane of the phenyl ring was computed, giving a maximum barrier to rotation of 2.2 kcal/mol. Similar calculations were carried out for two other aryl cyclopropanes, whose rings (naphthalene and anthracene) cannot adopt the bisecting position. Comparisons of experimental geometrical parameters as well as of the barriers to rotation are presented.on leave at the University of Houston, 1995–1996. 相似文献
7.
Single phase perovskite-based rare earth cobaltates (Ln1−xSrxCoO3−δ) (Ln=La3+, Pr3+, Nd3+, Sm3+, Gd3+, Dy3+, Y3+, Ho3+, Er3+, Tm3+ and Yb3+; 0.67?x?0.9) have been synthesized at 1100°C under 1 atmosphere of oxygen. X-ray diffraction of phases containing the larger rare earth ions La3+, Pr3+ and Nd3+ reveals simple cubic structures; however electron diffraction shows orientational twinning of a local, tetragonal (I4/mmm; ap×ap×2ap) superstructure phase. Orientational twinning is also present for Ln1−xSrxCoO3−δ compounds containing rare earth ions smaller than Nd3+. These compounds show a modulated intermediate parent with a tetragonal superstructure (I4/mmm; 2ap×2ap×4ap). Thermogravimetric measurements have determined the overall oxygen content, and these phases show mixed valence (3+/4+) cobalt oxidation states with up to 50% Co(IV). X-ray diffraction data and Rietveld techniques have been used to refine the structures of each of these tetragonal superstructure phases (Ln=Sm3+-Yb3+). Coupled Ln/Sr and oxygen/vacancy ordering and associated structural relaxation are shown to be responsible for the observed superstructure. 相似文献
8.
Intensive research in the last two decades on the degradation of commercial plastics has led to the development of new methods of degradation and innumerable experimental techniques to characterize the degraded products. During the period 1970–1980, there have been substantial advances in most of the important aspects of polymer degradation including that induced by heat, light, oxygen, high energy radiation, photooxidation, and biological factors; and accounts have been given at various times of the current position in most of these [1–30]. 相似文献
9.
R. M. Cassidy S. Elchuk 《International journal of environmental analytical chemistry》2013,93(3-4):287-294
Abstract The potential of high-performance liquid chromatography (HPLC) for the determination of U(VI) in ground waters and urine has been examined under a variety of HPLC experimental conditions. Conventional cross-linked and bonded-phase ion exchangers, both cation and anion, were studied with aqueous mobile phases containing tartrate, citrate, or α-hydroxyisobutyrate. The best chromatography was obtained on bonded-phase cation exchangers with an α-hydroxyisobutyrate eluent. The metal ions were detected either by visible spectrophotometry after a post-column reaction with a complexing reagent, or with a polarographic detector. Dectection after post-column reaction gave the best sensitivity; the detection limit (2 × baseline noise was 6 ng or 60 ng.ml?1 for 100 μl samples. In-line trace enrichment was used to decrease detection limits and linear calibration curves were observed in the ranges studied; 0.5 to 50 ng.mL?1 for ground waters and 25 to 400 ng.mL?1 for artificial urine. 相似文献
10.
Nobuo Nakabayashi Gerhard Wegner Harold G. Cassidy 《Journal of polymer science. Part A, Polymer chemistry》1969,7(5):1269-1274
Redox polyurethanes, polyesters, and alternate copolyurethanes and copolycarbonates from two kinds of benzoquinonyl glycol were prepared based on 2-(duroquinonyl)-propan-1,3-diol. The oxidized polymer is stable. When the fully reduced polymer in solution is exposed to air the durohydroquinonyl residues are oxidized to the quinone form while the less substituted hydroquinonyl glycol residues remain stable in the reduced form. There is thus prepared polymer with oxidized and reduced groups alternating along the chain. 相似文献