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81.
We have developed a one-step facile, flexible and readily scalable purification method for a recombinant protein, TM 1-99 (113 amino acid residues; 12,837 Da) based on reversed-phase high-performance liquid chromatography (RP-HPLC) from an E. coli cell lysate. Following cell lysis, the cell contents were extracted with 0.1% aqueous trifluoroacetic acid (TFA), applied directly under conditions of high sample load to a narrow bore RP-HPLC C(8) column (150 mm x 2.1 mm I.D.) and eluted by a shallow gradient of acetonitrile (0.1%/min). Loads of 23 and 48 mg of lyophilized crude cell extract produced 2.4 and 4.2mg of purified product (>94% pure), respectively, at >94% recovery. Our results show the excellent potential of one-step RP-HPLC for purification of recombinant proteins from cell lysates, where high yields of purified product and greater purity are achieved compared to affinity chromatography. Such an approach was also successful in purifying just trace levels (<0.1% of total contents of crude sample) of TM 1-99 from a cell lysate. 相似文献
82.
We define a logic D capable of expressing dependence of a variable on designated variables only. Thus D has similar goals to the Henkin quantifiers of [4] and the independence friendly logic of [6] that it much resembles. The logic D achieves these goals by realizing the desired dependence declarations of variables on the level of atomic formulas. By [3] and [17], ability to limit dependence relations between variables leads to existential second order expressive power. Our D avoids some difficulties arising in the original independence friendly logic from coupling the dependence declarations with existential quantifiers. As is the case with independence friendly logic, truth of D is definable inside D. We give such a definition for D in the spirit of [11] and [2] and [1]. 相似文献
83.
Jack C. Sharland Bo Wei David J. Hardee Timothy R. Hodges Wei Gong Eric A. Voight Huw M. L. Davies 《Chemical science》2021,12(33):11181
This study describes general methods for the enantioselective syntheses of pharmaceutically relevant 1-aryl-2-heteroaryl- and 1,2-diheteroarylcyclopropane-1-carboxylates through dirhodium tetracarboxylate-catalysed asymmetric cyclopropanation of vinyl heterocycles with aryl- or heteroaryldiazoacetates. The reactions are highly diastereoselective and high asymmetric induction could be achieved using either (R)-pantolactone as a chiral auxiliary or chiral dirhodium tetracarboxylate catalysts. For meta- or para-substituted aryl- or heteroaryldiazoacetates the optimum catalyst was Rh2(R-p-Ph-TPCP)4. In the case of ortho-substituted aryl- or heteroaryldiazoacetates, the optimum catalyst was Rh2(R-TPPTTL)4. For a highly enantioselective reaction with the ortho-substituted substrates, 2-chloropyridine was required as an additive in the presence of either 4 Å molecular sieves or 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). Under the optimized conditions, the cyclopropanation could be conducted in the presence of a variety of heterocycles, such as pyridines, pyrazines, quinolines, indoles, oxadiazoles, thiophenes and pyrazoles.The dirhodium tetracarboxylate-catalysed asymmetric cyclopropanation has been applied to the enantioselective syntheses of pharmaceutically relevant 1-aryl-2-heteroaryl- and 1,2-diheteroarylcyclopropane-1-carboxylates. 相似文献
84.
The Suzuki-Miyaura cross-coupling of sterically hindered and electron-rich ortho,ortho′-substituted aryl halides with potassium vinyltrifluoroborate utilizing microwave irradiation has been conducted while adjusting solvent ratio, irradiation time, and catalyst loading to find optimal conditions. Coupling of benzyl 3,5-bis(benzyloxy)-4-bromobenzoate leads to a mixture of the desired styrene derivative and the reduced product. 4-Bromo-1,3,5-trimethoxybenzene, methyl 4-bromo-3,5-dimethoxybenzoate, and mesitylene bromide were also coupled to test the breadth and scope of this methodology. Of these substrates tested only 4-bromo-1,3,5-trimethoxybenzene was not vinylated successfully, which is believed to be due to the electron-rich nature of this system. 相似文献
85.
Korb JP Hodges MW Gobron T Bryant RG 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》1999,60(3):3097-3106
1H nuclear magnetic relaxation dispersion experiments show remarkable differences between water and acetone in contact with microporous glass surfaces containing trace paramagnetic impurities. Analyzed with surface relaxation theory on a model porous system, the data obtained for water show that proton surface diffusion limited by chemical exchange with the bulk phase permits long-range effectively one-dimensional exploration along the pores. This magnetic-field dependence coupled with the anomalous temperature dependence of the relaxation rates permits a direct interpretation in terms of the proton translational diffusion coefficient at the surface of the pores. A universal rescaling applied to these data collected for different pore sizes and on a large variety of frequencies and temperatures, supports this interpretation. The analysis demonstrates that acetone diffuses more slowly, which increases the apparent confinement and results in a two-dimensional model for the molecular dynamics close to surface relaxation sinks. Surface-enhanced water proton diffusion, however, permits the proton to explore a greater spatial extent of the pore, which results in an apparent one-dimensional model for the diffusive motions of the water that dominate nuclear spin relaxation. 相似文献
86.
Weber HA Zart MK Hodges AE White KD Barnes SM Moody LA Clark AP Harris RK Overstreet JD Smith CS 《Journal of AOAC International》2003,86(3):476-483
A fast, practical ambient extraction methodology followed by isocratic liquid chromatography (LC) analysis with UV detection was validated for the determination of berberine, hydrastine, and canadine in goldenseal (Hydrastis canadensis L.) root powder. The method was also validated for palmatine, a major alkaloid present in the possible bioadulterants Coptis, Oregon grape root, and barberry bark. Alkaloid standard solutions were linear over the evaluated concentration ranges. The analytical method was linear for alkaloid extraction using 0.3-2 g goldenseal root powder/100 mL extraction solvent. Precision of the method was demonstrated using 10 replicate extractions of 0.5 g goldenseal root powder, with percent relative standard deviation for all 4 alkaloids < or = 1.6. Alkaloid recovery was determined by spiking each alkaloid into triplicate aliquots of neat goldenseal root powder. Recoveries ranged from 92.3% for palmatine to 101.9% for hydrastine. Ruggedness of the method was evaluated by performing multiple analyses of goldenseal root powder from 3 suppliers over a 2-year period. The method was also used to analyze Coptis root, Oregon grape root, barberry bark, and celandine herb, which are possible goldenseal bioadulterants. The resulting chromatographic profiles of the bioadulterants were significantly different from that of goldenseal. The method was directly transferred to LC with mass spectrometry, which was used to confirm the presence of goldenseal alkaloids tetrahydroberberastine, berberastine, canadaline, berberine, hydrastine, and canadine, as well as alkaloids from the bioadulterants, including palmatine, jatrorrhizine, and coptisine. 相似文献
87.
We report a new Mössbauer relaxation window which allows the fluctuation rate of a molecular field acting on an impurity in a strongly correlated spin system to be obtained. For a molecular field of 1 T, the fluctuation rate can be measured up to 10 THz, which is three orders of magnitude higher than for the classical relaxation window. The calculated line shapes show that Ising-like fluctuations of the molecular field can be distinguished from other types of fluctuations (in-plane or in space). An application and some other possible uses of this new relaxation window are discussed. 相似文献
88.
Summary A series of synthetic peptide HPLC standards has been designed for use in monitoring free silanols on silica-based reversed-phase
supports. The four standards (+ 1 to + 4 net charge) showed great versatility in monitoring silanol activity over a pH range
of 2.0 to 7.0. We have developed a silanol monitoring system based on the sensitivity of the standards to ionic interactions
with reversed-phase packings at pH 7.0. This monitoring procedure involves chromatographing the peptides at pH 7.0 with a
combined acetonitrile and sodium perchlorate linear AB gradient and is generally applicable to reversed-phase packings exhibiting
a wide range of silanol concentrations. These standards not only demonstrate the presence and extent of free silanols, they
also allow the researcher to determine what changes must be made to the mobile phase composition to minimize ionic interactions.
In addition, the standards, in conjunction with the double gradient monitoring system at pH 7.0, will aid researchers and
manufacturers in the improvement and development of reversed-phase matrices. 相似文献
89.
F. B. Foote D. T. Hodges H. B. Dyson 《International Journal of Infrared and Millimeter Waves》1981,2(4):773-782
Power and energy measurments in the sub-mm/near-mm wave spectral region are assuming greater importance as experimentation and data exchange increases. Much of the information on power and energy measurements of lasers and other sources is derived from common detectors constructed for operation at visible and near infrared wavelengths. This paper reports on recent progress in attempts to provide accurate calibrations for instruments such as pyroelectrics and calorimeters in the 40 m to 3 mm spectral region.This work was supported by the Department of Energy 相似文献
90.
A value for the nuclear magnetic moment of theI=2 (80.56 keV) level of166Er has been obtained by comparing measurements made by the Mössbauer effect on166Er with NMR measurements on the ground state of167Er in the same matrix. From measurements on ErFe2, ErAl2 and ErZn we obtain the value N (166Er; 80.56 keV)=0.650±0.010 n.m. This result is slightly higher than previously proposed values. 相似文献