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121.
Matthieu Baudelet Myriam Boueri Jin Yu Samuel S. Mao Vincent Piscitelli Xianglei Mao Richard E. Russo 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1329-1334
Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample. 相似文献
122.
Fabrication of a Single Layer and Bilayer Potentiometric Biosensors for Penicillin by Galvanostatic Entrapment of Penicillinase into Polypyrrole Films 总被引:1,自引:0,他引:1 下载免费PDF全文
A single layer and bilayer potentiometric biosensors for the detection of penicillin have been developed. The favourable conditions that were established for the polypyrrole‐penicillinase ((PPy‐P’nase) single layer biosensor were 0.03 M pyrrole, 50 U/mL P’nase, 0.01 M penicillin, applied current density of 0.9 mA/cm2 and a polymerisation time of 40 s. The optimum conditions for the formation of the outer layer of the bilayer were: (a) 0.1 M Py, 19 U/mL P’nase, 0.01 M pen, current density of 0.9 mA/cm2 and a polymerisation time of 40 s. The minimum detectable penicillin concentration with the bilayer potentiometric biosensor was 0.3 µM and the linear concentration range was 7.5–146 µM. The average percentage recovery of penicillin that was found in amoxycillin 500 mg was 113±24 %. The determination of penicillin in milk was fraught with problems of non‐specific binding of penicillin to the milk. 相似文献
123.
Dr. Thomas L. Gianetti Dr. Samuel P. Annen Dr. Gustavo Santiso‐Quinones Prof. Dr. Markus Reiher Prof. Dr. Matthias Driess Prof. Dr. Hansjörg Grützmacher 《Angewandte Chemie (International ed. in English)》2016,55(5):1854-1858
The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2 and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh?H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate. 相似文献
124.
Samuel F. Cousin Dr. Pavel Kadeřávek Baptiste Haddou Dr. Cyril Charlier Thorsten Marquardsen Jean‐Max Tyburn Dr. Pierre‐Alain Bovier Dr. Frank Engelke Dr. Werner Maas Prof. Dr. Geoffrey Bodenhausen Dr. Philippe Pelupessy Prof. Dr. Fabien Ferrage 《Angewandte Chemie (International ed. in English)》2016,55(34):9886-9889
Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two‐field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low‐field dimension. Two‐field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields. 相似文献
125.
A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State 下载免费PDF全文
Junpeng He Nolan W. Waggoner Samuel G. Dunning Dr. Alexander Steiner Dr. Vincent M. Lynch Prof. Simon M. Humphrey 《Angewandte Chemie (International ed. in English)》2016,55(40):12351-12355
A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air‐ and moisture‐stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal–organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with PdIICl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with CoII ions and structural resolution by single crystal X‐ray diffraction. The Pd?Cl groups inside the pores are accessible to post‐synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd?CH3 activated material undergoes rapid insertion of CO2 gas to give Pd?OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd?N3 modified version resists CO insertion under the same conditions. 相似文献
126.
Samuel A. Delp Colleen Munro-Leighton Chetna Khosla Joseph L. Templeton Nikki M. Alsop T. Brent Gunnoe Thomas R. Cundari 《Journal of organometallic chemistry》2009,694(9-10):1549-1556
Using 2D proton-coupled gHSQC pulse sequences in addition to 1D 15N NMR experiments of 15N labeled systems, 15N NMR chemical shifts of a range of transition metal amido and amine complexes were determined. Tungsten(II), ruthenium(II), platinum(IV) and copper(I) complexes with aniline and their anilido variants were studied and compared to free aniline, lithium anilido and anilinium tetrafluoroborate. Upon coordination of aniline to transition metals, upfield chemical shifts of 20–60 ppm were observed. Deprotonation of the amine complexes to form amido complexes resulted in downfield chemical shifts of 40–60 ppm for all of the complexes except for the tungsten d4 system. For the tungsten(II) complexes, the cationic aniline complex displayed a downfield shift of approximately 56 ppm relative to the neutral anilido complex. The change in chemical shift for amine to amido conversion is proposed to depend on the ability of the amido ligand to π-bond with the metal center, which influences the magnitude of the paramagnetic screening term. 相似文献
127.
Samuel Drouet 《Tetrahedron》2009,65(51):10693-2601
New symmetrical dendrimeric type super-porphyrin bearing sixteen fluorenyl donor groups sixteen fluorenylporphyrin SOFP (1) have been synthesized and characterized. Preliminary photophysical properties are reported; in comparison to the references first generation dendrimer tetrafluorenylporphyrin TOFP (2) bearing four peripheral fluorenyl and second generation dendrimer octafluorenylporphyrin OOFP (3) bearing eight peripheral fluorenyl, the luminescence properties are slightly improved. It is found that the excitation energy transfer occurs from the sixteen fluorenyl units to the porphyrin core, following what the porphyrin emits intense red light. 相似文献
128.
Camille Pierry Philippe Jubault Thierry Lequeux Samuel Couve-Bonnaire 《Tetrahedron letters》2009,50(3):264-7404
Grignard and organolithium reagents efficiently react with (S)-N-(tert-butanesulfinyl)-α-fluoroenimines to provide chiral allylamines in excellent yields and with diastereomeric ratios of up to 96:4. Acidic removal of the sulfinyl group and simple functional group transformations allow to get enantiopure fluoroolefin dipeptide mimics. 相似文献
129.
Plasencia MD Isailovic D Merenbloom SI Mechref Y Novotny MV Clemmer DE 《Journal of the American Society for Mass Spectrometry》2008,19(11):1706-1715
Ion mobility-mass spectrometry (IMS-MS) and molecular modeling techniques have been used to characterize ovalbumin N-linked
glycans. Some glycans from this glycoprotein exist as multiple isomeric forms. The gas-phase separation makes it possible
to resolve some isomers before MS analysis. Comparisons of experimental cross sections for selected glycan isomers with values
that are calculated for iterative structures generated by molecular modeling techniques allow the assignment of sharp features
to specific isomers. We focus here on an example glycan set, each having a m/z value of 1046.52 with formula [H5N4+2Na]2+, where H corresponds to a hexose, and N to a N-acetylglucosamine. This glycan appears to exist as three different isomeric forms that are assignable based on comparisons
of measured and calculated cross sections. We estimate the relative ratios of the abundances of the three isomers to be in
the range of ∼1.0:1.35:0.85 to ∼1.0:1.5:0.80. In total, IMS-MS analysis of ovalbumin N-linked glycans provides evidence for
19 different glycan structures corresponding to high-mannose and hybrid type carbohydrates with a total of 42 distinct features
related to isomers and/or conformers. 相似文献
130.
Abstract Poly(lactic acid) macromonomers with methacrylate terminal functionality have been synthesized from the cyclic dimer of lactic acid (referred to as lactide) with 2-hydroxyethyl methacrylate (HEMA) as initiator and stannous 2-ethyl hexanoate as catalyst. The macromonomers were characterized with FT-IR, NMR, GPC, DSC, WAXS, and CD. The molecular weights of the macromonomers ranging from M n 1425 to 19,169 are predictable from the lactide/HEMA ratio in the polymerization feeds. The properties of the macromonomers vary with the stereochemistry of the lactide and the composition. Circular dichroism measurements demonstrate that there is little racemization during polymerization. 相似文献