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41.
42.
Metabonomic/metabolomic studies can involve the analysis of large numbers of samples for the detection of biomarkers and confidence in the analytical data, generated by methods such as GC and HPLC-MS, requires active measures on the part of the analyst. However, quality control for complex multi-component samples such as biofluids, where many of the components of interest in the sample are unknown prior to analysis, poses significant problems. Here the repeat analysis of a pooled sample throughout the run, thereby enabling the analysis to be monitored and controlled using targeted inspection of the data and pattern recognition, is advocated as a pragmatic solution to this problem. 相似文献
43.
A wide range of N,O-bis-acylated hydroxylamine derivatives with chloro or arenesulfonyl leaving groups, and a related set of N-hydroxy-N-acylsulfonamides, have been synthesized and evaluated for nitroxyl (HNO) production. Mechanistic studies have revealed that the observed aqueous chemistry is more complicated than originally anticipated, and have been used to develop a new series of efficient HNO precursors (4u-4x, 7c-7d) with tunable half-lives. 相似文献
44.
We use coarse‐grained Langevin dynamics simulations of blends of generic conjugated polymers and acceptor molecules to show how architecture (e.g., side chains, backbone flexibility of oligomers) and the pair‐wise interactions between the constituents of the blend affect morphology and phase transition. Alkyl side chains on the conjugated oligomer backbones shift the liquid crystal (LC) transition temperature from that of bare conjugated backbones and the direction of the shift depends on backbone–backbone interactions. Rigid backbones and constrained side chains cause a layer‐by‐layer morphology of conjugated polymers and amorphous acceptors, whereas flexible backbones and unconstrained side chains facilitate highly ordered acceptor arrangement. Strong backbone–backbone attraction shifts LC transition to higher temperatures than weak backbone–backbone attraction, and strong acceptor–acceptor attraction increases acceptor aggregation. Pure macro‐phase separated domains form when all pair‐wise interactions in the blend are strongly attractive, whereas interconnected domains form at intermediate acceptor–acceptor attraction and strong polymer–polymer attractions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013 相似文献
45.
We prove several basic combinatorial identities and use them in two applications: the queue inference engine (QIE) and earliest
due date rule (EDD) scheduling. Larson (1990) introduced the QIE. His objective was to deduce the behavior of a multiserver
queueing system without observing the queue. With only a Poisson arrival assumption, he analyzed the performance during a
busy period. Such a period starts once all servers are busy with the queue empty, and it ends as soon as a server becomes
idle. We generalize the standard order statistics result for Poisson processes, and show how to sample a busy period in the
M/M/c system. We derive simple expressions for the variance of the total waiting time in the M/M/c and M/D/1 queues given that n Poisson arrivals and departures occur during a busy period. We also perform a probabilistic analysis of the EDD for a one-machine
scheduling problem with earliness and tardiness penalties. The schedule is without preemption and with no inserted idle time.
The jobs are independent and each may have a different due date. For large n, we show that the variance of the total penalty costs of the EDD is linear in n. The mean of the total penalty costs of the EDD is known to be proportional to the square root of n (see Harel (1993)).
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
46.
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48.
The novel complex trans-[PdCl2(η1-N-2-ethyl-2-oxazoline)2] is shown to be an active and oxidatively robust catalyst for C-C bond-forming reactions (Heck, Sonogashira, Ullman, Suzuki), which can be carried out in air without rigorous solvent/substrate purification and in the absence of additional free ligand. 相似文献
49.
Droplet collision is shown to be important in the propagation of nucleation through supercooled oil-in-water emulsions by the use of a novel membrane technique. On the other hand, nucleation mediated by Tween 20 micelles is shown to be of relatively much less importance in both n-hexadecane and cocoa butter oil-in-water emulsions. The droplet collision phenomenon probably occurs via a surfactant bridge between the colliding droplets. When this process is taken into account we show that the Turnbull model for crystal nucleation kinetics explains very well nucleation in cocoa butter oil-in-water emulsions by seed crystals. On the basis of this model we characterized the seed crystals in cocoa butter via isothermal crystallization studies at 14.2, 15.0, 15.5, and 15.8 degrees C. We suggest that there are few seed crystals whose size exceeds 0.28 μm at 80 degrees C. In our cocoa butter samples there were between 10(16) and 10(17) seed crystals m(-3) whose average size we inferred to be less than 0.09 μm. A value of 0.133 mJ m(-2) is obtained for the Gibbs free energy of the nucleating surface in our West African cocoa butter samples. There is evidence that the alpha-polymorph of POS comprises the nucleating layer in the seed crystal. There is no evidence that surfactant influences the primary nucleation of oil crystals. However, the surfactant has a big effect on the kinetics of the secondary nucleation process, mediated by droplet collision. Copyright 2000 Academic Press. 相似文献
50.
R.O. Ansell T. Dickinson A.F. Povey P.M.A. Sherwood 《Journal of Electroanalytical Chemistry》1979,98(1):79-89
The surface of molybdenum metal was examined by XPS after exposure to gaseous and liquid systems and after electrochemical treatment. The latter being conducted in a specially designed electrochemical cell situated in a vacuum chamber attached to the main spectrometer chamber. The results show that a clean molybdenum metal surface is unaffected by oxygen gas and deoxygenated sulphuric acid. It was slightly oxidized by deoxygenated water and appreciably oxidized by oxygenated water. The Mo(VI) oxide is not observed after cathodic polarisation. 相似文献