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81.
Qichao Zhao Jens Eichhorn William R. Pitner Jared L. Anderson 《Analytical and bioanalytical chemistry》2009,395(1):225-234
Ionic liquids (ILs) containing the tris(pentafluoroethyl)trifluorophosphate anion [FAP]− have attracted increased attention due to their unique properties including ultrahigh hydrophobicity, hydrolytic stability,
and wide electrochemical window. In this study, the solvation parameter model is used via gas chromatography to characterize
the solvation interactions of seven ILs containing amino, ester, and hydroxyl functional groups appended to the cation and
paired with [FAP]−, as well as three ILs containing the bis[(trifluoromethyl)sulfonyl]imide anion [NTf2]−. The role of the functional groups, nature of the counter anion, and cation type on the system constants were evaluated.
ILs containing [FAP]− possessed lower hydrogen bond basicity than NTf2-based ILs having the same cationic component; in the case of hydroxyl-functionalized cations, the presence of [FAP]− led to an enhancement of the hydrogen bond acidity, relative to the NTf2-analogs. The system constants support the argument that [FAP]− weakly coordinates the cation and any appended functional groups, promoting properties of the cation which might be masked
by stronger interactions with other anion systems. The chromatographic performance of the IL stationary phases was evaluated
by examining the retention behavior and separation selectivity for chosen analytes. The results from this work can be used
as a guide for choosing FAP-based ILs capable of exhibiting desired solvation properties while retaining important physical
properties including high thermal stability and high hydrophobicity.
Figure In this study, the solvation parameter model is used via gas chromatography to characterize the solvation interactions of
seven ILs containing amino, ester, and hydroxyl functional groups appended to the cation and paired with tris(pentafluoroethyl)trifluorophosphate
[FAP]−, as well as three ILs containing the bis[(trifluoromethyl)sulfonyl]imide anion [NTf2]−.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
82.
A novel microextraction method is introduced based on dispersive liquid–liquid microextraction (DLLME) in which an in situ
metathesis reaction forms a water-immiscible ionic liquid (IL) that preconcentrates aromatic compounds from water followed
by separation using high-performance liquid chromatography. The simultaneous extraction and metathesis reaction forming the
IL-based extraction phase greatly decreases the extraction time as well as provides higher enrichment factors compared to
traditional IL DLLME and direct immersion single-drop microextraction methods. The effects of various experimental parameters
including type of extraction solvent, extraction and centrifugation times, volume of the sample solution, extraction IL and
exchanging reagent, and addition of organic solvent and salt were investigated and optimized for the extraction of 13 aromatic
compounds. The limits of detection for seven polycyclic aromatic hydrocarbons varied from 0.02 to 0.3 μg L−1. The method reproducibility produced relative standard deviation values ranging from 3.7% to 6.9%. Four real water samples
including tap water, well water, creek water, and river water were analyzed and yielded recoveries ranging from 84% to 115%.
相似文献
83.
Wiedemann SH Lewis JC Ellman JA Bergman RG 《Journal of the American Chemical Society》2006,128(7):2452-2462
Evidence is presented for a proposed mechanism of C-H activation of 3-methyl-3,4-dihydroquinazoline (1) by (PCy(3))(2)RhCl. One intermediate (3), a coordination complex of 1 with (PCy(3))(2)RhCl, was identified along the path to the Rh-N-heterocyclic carbene product of this reaction (2). Isotopic labeling and reaction-rate studies were used to demonstrate that C-H activation takes place intramolecularly on the reaction coordinate between 3 and 2. Computational studies corroborate the proposed mechanism and suggest that the rate-limiting step is oxidative addition of the C-H bond to the metal center. The consequences of this mechanism for coupling reactions of N-heterocycles that occur via Rh-catalyzed C-H bond activation are discussed. 相似文献
84.
Wang J Scampicchio M Laocharoensuk R Valentini F Gonzalez-García O Burdick J 《Journal of the American Chemical Society》2006,128(14):4562-4563
Nanowires have received considerable attention owing to their broad potential applications. We report here on the application of nanowires for magnetic control of the electrochemical reactivity and demonstrate how one can modulate the electrocatalytic activity by orienting catalytic nanowires at different angles. Unlike early "on/off" magnetic switching studies based on functionalized magnetic spheres, the present magnetoswitchable protocol relies on modulating the electrochemical reactivity without removing the magnetic material from the surface. Such behavior is attributed to the reversible blocking of the redox processes and to changes in the tortuosity-dependent flux rate. The nanowire-based magnetoswitchable protocol may be extremely useful for adjusting the electrochemical reactivity, such as for tuning the power output of fuel cells (rather than switching the power on/off). 相似文献
85.
Casado J Ruiz Delgado MC Rey Merchán MC Hernández V López Navarrete JT Pappenfus TM Williams N Stegner WJ Johnson JC Edlund BA Janzen DE Mann KR Orduna J Villacampa B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(21):5458-5470
A series of tricyanovinyl (TCV)-substituted oligothiophenes was synthesized and investigated with a number of physical methods including UV/Vis, IR, and Raman spectroscopy, nonlinear optical (NLO) measurements, X-ray diffraction, and cyclic voltammetry. Mono- or disubstituted oligomers were prepared by the reaction of tetracyanoethylene with mono- or dilithiated oligomers. The comparative effects of the symmetric and asymmetric substitutions in the electronic and molecular properties have been addressed. These oligomers display dramatic reductions in both their optical and electrochemical band gaps in comparison with unsubstituted molecules. The analysis of the electronic properties of the molecules was assisted by density functional theory calculations, which are in excellent agreement with the experimental data. TCV substitution influences the energies of the frontier orbitals, especially with respect to the stabilization of LUMO orbitals. X-ray structural characterization of a monosubstituted oligomer exhibits pi-stacking with favorable intermolecular interactions. NLO results agree with the role of the intramolecular charge-transfer feature in the asymmetric samples. These results furthermore exalt the role of conformational flexibility in the disubstituted compounds and reveal an unexpected nonlinear optical activity for symmetric molecules. Regarding the electronic structure, the interpretation of the vibrational data reflects the balanced interplay between aromatic and quinoid forms, finely tuned by the chain length and substitution pattern. The electronic and structural properties are consistent with the semiconducting properties exhibited by these materials in thin film transistors (TFTs). 相似文献
86.
Mg(2.56)V(1.12)W(0.88)O(8) crystals were grown from a MgO/V(2)O(5)/WO(3) melt. X-ray single-crystal diffraction studies revealed that it is orthorhombic with space group Pnma, a = 5.0658(5) A, b = 10.333(1) A, c = 17.421(2) A, Z = 6, and is isostructural with Mg(2.5)VMoO(8). Raman spectra are reported, and the assignment of the Raman bands is made by comparing the metal-oxygen vibrations of VO(4)/WO(4) tetrahedra in Mg(2.5)VWO(8) with the metal-oxygen vibrations of VO(4)/MoO(4) tetrahedra in Mg(2.5)VMoO(8). The stretching vibrations appearing at 1016 and 1035 cm(-)(1) are assigned to Mo=O and W=O double bonds, respectively, associated with the Mg(2+) cation vacancies. 相似文献
87.
Jared B. Shaw Tzu-Yung Lin Franklin E. LeachIII Aleksey V. Tolmachev Nikola Tolić Errol W. Robinson David W. Koppenaal Ljiljana Paša-Tolić 《Journal of the American Society for Mass Spectrometry》2016,27(12):1929-1936
We provide the initial performance evaluation of a 21 Tesla Fourier transform ion cyclotron resonance mass spectrometer operating at the Environmental Molecular Sciences Laboratory at the Pacific Northwest National Laboratory. The spectrometer constructed for the 21T system employs a commercial dual linear ion trap mass spectrometer coupled to a FTICR spectrometer designed and built in-house. Performance gains from moving to higher magnetic field strength are exemplified by the measurement of peptide isotopic fine structure, complex natural organic matter mixtures, and large proteins. Accurate determination of isotopic fine structure was demonstrated for doubly charged Substance P with minimal spectral averaging, and 8158 molecular formulas assigned to Suwannee River Fulvic Acid standard with root-mean-square (RMS) error of 10 ppb. We also demonstrated superior performance for intact proteins; namely, broadband isotopic resolution of the entire charge state distribution of apo-transferrin (78 kDa) and facile isotopic resolution of monoclonal antibody under a variety of acquisition parameters (e.g., 6 s time-domains with absorption mode processing yielded resolution of approximately 1 M at m/z?=?2700). 相似文献
88.
Jared F. Bauters James R. Adleman Martijn J. R. Heck John E. Bowers 《Applied Physics A: Materials Science & Processing》2014,116(2):427-432
Planar waveguides with ultra-low propagation loss are necessary for integrating optoelectronic systems that require long optical time delay or narrowband optical filters. In this paper, we review an ultra-low loss planar waveguide platform that uses thin (<150 nm) Si3N4 cores and thick (>8 μm) SiO2 cladding layers. In particular, we discuss the performance of arrayed waveguide gratings (AWGs) fabricated with the platform. We propose the use of a practical design method that takes the statistical nature of worst-case crosstalk into account. We also demonstrate the measurement of amplitude and phase error distributions in an AWG using an optical backscatter reflectometer. We show that the waveguides have phase errors small enough to achieve AWG crosstalk below ?30 dB, while crosstalk below ?40 dB should also be possible with optimization of the component design. 相似文献
89.
The synthesis of 1,3-diaminated stereotriads via the bis-aziridination of allenes is reported. The reactive 1,4-diazaspiro[2.2]pentane intermediates undergo a mild Br?nsted acid-promoted rearrangement to yield 1,3-diaminated ketones in good yields with excellent stereocontrol. Directed reduction of the ketone can be achieved to yield a C-N/C-O/C-N stereotriad in high dr. The ability to transfer the axial chirality of the substrates to the products allows for the facile preparation of enantioenriched stereotriads from allenes in two simple steps. 相似文献
90.
Four mixtures of four fluorous-tagged quasiisomers have been synthesized, demixed, and detagged to make all 16 stereoisomers of the macrocyclic lactone natural product Sch725674. A new bare-minimum tagging pattern needs only two tags--one fluorous and one nonfluorous--to encode four isomers. The structure of Sch725674 is assigned as (5R,6S,8R,14R,E)-5,6,8-trihydroxy-14-pentyloxacyclotetradec-3-en-2-one. Various comparisons of spectra of 32 lactones (16 with tags, 16 without) and 16 ester precursors (8 with tags, 8 without) provide insights into when and why related compounds have the same or different spectra. 相似文献