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11.
Maneesh K. Yadav Cory J. Gerdts Ruslan Sanishvili Ward W. Smith L. Spencer Roach Rustem F. Ismagilov Peter Kuhn Raymond C. Stevens 《Journal of Applied Crystallography》2005,38(6):900-905
In situ X‐ray data collection has the potential to eliminate the challenging task of mounting and cryocooling often fragile protein crystals, reducing a major bottleneck in the structure determination process. An apparatus used to grow protein crystals in capillaries and to compare the background X‐ray scattering of the components, including thin‐walled glass capillaries against Teflon, and various fluorocarbon oils against each other, is described. Using thaumatin as a test case at 1.8 Å resolution, this study demonstrates that high‐resolution electron density maps and refined models can be obtained from in situ diffraction of crystals grown in microcapillaries. 相似文献
12.
Ruslan P. Liferovich 《Journal of solid state chemistry》2004,177(6):2188-2197
Ternary lanthanide scandates (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho) have been synthesized at ambient pressure. Their structure has been investigated at room temperature by Rietveld analysis of powder X-ray diffraction data. The Ln-scandates are orthorhombic perovskites, adopting space group Pbnm (? 62), a≈b≈√2ap, c≈2ap, Z=4. Heavy lanthanides (Er-Lu), and Y do not form perovskites at ambient conditions. Compositionally driven phase transitions were not observed. The unit-cell parameters decrease with increasing ScO6 octahedron rotation and atomic number of the Ln cation. In common with lanthanide orthoferrites, the uniform structural evolution is interrupted at the middle-heavy part of the lanthanide sequence. This is probably due to an interplay between: (i) enlargement of the ScO6 octahedra relative to BO6 in other perovskites (e.g., FeO6 in GdFeO3); (ii) reduction in size of the first coordination sphere of Ln3+ coincident with the lanthanide contraction; (iii) coincident expansion of the second coordination sphere due to screening effects of OI1 on OI2, and entry of Sc to the lanthanide coordination sphere; (iv) complex mixing between oxygen and lanthanide lanthanide f- and scandium d-orbitals. In the series studied, Ln3+ are in eight-fold coordination (tetragonal antiprism), and are considerably displaced from the center of the LnO8 polyhedron along [001]. Evolution of the crystallochemical characteristics through the Ln orthoscandate series is complex due to both the antipathetic distortions of A- and B-site coordination polyhedra and interaction of the orbitals of oxygen, Ln and Sc. Empirically obtained limits of Goldschmidt and observed viiito tolerance factors for ternary LnBO3 compounds adopting the Pbnm structure are 0.795 and 0.841, respectively. 相似文献
13.
Dorofeeva VN Kolotilov SV Kiskin MA Polunin RA Dobrokhotova ZV Cador O Golhen S Ouahab L Eremenko IL Novotortsev VM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(16):5006-5012
Trinuclear building block {Fe(2)NiO(Piv)(6)} (Piv = pivalate), which possessed pseudo-D(3h) symmetry, was linked by two ligands, pseudo-D(3h) ligand tris-(4-pyridyl)pyridine (L1) and C(2v) ligand 4-(N,N-dimethylamino)phenyl-2,6-bis(4-pyridyl)pyridine (L2) into two products with different topologies: 2D coordination polymer [Fe(2)NiO(Piv)(6)(L1)](n) (1), and discrete molecule [{Fe(2)NiO(Piv)(6)}(8) {L2}(12)], which had a nanocube structure (2). In compound 1, trinuclear {Fe(2)NiO(Piv)(6)} blocks were linked through ligand L1 into layers with honeycomb topology. In compound 2, eight trinuclear blocks were located in the vertices of the nanocube, with each L2 ligand linked to two {Fe(2)NiO(Piv)(6)} units. In the crystal structure, these nanocubes formed infinite catenated chains. Analysis of possible structures that could be assembled from these building blocks showed that compounds 1 and 2 corresponded to their respective predicted topologies. Compound [1?solvent] possessed a porous structure, in which the voids were filled by solvent molecules (DMF or DMSO). This structure was retained following desolvation, and compound 1 absorbed significant quantities of N(2) and H(2) at 78?K (S(BET) = 730?m(2) g(-1), H(2) sorption capacity: 0.9?% by weight at 865?Torr). Desolvation of [2?solvent] led to disorder of its crystal structure, and compound 2 only adsorbed negligible quantities of N(2) but adsorbed 0.27?% H(2) (by weight) at 855?Torr and 78?K. The magnetic properties of these complexes (temperature dependence of molar magnetic susceptibility) were governed by the magnetic properties of the trinuclear "building block". 相似文献
14.
Andriy B. Zaborovskiy Ruslan E. Prystansky Vitaliy I. Timokhin 《Journal of organometallic chemistry》2004,689(18):2912-2919
The interaction of (Me3Si)3SiH with O2 is known to afford (Me3SiO)2Si(H)SiMe3 in which the two oxygen atoms arise from the same oxygen molecule. In order to investigate the mechanism of this unusual reaction, the oxidation rates were measured in the temperature range 30-70 °C by following oxygen uptake in the presence and absence of hydroquinone as inhibitor. The rate constant for the spontaneous reaction of (Me3Si)3SiH with O2 was determined at 70 °C to be ∼3.5 × 10−5 M−1 s−1. A sequence of the propagation steps is proposed by combining the previous and present experimental findings with some theoretical results obtained at the semiempirical level. These calculations showed that the silylperoxyl radical (Me3Si)3SiOO undergoes three consecutive unimolecular steps to give (Me3SiO)2Si()SiMe3. Evidence has been obtained that the rate determining step is the rearrangement of silylperoxyl radical to a dioxirand-like pentacoordinated silyl radical. Our findings are of considerable importance for the understanding of the oxidation of hydrogen-terminated silicon surfaces. 相似文献
15.
Yashin R Rudchenko S Stojanovic MN 《Journal of the American Chemical Society》2007,129(50):15581-15584
Microparticles covered with DNA-based computing elements that sense inputs and release oligonucleotides as outputs could be used to construct autonomous networks with increasingly complex functions. We demonstrate cascades of particles with up to three layers and a nonlinear network with an AND gate hub. In order to establish functional networks, particles do not have to be in direct physical contact. 相似文献
16.
17.
McCullough DH Grygorash R Hsu JT Regen SL 《Journal of the American Chemical Society》2007,129(27):8663-8667
Permeation measurements have been made for He, CO2, and N2 across single Langmuir-Blodgett (LB) bilayers derived from 1,2,4,5-tetrakis[(N-(undecanoamidoethyl)-N,N-dimethyl ammonium) methyl]benzene tetrabromide (2) and 1,2,4,5-tetrakis[(N-(perfluoroundecanoamidoethyl)-N,N-dimethyl ammonium)methyl]benzene tetrabromide (3) in the absence and in the presence of entrapped poly(acrylic acid) (PAA). In the absence of PAA, single LB bilayers of 3 show a higher permeance for He and N2 but a lower permeation rate of CO2, as compared with analogous LB bilayers made from 2. The relatively low permeation rate of CO2 for the former has been attributed to reduced associative interactions with the fluorocarbon-rich bilayer. The same behavior has also been observed for LB bilayers containing PAA, formed under conditions that yield glued bilayers of 2 and 3 having similar diffusional pathways, as judged by He/N2 selectivities. These results, together with the fact that glued bilayers of 2 (having a thinner PAA layer as compared with those made from 3) exhibit lower He and N2 permeances, provide compelling evidence that the main barrier for gas transport is the combination of surfactant plus PAA and not simply a thin PAA layer that is encased within the surfactant bilayer. 相似文献
18.
We review our recent work on the direct calculation of the interfacial free energy, gamma, of the crystal-melt interface via molecular dynamics computer simulation for a number of model systems. The value of gamma as a function of crystal orientation is determined using a thermodynamic integration technique employing moving cleaving walls [Phys. Rev. Lett. 2000, 85, 4751]. The calculation is sufficiently precise to resolve the small anisotropy in gamma, which is crucial in determining the kinetics and morphology of dendritic growth. We report values of gamma for the hard-sphere and Lennard-Jones systems, as well as recent results on the series of inverse-power potentials. For the inverse sixth-, seventh-, and eighth-power systems, we determine gamma for both fcc and bcc crystal structures. For these systems, the bcc-melt gamma is lower than that for fcc crystals by about 25%, consistent with recent experiments and computer simulations on fcc-forming systems that show preferential formation of bcc nuclei in the initial stages of crystallization. In addition, we show that our results give a molecular interpretation of Turnbull's rule, which is the empirical relationship between gamma and the enthalpy of fusion. 相似文献
19.
Ruslan I. Vaskevych Alla I. Vaskevych Eduard B. Rusanov Oksana Ya. Mel'nyk Mykhailo V. Vovk 《Journal of heterocyclic chemistry》2020,57(8):3202-3212
Selective iodocyclization of 6-(alkenylamino)-1-allylpyrazolo[3,4-d]pyrimidines provided hydrogenated derivatives of 1-allyl-8(9)-iodomethylimidazo(pyrimido)[1,2-a]pyrazolo[4,3-e]pyrimidines which were further reacted with NaN3 at 75°С to 80°С to give a series of new-type 1,3,6-triazocines annulated with the pyrazole, pyrimidine, imidazole (or pyrimidine), and 1,2,3-triazole rings. The compounds synthesized were structurally characterized by analytical, spectral (IR, 1H and 13C NMR, HPLC-mass), and X-ray diffraction data. 相似文献
20.
Digital marketing has been extensively researched and developed remarkably rapidly over the last decade. Within this field, hundreds of scientific publications and patents have been produced, but the accuracy of prediction technologies leaves much to be desired. Conversion prediction remains a problem for most marketing professionals. In this article, the authors, using a dataset containing landing pages content and their conversions, show that a detailed analysis of text readability is capable of predicting conversion rates. They identify specific features that directly affect conversion and show how marketing professionals can use the results of this work. In their experiments, the authors show that the applied machine learning approach can predict landing page conversion. They built five machine learning models. The accuracy of the built machine learning model using the SVM algorithm is promising for its implementation. Additionally, the interpretation of the results of this model was conducted using the SHAP package. Approximately 60% of purchases are made by nonmembers, and this paper may be suitable for the cold-start problem. 相似文献