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351.
Discrete Conditional Phase-type models (DC-Ph) consist of a process component (survival distribution) preceded by a set of related conditional discrete variables. This paper introduces a DC-Ph model where the conditional component is a classification tree. The approach is utilised for modelling health service capacities by better predicting service times, as captured by Coxian phase-type distributions, interfaced with results from a classification tree algorithm. To illustrate the approach, a case-study within the healthcare delivery domain is given, namely that of maternity services. The classification analysis is shown to give good predictors for complications during childbirth. Based on the classification tree predictions, the duration of childbirth on the labour ward is then modelled as either a two or three-phase Coxian distribution. The resulting DC-Ph model is used to calculate the number of patients and associated bed occupancies, patient turnover, and to model the consequences of changes to risk status. 相似文献
352.
353.
Zolot AM Harper WW Perkins BG Dagdigian PJ Nesbitt DJ 《The Journal of chemical physics》2006,125(2):21101
Exothermic reactive scattering of F atoms at the gas-liquid interface of a liquid hydrocarbon (squalane) surface has been studied under single collision conditions by shot noise limited high-resolution infrared absorption on the nascent HF(v,J) product. The nascent HF(v,J) vibrational distributions are inverted, indicating insufficient time for complete vibrational energy transfer into the surface liquid. The HF(v=2,J) rotational distributions are well fit with a two temperature Boltzmann analysis, with a near room temperature component (T(TD) approximately equal to 290 K) and a second much hotter scattering component (T(HDS) approximately equal to 1040 K). These data provide quantum state level support for microscopic branching in the atom abstraction dynamics corresponding to escape of nascent HF from the liquid surface on time scales both slow and fast with respect to rotational relaxation. 相似文献
354.
Chevallier C Bugni TS Feng X Harper MK Orendt AM Ireland CM 《The Journal of organic chemistry》2006,71(6):2510-2513
Cytotoxicity-guided fractionation of the crude methanol extract of a marine sponge, Ircinia sp., yielded tedanolide C (1), a new 18-membered macrolide. The structure was solved by interpreting NMR and MS data, and the relative stereochemistry was determined from a combination of homo- and heteronuclear coupling constants in conjunction with molecular modeling. Compound 1 exhibited potent cytotoxicity against HCT-116 cells in vitro. Cell cycle analysis showed that treatment of cells with compound 1 arrested cells in the S-phase. 相似文献
355.
H K?SmithEmail author G?Laporte P R?Harper 《The Journal of the Operational Research Society》2009,60(1):S140-S148
Locational analysis has grown to maturity over the last decades, from its earliest roots, to fruitfulness in a wide-ranging number of strands that join with other disciplines and applications such as environmental planning and supply chain management. This paper charts the progress of location theory in three stages: a period of early contributions, when a number of seminal geometrical and geographical problems were studied; a ‘coming of age’ with the development of defining or classical problems that have proved fundamental to much later research and a third period of new models and new applications. 相似文献
356.
Angela F. Harper Steffen P. Emge Pieter C. M. M. Magusin Clare P. Grey Andrew J. Morris 《Chemical science》2023,14(5):1155
Understanding a material''s electronic structure is crucial to the development of many functional devices from semiconductors to solar cells and Li-ion batteries. A material''s properties, including electronic structure, are dependent on the arrangement of its atoms. However, structure determination (the process of uncovering the atomic arrangement), is impeded, both experimentally and computationally, by disorder. The lack of a verifiable atomic model presents a huge challenge when designing functional amorphous materials. Such materials may be characterised through their local atomic environments using, for example, solid-state NMR and XAS. By using these two spectroscopy methods to inform the sampling of configurations from ab initio molecular dynamics we devise and validate an amorphous model, choosing amorphous alumina to illustrate the approach due to its wide range of technological uses. Our model predicts two distinct geometric environments of AlO5 coordination polyhedra and determines the origin of the pre-edge features in the Al K-edge XAS. From our model we construct an average electronic density of states for amorphous alumina, and identify localized states at the conduction band minimum (CBM). We show that the presence of a pre-edge peak in the XAS is a result of transitions from the Al 1s to Al 3s states at the CBM. Deconvoluting this XAS by coordination geometry reveals contributions from both AlO4 and AlO5 geometries at the CBM give rise to the pre-edge, which provides insight into the role of AlO5 in the electronic structure of alumina. This work represents an important advance within the field of solid-state amorphous modelling, providing a method for developing amorphous models through the comparison of experimental and computationally derived spectra, which may then be used to determine the electronic structure of amorphous materials.A first principles model of amorphous Al2O3 is constructed which reproduces the features of experimental 27Al NMR and Al K-edge XAS spectra on an ALD-deposited sample of amorphous Al2O3. 相似文献
357.
358.
H. F. Wiebe D. R. Harper L. Holborn F. Henning H. L. Callendar E. H. Griffiths C. W. Waidner G. K. Burgess A. L. Day R. B. Sosman L. H. Adams J. Johnston G. Moeller F. Hoffmann W. Meissner J. G. L. Stern Th. W. Richards R. C. Wells W. Meissner Th. W. Richards F. G. Jackson C. Kellner H. F. Wiebe P. Hebe P. Hebe und M. Freund 《Fresenius' Journal of Analytical Chemistry》1913,52(5):304-308
Ohne Zusammenfassung 相似文献
359.
Shannon Sestile David Richardson Ryan Toomey Laurence G. Cool James K. Harper 《Magnetic resonance in chemistry : MRC》2021,59(1):23-33
The connectivity, conformation, tautomeric form, and dynamics of a new depsidone (perisalazinic acid) were characterized using one‐bond 13C? 13C NMR scalar couplings (1JCC) obtained from the INADEQUATE experiment. Characterization of perisalazinic acid using more conventional NMR techniques is problematic due to the extremely limited number of C? H protons present. In the present study, 81 candidate structures were considered and a best fit structure was selected by comparing computed 1JCC values for each candidate to 15 experimental values. Of the six flexible moieties in perisalazinic acid, three are adequately represented by a single orientation stabilized by intramolecular hydrogen bonding. The three remaining groups are present as mixtures of conformers with two sites consisting of a pair of conformations and another disordered over six orientations. This study demonstrates the feasibility of complete three‐dimensional structural characterization of an unknown using only theoretical and experimental 1JCC values. 相似文献
360.
Alberto F. Garrido-Castro Yuta Hioki Yoshifumi Kusumoto Kyohei Hayashi Jeremy Griffin Kaid C. Harper Yu Kawamata Phil S. Baran 《Angewandte Chemie (International ed. in English)》2023,62(42):e202309157
A mild, scalable (kg) metal-free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access to valuable olefins from simple carboxylic acid feedstocks. This robust method relies on alternating polarity to maintain the quality of the electrode surface and local pH, providing a deeper understanding of the Hofer-Moest process with unprecedented chemoselectivity. 相似文献