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551.
Davis WC Venzie JL Willis B Coffee RL Arya DP Marcus RK 《Rapid communications in mass spectrometry : RCM》2003,17(15):1749-1758
Use of a particle beam glow discharge (PB-GD) source for mass spectrometric determinations of deoxy- and ribonucleosides and nucleotides is described. Use of this combination of sample introduction and ion source decouples the vaporization and ionization steps, leading to very simple spectral structure. The mass spectra of these compounds are EI-like in nature, with clearly identified molecular ions and fragmentation patterns that are easily rationalized. The PB-GDMS combination can be operated in a flow injection mode wherein the analyte is injected directly into the solvent flow, or can also be coupled to a high-performance liquid chromatography (HPLC) system allowing LC/MS analysis of mixtures. Mass spectra obtained for nucleic acid bases, nucleosides, and nucleotides are readily obtained with injections of low-nanomole quantities. Representative PB-GDMS spectra for deoxy- and ribonucleosides, nucleotides, and mixed-base oligonucleotides are presented to demonstrate the capabilities of the GD source. Characteristic fragmentation peaks from the spectra of adenine, cytosine, guanine, and thymine were identified in 22-base sequences of single-stranded DNA. The PB-GD source is capable of producing spectra that may be used to identify the individual bases present in mixed-base DNA and RNA fragments. 相似文献
552.
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554.
The bidentate ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene ( 1 ) was synthesized from 2,11-dimethyl-benzo[c]phenanthrene ( 3 ) via the corresponding bromomethyl derivative 9. 3 was obtained from the cyclization with boron trifluoride etherate of 1,1-di-(p-methylphenethyl)-epoxyethane ( 7 ), which was prepared from 1,5-di(p-tolyl)-pentan-3-one ( 6 ). 相似文献
555.
Leavens WJ Lane SJ Carr RM Lockie AM Waterhouse I 《Rapid communications in mass spectrometry : RCM》2002,16(5):433-441
A simple method for the derivatization of primary amines and carboxylic acids with tris(trimethoxyphenyl)phosphonium (TMPP) reagents to enhance their detection by electrospray mass spectrometry (ESI-MS) has been developed. The synthesis of novel TMPP reagents and their stable isotopically labelled analogues is described. Through the use of stable isotopically labelled TMPP "tags", incorporation of a doublet (1:1, (1)H/(2)H or (12)C/(13)C) into the target molecule can be achieved, enabling the use of isotopic target analysis to detect compounds of unknown molecular weight but with a characteristic isotope pattern and accurate mass difference. 相似文献
556.
The effect of polarization functions for ab initio molecular orbital calculations at the 3-21G* level has been studied for disiloxane. Calculated molecular geometry, dipole moment, and the linearization barrier variation were analyzed for different uncontracted polarization functions. It was concluded that variation of the polarization function on oxygen has only a minor influence on the molecular properties of disiloxane, but its presence is required to obtain a bent geometry for the disiloxane bond. The calculated molecular properties of disiloxane are greatly influenced when the polarization function on silicon is varied. Two different values (0.3 and 0.9) for the exponent of the silicon polarization function provide results comparable to the experimental values for disiloxane. The only significant differences between the results obtained from ab initio calculations using the two polarization functions are in net atomic charges. The uncontracted polarization function of silicon with a value of 0.3 for its exponent is transferable to other organosilicon compounds. Calculated molecular geometries of flexible or rigid structures are in very good agreement with the experimental values. 相似文献
557.
Ion chromatography was used to detect levels of copper and zinc in blood plasma from renal dialysis patients on continuous ambulatory peritoneal dialysis (CAPD) and haemodialysis (HD). The developed method used cobalt as an internal standard and when combined with the standard additions method improved the overall precision of the results by between -0.3 and 6.0% and -0.8 and 5.7% for copper and zinc, respectively. The method was compared with inductively coupled plasma optical emission spectrometry (ICP-OES) and the results indicated no significant difference between the two methods with or without an internal standard. Without an internal standard, tcalc was 0.869 with a tcrit of 2.201 (n = 12, P = 0.05) and with an internal standard, tcalc was 0.189 compared to a tcrit of 2.201 (n = 12, P = 0.05). The copper and zinc levels in blood plasma in both dialysis groups were not significantly different to the copper and zinc levels in blood plasma of the control patients. A convenient method of analysis of trace elements in blood such as ion chromatography with UV/VIS detection is useful for determining whether inorganic elements may be disrupted in the body due to changes in the state of health. 相似文献
558.
Silicon-29 NMR shifts for a series of 2,2-diphenyl-1,3,2-dioxasilacycloalkanes are reported and reveal a clear dependence of shift on ring size for rings of 5–14 atoms. 相似文献
559.
A simple procedure to analyze ammonia in ethylene by ion mobility spectrometry is described. The spectrometer is operated with a silane polymer membrane., 63Ni ion source, H+ (H2O)n reactant ion, and nitrogen drift and source gas. Ethylene containing parts per billion (ppb) (v/v) concentrations of ammonia is pulled across the membrane and diffuses into the spectrometer. Preconcentration or preseparation is unnecessary, because the ethylene in the spectrometer has no noticeable effect on the analytical results. Ethylene does not polymerize in the radioactive source. Ethylene's flammability is negated by the nitrogen inside the spectrometer. Response to ammonia concentrations between 200 ppb and 1.5 ppm is near linear, and a detection limit of 25 ppb is calculated. 相似文献
560.
Shen HC Wang J Cole KP McLaughlin MJ Morgan CD Douglas CJ Hsung RP Coverdale HA Gerasyuto AI Hahn JM Liu J Sklenicka HM Wei LL Zehnder LR Zificsak CA 《The Journal of organic chemistry》2003,68(5):1729-1735
A detailed account regarding a formal [3 + 3] cycloaddition method using 4-hydroxy-2-pyrones and 1,3-diketones is described here. This formal cycloaddition reaction or annulation reaction is synthetically useful for constructing 2H-pyranyl heterocycles. The usage of alpha,beta-unsaturated iminium salts is significant in controlling competing reaction pathways to give exclusively 2H-pyrans. Most significantly, experimental evidence is provided to support the mechanism of this reaction that involves a sequential Knoevenagel condensation and a reversible 6pi-electron electrocyclic ring-closure of 1-oxatrienes. 相似文献