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51.
Morozova OB Ivanov KL Kiryutin AS Sagdeev RZ Köchling T Vieth HM Yurkovskaya AV 《Physical chemistry chemical physics : PCCP》2011,13(14):6619-6627
Chemically Induced Dynamic Nuclear Polarization (CIDNP) of the diamagnetic products of radical reactions is exploited for the purpose of determination of the hyperfine coupling constants (HFCCs) of the radical intermediates. A simple proportionality relation between geminate CIDNP of a nucleus and its HFCC at the radical stage is established. The applicability range of this relation is determined: the relation is fulfilled in the case of a large difference in g-factor between the radicals involved and for the situation where the number of magnetic nuclei in the system is sufficiently large. The validity of the relation was confirmed by CIDNP experiments on radical pairs with precisely known HFCCs. Using the proportionality relation we were able to measure the HFCCs in various short-lived radicals of the amino acids histidine and tryptophan and of the S-N-centered cyclic radical of methionine derived from the methionine-glycine dipeptide in aqueous solution. 相似文献
52.
A. Hoser W. Prandl P. Schiebel G. Heger 《Zeitschrift für Physik B Condensed Matter》1990,81(2):259-263
The ND3 group is in the high temperature phase of the title compound dynamically disordered. Fourier maps derived from the analysis of neutron single crystal Bragg data with phases based on a split atom and a Frenkel model show uniquely that each D3 group has four density maxima occupying the corners of a square. Neither one nor three dimensional models of purely rotational disorder can describe the observations adequately. 相似文献
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Ratios of K/L shell X-ray yields by 10–20 MeV electrin and positron impact on Au have been measured with an accuracy of better than ±1.6%. The results show that the K-shell X-ray production cross section by electron impact is about 2% larger than by positron impact. 相似文献
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Dom JJ van der Veken BJ Michielsen B Jacobs S Xue Z Hesse S Loritz HM Suhm MA Herrebout WA 《Physical chemistry chemical physics : PCCP》2011,13(31):14142-14152
A vibrational assignment of the anaesthetic sevoflurane, (CF(3))(2)CHOCH(2)F, is proposed and its interaction with the aromatic model compound benzene is studied using vibrational spectroscopy of supersonic jet expansions and of cryosolutions in liquid xenon. Ab initio calculations, at the MP2/cc-pVDZ and MP2/aug-cc-pVDZ levels, predict two isomers for the 1?:?1 complex, one in which the near-cis, gauche conformer of sevoflurane is hydrogen bonded through its isopropyl-hydrogen atom, the other in which the same conformer is bonded through a bifurcated hydrogen bond with the fluoromethyl hydrogen atoms. From the experiments it is shown that the two isomers are formed, however with a strong population dominance of the isopropyl-bonded species, both in the jet and liquid phase spectra. The experimental complexation enthalpy in liquid xenon, ΔH(o)(LXe), of this species equals -10.9(2) kJ mol(-1), as derived from the temperature dependent behaviour of the cryosolution spectra. Theoretical complexation enthalpies in liquid xenon were obtained by combining the complete basis set extrapolated complexation energies at the MP2/aug-cc-pVXZ (X = D,T) level with corrections derived from statistical thermodynamics and Monte Carlo Free Energy Perturbation calculations, resulting in a complexation enthalpy of -11.2(3) kJ mol(-1) for the isopropyl-bonded complex, in very good agreement with the experimental value, and of -11.4(4) kJ mol(-1), for the fluoromethyl-bonded complex. The Monte Carlo calculations show that the solvation entropy of the isopropyl-bonded species is considerably higher than that of the fluoromethyl-bonded complex, which assists in explaining its dominance in the liquid phase spectra. 相似文献
58.
Brügger G Frey HM Steinegger P Kowalewski P Leutwyler S 《The journal of physical chemistry. A》2011,115(44):12380-12389
We combine the technique of femtosecond degenerate four-wave mixing (fs-DFWM) with a high repetition-rate pulsed supersonic jet source to obtain the rotational coherence spectrum (RCS) of cold cyclohexane (C(6)H(12)) with high signal/noise ratio. In the jet expansion, the near-parallel flow pattern combined with rapid translational cooling effectively eliminate dephasing collisions, giving near-constant RCS signal intensities over time delays up to 5 ns. The vibrational cooling in the jet eliminates the thermally populated vibrations that complicate the RCS coherences of cyclohexane at room temperature [Brügger, G.; et al. J. Phys. Chem. A 2011, 115, 9567]. The rotational cooling reduces the high-J rotational-state population, yielding the most accurate ground-state rotational constant to date, B(0) = 4305.859(9) MHz. Based on this B(0), a reanalysis of previous room-temperature gas-cell RCS measurements of cyclohexane gives improved vibration-rotation interaction constants for the ν(32), ν(6), ν(16), and ν(24) vibrational states. Combining the experimental B(0)(C(6)H(12)) with CCSD(T) calculations yields a very accurate semiexperimental equilibrium structure of the chair isomer of cyclohexane. 相似文献
59.
Axel Treu Miriam Rittner Dorit Kemken Hans‐Martin Schiebel Peter Spiteller Thomas Dülcks 《Journal of mass spectrometry : JMS》2015,50(8):978-986
The fragment spectra of protonated nitro‐substituted benzodiazepines show an unusual fragment [M + H ‐ 14]+, which is shown by accurate mass measurement to be due to the loss of a nitrogen atom. Our investigations show that this apparent loss of atomic nitrogen is rather an attachment of molecular oxygen to the [M + H ‐ NO2]+? ion, which is the main fragment ion in these spectra. The oxygen attachment is exothermic, and rate constants have been derived. MSn spectra show that it is not easily reversible upon fragmentation of the adduct ion and that it is also observed with some secondary and tertiary fragments, which allows to limit the attachment site to the aromatic ring annulated to the diazepine moiety. Fragments of the oxygen adduct ion indicate that the O2 molecule dissociates in the adduct formation process, and the two oxygen atoms are bound to different sites of the ion. Comparison with radical cations generated by fragmentation of non‐nitro‐substituted benzodiazepines, none of which showed an oxygen attachment, and the fragmentation mechanisms involved in their formation indicates that the [M + H ‐ NO2]+? ion is a distonic ion with the charge and radical site neighbored on the aromatic ring. From these results, we derive a proposal for the formation and structure of the [M + H ‐ NO2 + O2]+? ion, which explains the experimental observations. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
60.
Sarah P. Niehs Benjamin Dose Sophie Richter Dr. Sacha J. Pidot Dr. Hans-Martin Dahse Prof. Timothy P. Stinear Prof. Dr. Christian Hertweck 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7840-7845
A spider-transmitted fungus (Rhizopus microsporus) that was isolated from necrotic human tissue was found to harbor endofungal bacteria (Burkholderia sp.). Metabolic profiling of the symbionts revealed a complex of cytotoxic agents (necroximes). Their structures were characterized as oxime-substituted benzolactone enamides with a peptidic side chain. The potently cytotoxic necroximes are also formed in symbiosis with the fungal host and could have contributed to the necrosis. Genome sequencing and computational analyses revealed a novel modular PKS/NRPS assembly line equipped with several non-canonical domains. Based on gene-deletion mutants, we propose a biosynthetic model for bacterial benzolactones. We identified specific traits that serve as genetic handles to find related salicylate macrolide pathways (lobatamide, oximidine, apicularen) in various other bacterial genera. Knowledge of the biosynthetic pathway enables biosynthetic engineering and genome-mining approaches. 相似文献