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91.
Yu. A. Babanov O. M. Nemtsova T. Reich L. N. Romashev M. A. Milyaev V. V. Ustinov 《Journal of Structural Chemistry》2008,49(1):165-169
The possibility of determining the concentration profile of interfaces in multilayered nanoheterostructures according to the data of the angular dependence of X-ray photoelectron spectra was shown. To solve this ill-posed inverse problem, we used Tikhonov’s regularization method with iterative refinement. To determine the optimum parameter of regularization, we used the L curve technique. The programs used for this study allowed high accuracy of calculations. All this made it possible to obtain information about the distribution of atoms of a definite sort with a resolution of 0.1–0.15 nm in depth. The results of numerical simulation of XPS spectra are given for a three-layered Cr/Fe structure. Solving the inverse problem for the initial data distorted by the statistical noise afforded a concentration distribution over depth for Cr and Fe atoms. The stability of the solution against experimental errors was determined. 相似文献
92.
Current Good Manufacturing Practices (cGMP) for botanicals stipulates the use of appropriate methods for identification of raw materials. Due to natural variability, chemical analysis of plant material is a great challenge and requires special approaches. This paper presents a comprehensive proposal to the process of validating qualitative high-performance thin-layer chromatographic (HPTLC) methods, proving that such methods are suitable for the purpose. The steps of the validation process are discussed and illustrated with examples taken from a project aiming at validation of methods for identification of green tea leaf, ginseng root, eleuthero root, echinacea root, black cohosh rhizome, licorice root, kava root, milk thistle aerial parts, feverfew aerial parts, and ginger root. The appendix of the paper, which includes complete documentation and method write-up for those plants, is available on the J. AOAC Int. Website (http://www.atypon-link.com/AOAC/loi/jaoi). 相似文献
93.
Solution properties of enolates generated using the phosphazene (Schwesinger) base P4-tBu were investigated by NMR spectroscopy. With a full equivalent of base the benzyl ketones 1a and 1b, the acetophenone 2, the arylacetaldehyde 1c, and the methyl arylacetate 1d formed the expected "naked" (P4H+) enolates 3 and 7. However, at a half-equivalent of base the ketones 1a and 1b as well as the aldehyde 1c formed solutions of stable hydrogen-bonded dimeric (enol-enolate) structures (4). The acetophenone 2, on the other hand, forms only traces of the H-bonded dimer 8 during deprotonation of 2. The thermodynamic product was the isomeric self-aldol condensation product 12. The mechanism of this condensation was elucidated by low temperature rapid-injection (RI) NMR spectroscopy. Solutions of 8 stable enough for NMR characterization could be transiently generated by semiprotonation of the enolate 7 with HCl.OEt2 at -130 degrees C using RINMR. The ester enolate 1d gave no trace of 4d even on a time scale as short as a few seconds at -130 degrees C either during the semideprotonation of 1d, or during semiprotonation of the enolate 3d. Long-lived solutions of the enols derived from 1a, 1b, 1c, and 2 (but not 1d) could be produced by full protonation of the phosphazene enolates with HCl.OEt2 at low temperature. 相似文献
94.
Jones AC Sanders AW Sikorski WH Jansen KL Reich HJ 《Journal of the American Chemical Society》2008,130(19):6060-6061
Low-temperature rapid-injection NMR (RINMR) experiments were performed on tris(trimethylsilyl)methyllithium. In THF/Me2O solutions, the separated ion (1S) reacted faster than can be measured at -130 degrees C with MeI and substituted benzaldehydes (k >/= 2 s -1), whereas the contact ion (1C) dissociated to 1S before reacting. Unexpectedly, the triple ion reacted faster with electron-rich benzaldehydes relative to electron-deficient ones. The addition of HMPA had no effect on the rate of reaction of the triple ion with p-diethylaminobenzaldehyde, and the immediate product of the reaction was the HMPA-solvated separated ion 1S, with the Peterson product forming only slowly. Thus, the aldehyde is catalyzing the dissociation of the triple ion. HMPA greatly decelerated the reaction of 1S (<10 -10), providing an estimate of the Lewis acid activating effect of a THF-solvated lithium cation in an organolithium addition to an aldehyde. 相似文献
95.
Han Fu K. V. Reich B. I. Shklovskii 《Journal of Experimental and Theoretical Physics》2016,122(3):456-471
This mini-review is dedicated to the 85th birthday of Prof. L.V. Keldysh, from whom we have learned so much. In this paper, we study the potential and electron density depth profiles in surface accumulation layers in crystals with a large and nonlinear dielectric response such as SrTiO3 (STO) in the cases of planar, spherical, and cylindrical geometries. The electron gas can be created by applying an induction D0 to the STO surface. We describe the lattice dielectric response of STO using the Landau–Ginzburg free energy expansion and employ the Thomas–Fermi (TF) approximation for the electron gas. For the planar geometry, we arrive at the electron density profile n(x) ∝ (x + d)–12/7, where d ∝ D0–12/7. We extend our results to overlapping electron gases in GTO/STO/GTO heterojunctions and electron gases created by spill-out from NSTO (heavily n-type doped STO) layers into STO. Generalization of our approach to a spherical donor cluster creating a big TF atom with electrons in STO brings us to the problem of supercharged nuclei. It is known that for an atom with a nuclear charge Ze where Z > 170, electrons collapse onto the nucleus, resulting in a net charge Zn < Z. Here, instead of relativistic physics, the collapse is caused by the nonlinear dielectric response. Electrons collapse into the charged spherical donor cluster with radius R when its total charge number Z exceeds the critical value Zc ≈ R/a, where a is the lattice constant. The net charge eZn grows with Z until Z exceeds Z* ≈ (R/a)9/7. After this point, the charge number of the compact core Zn remains ≈ Z*, with the rest Z* electrons forming a sparse TF atom with it. We extend our studies of collapse to the case of long cylindrical clusters as well. 相似文献
96.
A feasible approach to all-electronic digital labeling and readout for cell identification 总被引:1,自引:0,他引:1
We present two critical innovations that enable a unique, purely electronic approach to microfluidic whole-cell analysis, focusing on the problem of cell identification and sorting. We used fully-scalable lithographic techniques to microfabricate digital barcodes, providing a means for low-cost, large volume production. We have demonstrated molecular functionalization of the barcodes, using biotin-streptavidin, as well as human CD4 antibody, and we have successfully linked the barcodes to polystyrene beads using the biotin-streptavidin complex. This functionalization allows unique barcodes to be attached to specific cell types, based on phenotype. We have also implemented an electronic barcode readout scheme, using a radio frequency microsensor integrated in an elastomeric microfluidic channel, that can read individual barcodes at rates in excess of 1000 labels s(-1). The barcodes are biologically compatible, and coupled with the electronic sensing technology, provide a route to compact, inexpensive, disposable cell identification, sorting and purification. 相似文献
97.
A heterogeneous PNA-based SERS method for DNA detection 总被引:1,自引:0,他引:1
Fabris L Dante M Braun G Lee SJ Reich NO Moskovits M Nguyen TQ Bazan GC 《Journal of the American Chemical Society》2007,129(19):6086-6087
98.
C. Thomsen S. Reich H. Jantoljak I. Loa K. Syassen M. Burghard G.S. Duesberg S. Roth 《Applied Physics A: Materials Science & Processing》1999,69(3):309-312
The pressure dependence of the high-energy Raman modes in single- and multi-walled carbon nanotubes was measured in the range
0–10 GPa. We found the pressure coefficient to be linear in both materials but 25% smaller in MWNT. Given that the curvature
effects on vibrational properties of the rolled-up graphene sheets are small, we can explain this difference simply with elasticity
theory.
Received: 17 May 1999 / Accepted 18 May 1999 / Published online: 4 August 1999 相似文献
99.
Preparation, Isolation, and Characterization of Ba@C74 For the first time Ba@C74 has been isolated in pure form. The title compound has been isolated from a raw material, produced in a radio‐frequency‐furnace, consisting of a mixture of fullerenes and endohedral Bariumfullerenes. Ba@C74 was separated by two stage sublimation and subsequent high‐performance liquid chromatography (HPLC) using a Buckyprep column. The capacity factor for Ba@C74 is 6.0. Its endohedral character has been deduced from the fragmentation pattern obtained by time‐of‐flight mass spectroscopy while the composition has been confirmed by comparison of calculated and measured isotopic pattern of the parent peak. Further characterization was performed by VIS/NIR‐spectroscopy and electron‐paramagnetic‐resonance spectroscopy (EPR). 相似文献
100.