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Prof. Dr. Glen G. Briand Tanner George Gregory A. MacNeil Prof. Dr. Jason D. Masuda Prof. Dr. Brian J. MacLean Michael W. R. Mosher Dr. Gregory M. Sandala Padmapriya Srinivasan Alexander H. Stockli Rachel L. Vanderkloet Prof. Dr. Charles J. Walsby 《欧洲无机化学杂志》2023,26(7):e202200542
Organoindium compounds of redox active 1,2-benzenedithiolate and 2-amidobenzenethiolate ligands were synthesized and tested for reactivity against mild oxidants. The reaction of Me3In and (NCN)InMe2 [NCN=2,6-bis(dimethylaminomethy)phenyl] with 3,4-toluenedithiol (H2tdt) at room temperature afforded [MeIn(tdt)(py)]2 ( 1 ) and (NCN)In(tdt) ( 2 ), respectively. A similar reaction of Me3In with 2-aminobenzenethiol (H2abt) in toluene under reflux afforded [MeIn(abt)(py)]2 ( 3 ). The reaction of (NCN)InCl2 with one equivalent of Li2(abt) or two equivalents of Li(Habt) afforded the compounds [(NCN)In(abt)]⋅LiCl(thf)2 ( 4 ⋅LiCl(thf)2) and (NCN)In(Habt)2 ( 5 ), respectively. The X-ray crystal structures of 1 and 3 are similar and show dimeric structures via μ-S-(tdt) and μ-N-(abt) ligands, respectively. Compounds 2 and 4 possess similar monomeric structures and tridentate NCN pincer ligands. DFT computational studies have been used to rationalize the observed solid-state structures and discern the potential reactivity of compounds 1 – 4 against oxidants. The reaction of 1 and 2 with excess iodine resulted in loss of the 3,4-toluenedithiolate ligand and the formation of the oligomeric disulfide [tdt]n, while 3 and 4 showed no reactivity under similar conditions. This contrasts the reactivity of previously reported organoindium o-amidophenolate complexes which undergo oxidative addition of iodine to afford ligand-centered radical species. 相似文献
44.
Volegov PL Mosher JC Espy MA Kraus RH 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2005,175(1):103-113
Growing interest in magnetic resonance imaging (MRI) at ultra-low magnetic fields (ULF, approximately muT fields) has been motivated by several advantages over its counterparts at higher magnetic fields. These include narrow line widths, the possibility of novel imaging schemes, reduced imaging artifacts from susceptibility variations within a sample, and reduced system cost and complexity. In addition, ULF NMR/MRI with superconducting quantum interference devices is compatible with simultaneous measurements of biomagnetic signals, a capability conventional systems cannot offer. Acquisition of MRI at ULF must, however, account for concomitant gradients that would otherwise result in severe image distortions. In this paper, we introduce the general theoretical framework that describes concomitant gradients, explain why such gradients are more problematic at low field, and present possible approaches to correct for these unavoidable gradients in the context of a non-slice-selective MRI protocol. 相似文献
45.
Michael D. Mosher Laura G. Emmerich Katherine S. Frost Benjamin Anderson 《Journal of heterocyclic chemistry》2006,43(3):535-539
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Lee Mosher 《Journal of Pure and Applied Algebra》1996,110(3):305-314
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Electrokinetic processes that lead to pH gradient instabilities in carrier ampholyte-based IEF are reviewed. In addition to electroosmosis, there are four of electrophoretic nature, namely (i) the stabilizing phase with the plateau phenomenon, (ii) the gradual isotachophoretic loss of carrier ampholytes at the two column ends in presence of electrode solutions, (iii) the inequality of the mobilities of positively and negatively charged species of ampholytes, and (iv) the continuous penetration of carbonate from the catholyte into the focusing column. The impact of these factors to cathodic and anodic drifts was analyzed by simulation of carrier ampholyte-based focusing in closed and open columns. Focusing under realistic conditions within a 5 cm long capillary in which three amphoteric low molecular mass dyes were focused in a pH 3–10 gradient formed by 140 carrier ampholytes was investigated. In open columns, electroosmosis displaces the entire gradient toward the cathode or anode whereas the electrophoretic processes act bidirectionally with a transition around pH 4 (drifts for pI > 4 and pI < 4 typically toward the cathode and anode, respectively). The data illustrate that focused zones of carrier ampholytes have an electrophoretic flux and that dynamic simulation can be effectively used to assess the magnitude of each of the electrokinetic destabilizing factors and the resulting drift for a combination of these effects. Predicted drifts of focused marker dyes are compared to those observed experimentally in a setup with coated capillary and whole column optical imaging. 相似文献
48.
The production of anodic, cathodic and symmetrical drifts of a pH 3.5-10 gradient formed by isoelectric focusing in polyacrylamide gels is demonstrated experimentally by manipulation of the electrolyte concentrations. Experimental behavior is reproduced by computer simulation of a model mixture of 15 hypothetical carrier ampholytes whose pIs span the pH range 3-10. The mechanism which produces the drifts is elucidated and approaches to minimize such drifts are discussed. The data suggest why most experimentally observed drifts are cathodic. 相似文献
49.
Low-lying triplet electronic states have been detected in furan, thiophene, and pyrrole by the method of variable-angle, electron-impact spectroscopy. Singlet → triplet transitions occur with maximum intensity at 3.99 eV and 5.22 eV in furan, 3.75 eV and 4.62 eV in thiophene, and 4.21 eV in pyrrole. A weak transition at 5.22 eV in pyrrole is assigned as the lowest observed singlet → singlet excitation in that molecule. 相似文献
50.