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191.
Virgil Barboiu Emilia Streba Cornelia Luca Ionela Radu George Ervant Grigoriu 《Journal of polymer science. Part A, Polymer chemistry》1998,36(10):1615-1623
Unsaturated macromolecular carboxybetaines were obtained by reaction of poly(4-vinylpyridine) and poly(N-vinylimidazole) with propiolic acid. A kinetic model was presented for 4-methylpyridine. It consists of three coupled reactions: neutralization, addition which involves two molecules of acid and leads to a cation–anion pair structure, where the cation results from the addition of the amine nitrogen to the triple bond of acid, and an equilibrium reaction between the ion-pair structure and the betaine structure. The addition rate was found to be higher for poly(4-vinylpyridine) than for poly(N-vinylimidazole); it was also higher in water than in a water–methanol mixture. The reaction with acetylenedicarboxylic acid was carried out on poly(N-vinylimidazole), but the transformed units showed the structure that results from propiolic acid. The betaine products from 4-methylpyridine did not polymerize by radical initiation. The polymeric products show characteristics of photocrosslinking polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1615–1623, 1998 相似文献
192.
Stephen Z. D. Cheng Yeocheol Yoon Anqiu Zhang Edward P. Savitski Jae-Young Park Virgil Percec Peihwei Chu 《Macromolecular rapid communications》1995,16(8):533-542
Based on our differential scanning calorimetry observations, a polyether 1 synthesized from 4′-[2-(4-hydroxyphenyl)propyl]-4-biphenylol and 1,9-dibromononane shows multiple transition behavior during cooling and heating. Furthermore, these transition temperatures do not exhibit significant supercooling dependence. Detailed analyses of the wide-angle X-ray diffraction powder and fiber patterns at different temperatures have indicated that highly ordered smectic F and G phases exist in this polyether and are differentiated from traditional crystalline phases. 相似文献
193.
Vicente Samano Virgil L. Styles Joseph H. Chan 《Journal of heterocyclic chemistry》2000,37(1):183-185
This paper describes the synthesis of 2‐amino‐5‐[(4‐chlorophenyl)thio]‐4‐morpholinopyrimidine (BW 394U, compound 4 ), a potential antisenility agent. The key intermediates 3a/3b were obtained from an in situ‐generated Vilsmeier‐Haack reagent that simultaneously protected the 2‐amino group prior to further manipulations. Displacement of the chloro group in 3a gave 4 in 40% yield and 4‐dimethylamino analogue 5. However, displacement of 3b with morpholine followed by treatment with aqueous base gave 4 in 74% yield. 相似文献
194.
Yong Ku Kwon Craig Danko Sergei Chvalun John Blackwell James A. Heck Virgil Percec 《Macromolecular Symposia》1994,87(1):103-114
Insight into the supramolecular structure formed by a polymethacrylate with a highly tapered side chain is obtained from parallel X-ray analysis of oriented fibers of the polymer and its monomeric precursor. The polymer is poly(2-{2-[2-(2-methacryloyloxyethoxy)ethoxy]ethoxy}ethyl 3,4,5-tris(p-dodecyloxybenzyloxy)benzoate) (abbreviated to 12-ABG-4EO-PMA); the monomeric precursor is the hydroxy-terminated side chain 2-{2-[2-(2-hydroxyethoxy)-ethoxy]ethoxy}ethyl 3,4,5-tris(p-dodecyloxybenzyloxy)benzoate (12-ABG-4EO-OH). The polymer and precursor both form ordered solid state structures that are converted to columnar hexagonal liquid crystalline (φh) phases at approximately 40°C and 50°C, respectively. The ordered solid state structures consist of ordered hexagonally packed cylindrical columns, in which the monomer units are probably packed with helical symmetry. For the polymer at 25°C, the column diameter is 60.4Å with an axial repeat of 5.03Å containing eight monomer units. For the precursor at 25°C, the column diameter is reduced to 53.5Å, probably due to the absence of the polymer backbone from the center of the column, and the axial repeat is doubled to 10.04Å. The X-ray data are compatible with a tighter winding of the monomers in a helical structure, but otherwise suggest that there are common features in the stacking of the aromatic groups in the two structures. 相似文献
195.
Nga H. Nguyen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2011,49(22):4756-4765
Single electron transfer‐living radical polymerization (SET‐LRP) of methyl acrylate (MA) in methanol, catalyzed with nonactivated and activated Cu(0) wires, was performed in the presence of nondeoxygenated reagents and was investigated under a simple blanket of nitrogen. The addition of a small amount of hydrazine hydrate mediates the deoxygenation of the reaction mixture by the consumption of oxygen through its use to oxidize Cu(0) to Cu2O, followed by the reduction of Cu2O with hydrazine back to the active Cu(0) catalyst. SET‐LRP of MA in methanol in the presence of air requires a smaller dimension of Cu(0) wire, compared to the nonactivated Cu(0) wire counterpart. Activation of Cu(0) wire allowed the polymerization in air to proceed with no induction period, linear first‐order kinetics, linear correlation between the molecular weight evolution with conversion, and narrow molecular weight distribution. The retention of chain‐end functionality of α,ω‐di(bromo) poly(methyl acrylate) (PMA) prepared by SET‐LRP was demonstrated by a combination of experiments including 1H NMR spectroscopy and matrix‐assisted laser desorption ionization–time of flight mass spectrometry after thioetherification of α,ω‐di(bromo) PMA with thiophenol. In SET‐LRP of MA in the presence of limited air, bimolecular termination is observed only above 85% conversion. However, for bifunctional initiators, the small amount of bimolecular termination observed at high conversion maintains a perfectly bifunctional polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
196.
Two-dimensional (2D) polarization patterns are achieved by the interference of two pairs of beams with perpendicular planes of incidence and orthogonal polarizations (i.e. linear or circular). In both cases, imposing a phase shift of π/2 between consecutive beams contains the amplitude modulation of the optical field in the superposition region and, thus, pure 2D polarization patterns are created. The recording of these interference fields in a polarization-sensitive material, namely an amorphous azopolymer, creates reconfigurable 2D periodic microstructures with peculiar diffraction properties. 相似文献
197.
In the fluorescence spectra only morphine exhibits large red shifts of the maxima on increasing solvent polarity. In the phosphorescence spectra, phenol, anisole, and 3-methoxyphenol exhibit large red shifts of the maxima on going from nonpolar to polar solvents. For the latter, the results are interpreted in terms of charge-transfer-to-solvent (CTTS) transitions. For morphine, 2- and 4-methoxyphenol, the phosphorescence maxima occur at long wavelengths in both nonpolar and polar solvents, and this is interpreted in terms of CTTS and intramolecular charge transfer processes. The red-shift of the morphine fluorescence band on going to polar solvents is similarly interpreted as a combination of CTTS and intramolecular charge transfer transitions. 相似文献
198.
Abstract The ir and nmr spectra of 24 3-naphthyl-4-quinazolones were examined. There are three principal ir bands in the 1500 and 1705 cm?1 region of the spectra. The first at 1685–1705 cm?1 is assigned to the tertiary amide carbonyl (ArCONR2), the second at 1593–1645 cm?1 to the anil chromophore (ArN=C-N) and the third to the naphthalene ring at 1600 cm?1. The nmr band assignments are straight forward. 相似文献
199.
Virgil Percec 《Molecular Crystals and Liquid Crystals》2013,570(3-4)
1H- and 13C-NMR studies carried out on poly(phenylacetylene)s and poly(pentadeutero-phenylacetylene)s prepared with Ziegler and metathesis type catalysts, revealed two different mechanisms which control the microstructure of acetylenic polymers. For the Ziegler-type catalysts, thermal induced reactions (intramolecular cyclization, aromatization, chain scission and cis-trans isomerization) of the cis-double bonds (isomerization after double bond formation) are responsible for the polymer microstructure. (For a review see: Progr. Polym. Sci., 8, 133 (1982).) Both isomerization "after” double bond formation as well as isomerization “before” double bond formation are responsible for the microstructure of polymers obtained with metathesis type catalysts. In both cases, the polymer molecular weight is controlled by the intramolecular cyclization of the cis-polymer chain end. Under reaction conditions where isomerization occurs mainly "before double bond formation, “pure” trans polymers having very high molecular weight are obtained (Polym. Prepr., 24 (1), 239 (1983); Polym. Bull., 9, 548 (1983)). The microstructure of several other acetylenic polymers will be commented on in relation with the polymerization mechanism and with the microstructure of (CH)x. 相似文献
200.
Zhang N Hoffman DJ Gutsche N Gupta J Percec V 《The Journal of organic chemistry》2012,77(14):5956-5964
The efficiency of arylboron-based nucleophiles, boronic acid, potassium trifluoroborate, neopentylglycolboronate, and pinacol boronate in nickel-catalyzed Suzuki-Miyaura cross-coupling reactions with the two C-O electrophiles, mesylates, and sulfamates was compared. Arylboronic acid is the most reactive and most atom-economic of the four boron species studied. Arylpotassium trifluoroborate cross-couples efficiently only in the presence of water. In the absence of water, aryl neopentylglycolboronate is more efficient, less expensive, and more atom-economic than aryl pinacolboronate. 相似文献