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61.
Lake DA Johnson MV McEwen CN Larsen BS 《Rapid communications in mass spectrometry : RCM》2000,14(11):1008-1013
An automated sample preparation for high throughput accurate mass determinations by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) has been developed. Sample preparation was performed with an automated workstation and automated mass analyses were performed with a commercial MALDI-TOF mass spectrometer. The method was tested with a 41-sample library. MALDI-TOFMS was found to give the needed sensitivity, accurate mass measurement, and soft ionization necessary for structure confirmation, even of mixtures. A mass accuracy of 5 ppm or less was obtained in over 80% of known compound measurements. A mass accuracy better than 10 ppm was obtained for all measurements of known compounds. Analyses of parallel synthesis products resulted in 77% of the measurements with a mass accuracy of 5 ppm or better. 相似文献
62.
D. Mihrin Dr. P. W. Jakobsen A. Voute Dr. L. Manceron Prof. R. Wugt Larsen 《Chemphyschem》2019,20(23):3238-3244
The high-resolution infrared absorption spectrum of the donor bending fundamental band ν of the homodimer (HCN)2 has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν transition has the typical appearance of a perpendicular type band associated with a Σ–Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν0 of 779.05182(50) cm−1 together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm−1 relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol−1. The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19 , 3257–3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol−1 for the dissociation energy D0 of this prototypical homodimer. 相似文献
63.
Erik Larsen Abdel Aleem H. Abdel Aleem Erik B. Pedersen 《Journal of heterocyclic chemistry》1995,32(5):1645-1646
α-Thymidine (4) was synthesized from thymidine (1) in 3 steps in 36% overall yield without using chro-matography and with the possibility of increasing the yield to 85% by reusing the remaining α,β-mixture. 1-(2-Deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl)thymine (3) was further converted to 1-(2-deoxy-α-D-erythro-pentofuranosyl)-5-methylcytosine (5) . 相似文献
64.
Hewlett-Packard 8460A microwave spectrometer has been connected to a microcomputer based on the Motorola MC6800 microprocessor. The microcomputer is programmed to control frequency and Stark voltage and to perform conversion, storage and accumulation of intensities.The microcomputer is connected to a larger local computer, the RC4000, from which it may be loaded with a program, started and stopped, and from which data transfer between the storages of the two computers is controlled. This transfer may be performed, while the microcomputer is running a spectrum. 相似文献
65.
Jrgen Mller Carl Th. Pedersen Helge Egsgaard Elfinn Larsen 《Journal of mass spectrometry : JMS》1980,15(9):456-458
Electron impact spectra of thermolysis products of organic salts heated in the ion source of a mass spectrometer may give rise to organic ions corresponding to the cation of the salt. Field ionization mass spectrometry has been used as a facile method for detemining whether such an ion is due to ionization of the corresponding radical present in the gas phase, or to an electron impact induced fragmentation of a reaction product of higher mass. By comparison of the electron impact and field ionization spectra of a series of N-methyl pyridinium, tropylium and 1,2-dithiolylium salts it has been found possible to identify the radicals formed thermolytically, when present. 相似文献
66.
An analytical method for the speciation of selenomethionine, selenocystine, selenite and selenate by high performance liquid chromatography (HPLC) with atomic spectrometric detection is presented. An organic polymeric strong anion exchange column was used as the stationary phase in combination with an aqueous solution of 6 mmol L–1 of salicylate ion at pH 8.5 as the mobile phase which allowed the isocratic separation of the four selenium analytes within 8 minutes. The separated selenium species were detected on-line by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma mass spectrometry (ICP-MS). The signal-to-noise ratio of the FAAS detector was optimized using a hydrogen-argon entrained-air flame and a slotted-tube atom trap (STAT) in the flame. The limit of detection (3 σ) achieved by the HPLC-FAAS system was 1 mg L–1 of selenium (100 μL injections) for each of the four selenium species. More powerful selenium detection was achieved using an ELAN 5000 ICP-MS instrument. Selenium was measured at m/z = 82. The ICP-MS signal intensity was enhanced by a factor of 3–4 after addition of 3% methanol to the chromatographic mobile phase and by using an increased plasma power input of 1300 W. The limit of detection achieved under these conditions was 1 μg L–1 (100 μL injections). The HPLC-ICP-MS system was used for selenium speciation of selenite and selenate in aqueous solutions during a BCR certification exercise and for selenium speciation in the certified reference material, BCR No. 402 White Clover. Extraction experiments revealed that the selenium species in the biological material were extractable only in the presence of water in the extraction medium. The results indicated that selenate and a compound of unknown identity U were present in the plant sample. 相似文献
67.
The air-gap electrode has been used in kinetic chemical analysis, illustrated by the assay of the activities of the enzymes urease and arginase. The determinations are based on monitoring the initial reaction rates of the selective release of ammoniacal nitrogen, which in the arginine—arginase system was ensured by adding excess of urease. The reaction rates measured are in the range 2.5 · 10-5—1.5 · 10-3M min-1; the relative standard deviation is ca. 2.8 %. 相似文献
68.
69.
Petersson B Nielsen BB Rasmussen H Larsen IK Gajhede M Nielsen PE Kastrup JS 《Journal of the American Chemical Society》2005,127(5):1424-1430
The X-ray structure of a partly self-complementary peptide nucleic acid (PNA) decamer (H-GTAGATCACT-l-Lys-NH(2)) to 2.60 A resolution is reported. The structure is mainly controlled by the canonical Watson-Crick base pairs formed by the self-complementary stretch of four bases in the middle of the decamer (G(4)A(5)T(6)C(7)). One right- and one left-handed Watson-Crick duplex are formed. The two PNA units C(9)T(10) change helical handedness, so that each PNA strand contains both a right- and a left-handed section. The changed handedness in C(9)T(10) allows formation of Hoogsteen hydrogen bonding between C(9)T(10) and G(4)A(5) of a PNA strand in an adjacent Watson-Crick double helix of the same handedness. Thereby, a PNA-PNA-PNA triplex is formed. The PNA unit A(3) forms a noncanonical base pair with A(8) in a symmetry-related strand of opposite handedness; the base pair is of the A-A reverse Hoogsteen type. The structural diversity of this PNA demonstrates how the PNA backbone is able to adapt to structures governed by the stacking and hydrogen-bonding interactions between the nucleobases. The crystal structure further shows how PNA oligomers containing limited sequence complementarity may form complex hydrogen-bonding networks. 相似文献
70.