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131.
Paramonov PB Lyuksyutov SF Mayevska OV Reagan MA Umemura K Tobari H Hara M Vaia RA Juhl S 《Langmuir : the ACS journal of surfaces and colloids》2006,22(15):6555-6561
Chemically induced rearrangements of amphifunctional molecules have been demonstrated using strong nonuniform electric fields (10(8)-10(10) V m(-1)) induced in the vicinity of nanoscale asperities. Electrostatic interactions utilizing these rearrangements of alkylthiolates assembled on Au(111) result in the nanopatterning of raised nanostructure (1.5-9 nm high, 15-100 nm wide) arrays on a second time scale by manipulating an atomic force microscope (AFM) tip above the monolayer. It is suspected that, as a result of the oxidative cleavage initiated by a weak bias of the tip, the S end of the alkylthiolate chain carrying a sulfenium cation is attracted to the (lifting) tip, forming bi- and higher-layer structures in the vicinity of the tip apex. Stabilization of the multiple-layered structures is accomplished via mutual attraction and entanglement of hydrocarbon chains. The rearrangements suggest a novel and general approach for nanoscale architecture in self-assembled systems. 相似文献
132.
Doss RM Marques MA Foister S Chenoweth DM Dervan PB 《Journal of the American Chemical Society》2006,128(28):9074-9079
The four Watson-Crick base pairs of DNA can be distinguished in the minor groove by pairing side-by-side three five-membered aromatic carboxamides, imidazole (Im), pyrrole (Py), and hydroxypyrrole (Hp), four different ways. On the basis of the paradigm of unsymmetrical paired edges of aromatic rings for minor groove recognition, a second generation set of heterocycle pairs, imidazopyridine/pyrrole (Ip/Py) and hydroxybenzimidazole/pyrrole (Hz/Py), revealed that recognition elements not based on analogues of distamycin could be realized. A new set of end-cap heterocycle dimers, oxazole-hydroxybenzimidazole (No-Hz) and chlorothiophene-hydroxybenzimidazole (Ct-Hz), paired with Py-Py are shown to bind contiguous base pairs of DNA in the minor groove, specifically 5'-GT-3' and 5'-TT-3', with high affinity and selectivity. Utilizing this technology, we have developed a new class of oligomers for sequence-specific DNA minor groove recognition no longer based on the N-methyl pyrrole carboxamides of distamycin. 相似文献
133.
Oefner C Binggeli A Breu V Bur D Clozel JP D'Arcy A Dorn A Fischli W Grüninger F Güller R Hirth G Märki H Mathews S M ller M Ridley RG Stadler H Vieira E Wilhelm M Winkler F Wostl W 《Chemistry & biology》1999,6(3):127-131
BACKGROUND: The aspartic proteinase renin catalyses the first and rate-limiting step in the conversion of angiotensinogen to the hormone angiotensin II, and therefore plays an important physiological role in the regulation of blood pressure. Numerous potent peptidomimetic inhibitors of this important drug target have been developed, but none of these compounds have progressed past clinical phase II trials. Limited oral bioavailability or excessive production costs have prevented these inhibitors from becoming new antihypertensive drugs. We were interested in developing new nonpeptidomimetic renin inhibitors. RESULTS: High-throughput screening of the Roche compound library identified a simple 3, 4-disubstituted piperidine lead compound. We determined the crystal structures of recombinant human renin complexed with two representatives of this new class. Binding of these substituted piperidine derivatives is accompanied by major induced-fit adaptations around the enzyme's active site. CONCLUSIONS: The efficient optimisation of the piperidine inhibitors was facilitated by structural analysis of the renin active site in two renin-inhibitor complexes (some of the piperidine derivatives have picomolar affinities for renin). These structural changes provide the basis for a novel paradigm for inhibition of monomeric aspartic proteinases. 相似文献
134.
Strebel C Murphy S Nielsen RM Nielsen JH Chorkendorff I 《Physical chemistry chemical physics : PCCP》2012,14(22):8005-8012
The active sites for CO dissociation were probed on mass-selected Ru nanoparticles on a HOPG support by temperature programmed desorption spectroscopy using isotopically labelled CO. Combined with transmission electron microscopy we gain insight on how the size and morphology of the nanoparticles affect the CO dissociation activity. The Ru nanoparticles were synthesized in a UHV chamber by gas-aggregation magnetron sputtering in the size range from 3 to 15 nm and the morphology was investigated in situ by scanning tunneling microscopy and ex situ by high resolution transmission electron microscopy. Surprisingly, it was found that larger particles were more active per surface area for CO dissociation. It is suggested that this is due to larger particles exposing a more rough surface than the smaller particles, giving rise to a higher relative amount of under-coordinated adsorption sites on the larger particles. The induced surface roughness is proposed to be a consequence of the growth processes in the gas-aggregation chamber. 相似文献
135.
We report on the integration of a size-based three-dimensional filter, with micrometre-sized pores, in a commercial microfluidic chip. The filter is fabricated inside an already sealed microfluidic channel using the unique capabilities of two-photon polymerization. This direct-write technique enables integration of the filter by post-processing in a chip that has been fabricated by standard technologies. The filter is located at the intersection of two channels in order to control the amount of flow passing through the filter. Tests with a suspension of 3 μm polystyrene spheres in a Rhodamine 6G solution show that 100% of the spheres are stopped, while the fluorescent molecules are transmitted through the filter. We demonstrate operation up to a period of 25 minutes without any evidence of clogging. Preliminary validation of the device for plasma separation from whole blood is shown. Moreover, the filter can be cleaned and reused by reversing the flow. 相似文献
136.
137.
A common task in microscopy is to fit an image of a fluorescent probe to a point spread function (PSF) in order to estimate the position of the probe. The PSF is often approximated as a Gaussian for mathematical simplicity. We show that the separable property of the Gaussian PSF enables a reduction of computational time from O(L2) to O(L), where L is the width (in pixels) of the image. When tested on realistic simulated data, our algorithm is able to localize the probes with precision close to the Cramér-Rao lower bound. 相似文献
138.
A reappraisal of the 1929 analysis of luminescence by Soleillet reveals the form of the Mueller matrix for fluorescence scattering whose parameters are directly defined in terms of the now-familiar fluorescence anisotropy parameter. If the scattering analyte is optically active, it is further shown how fluorescence detected circular dichroism and circularly polarized luminescence can be recovered, simultaneously and free of artifacts. 相似文献
139.
Farhad Haghjoo Nicholas A. Barnes Robin Pritchard Stephen M. Godfrey Shane Ratcliffe 《Acta Crystallographica. Section C, Structural Chemistry》2012,68(6):o216-o219
In the title compound, C36H25F6O2P2+·I3−, hydrogen‐bonded [{(p‐FC6H4)3PO}2H]+ dimers assemble along the crystallographic c axis to form channels that house extended chains of triiodide anions. Although the I—I bond lengths of 2.9452 (14) and 2.9023 (15) Å are typical, the inter‐ion I...I distance of 3.5774 (10) Å is unusually short. A posteriori modelling of nonmerohedral twinning about (100) has been only partially successful, achieving a reduction in the maximum residual electron density from 5.28 to 3.24 e Å−3. The inclusion of two low‐occupancy I‐atom sites (total 1.7%), which can be interpreted as translational disorder of the triiodide anions along the channels, reduced the maximum residual electron density to 2.03 e Å−3. The minor fractional contribution volume of the nonmerohedral twin domains refined to 0.24 and simultaneous refinement of the inversion twin domains showed the crystal to be a 0.5:0.5 inversion twin. 相似文献
140.
Igor Dubenko Tapas Samanta Arjun Kumar Pathak Alexandr Kazakov Valerii Prudnikov Shane Stadler Alexander Granovsky Arcady Zhukov Naushad Ali 《Journal of magnetism and magnetic materials》2012
The studies of magnetocaloric properties, phase transitions, and phenomena related to magnetic heterogeneity in the vicinity of the martensitic transition (MT) in Ni–Mn–In and Ni–Mn–Ga off-stoichiometric Heusler alloys are summarized. The crystal structure, magnetocaloric effect (MCE), and magnetotransport properties were studied for the following alloys: Ni50Mn50−xInx, Ni50−xCoxMn35In15, Ni50Mn35−xCoxIn15, Ni50Mn35In14Z (Z=Al, Ge), Ni50Mn35In15−xSix, Ni50−xCoxMn25+yGa25−y, and Ni50–xCoxMn32−yFeyGa18. It was found that the magnetic entropy change, ΔS, associated with the inverse MCE in the vicinity of the temperature of the magneto-structural transition, TM, persists in a range of (125-5) J/(kg K) for a magnetic field change ΔH=5 T. The corresponding temperature varies with composition from 143 to 400 K. The MT in Ni50Mn50−xInx (x=13.5) results in a transition between two paramagnetic states. Associated with the paramagnetic austenite-paramagnetic martensite transition ΔS=24 J/(kg K) was detected for ΔH=5 T at T=350 K. The variation in composition of Ni2MnGa can drastically change the magnetic state of the martensitic phase below and in the vicinity of TM. The presence of the martensitic phase with magnetic moment much smaller than that in the austenitic phase above TM leads to the large inverse MCE in the Ni42Co8Mn32−yFeyGa18 system. The adiabatic change of temperature (ΔTad) in the vicinity of TC and TM of Ni50Mn35In15 and Ni50Mn35In14Z (Z=Al, Ge) was found to be ΔTad=−2 K and 2 K for ΔH=1.8 T, respectively. It was observed that |ΔTad|≈1 K for ΔH=1 T for both types of transitions. The results on resistivity, magnetoresistance, Hall resistivity in some In-based alloys are discussed. 相似文献