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21.
13C NMR spectra for a variety of isoflavones are presented and analysed. The novel isoflavone, Millettin (Xa) is shown to be closely related to Auriculatin (II). While comparison of the 13C NMR spectra did not readily prove the orientation of the fused pyran ring, the use of acetylation shifts showed unambiguously that the fusion in linear, rather than angular. 相似文献
22.
Sahai MA Kehoe TA Koo JC Setiadi DH Chass GA Viskolcz B Penke B Pai EF Csizmadia IG 《The journal of physical chemistry. A》2005,109(11):2660-2679
Ab initio molecular orbital computations were carried out at three levels of theory: RHF/3-21G, RHF/6-31G(d), and B3LYP/6-31G(d), on four model systems of the amino acid proline, HCO-Pro-NH2 [I], HCO-Pro-NH-Me [II], MeCO-Pro-NH2 [III], and MeCO-Pro-NH-Me [IV], representing a systematic variation in the protecting N- and C-terminal groups. Three previously located backbone conformations, gammaL, epsilonL, and alphaL, were characterized together with two ring-puckered forms syn (gauche+ = g+) or "DOWN" and anti (gauche- = g-) or "UP", as well as trans-trans, trans-cis, cis-trans, and cis-cis peptide bond isomers. The topologies of the conformational potential energy cross-sections (PECS) of the potential energy hypersurfaces (PEHS) for compounds [I]-[IV] were explored and analyzed in terms of potential energy curves (PEC), and HCO-Pro-NH2 [I] was also analyzed in terms of potential energy surfaces (PESs). Thermodynamic functions were also calculated for HCO-Pro-NH2 [I] at the CBS-4M and G3MP2 levels of theory. The study confirms that the use of the simplest model, compound [I] with P(N) = P(C) = H, along with the RHF/3-21G level of theory, is an acceptable practice for the analysis of peptide models because only minor differences in geometry and stability are observed. 相似文献
23.
24.
Law JM Szori M Izsak R Penke B Csizmadia IG Viskolcz B 《The journal of physical chemistry. A》2006,110(18):6100-6111
Polyunsaturated fatty acids (PUFA) like stearidonic acid (SDA;18:4 n-3) eicosapentaenoic acid (EPA; 20:5 n-3), and docosahexaenoic acid (DHA; 22:6 n-3) and its chain fragment models were studied at B3LYP/6-31G(d) levels of theory. Significant conformations for the cis and trans isomers were selected to obtained the thermodynamic functions (DeltaH, DeltaS, DeltaG) for the cis-trans isomerization and for folding using the B3LYP/6-311+G(2d,p)//B3LYP/6-31G(d) level of theory. The structural analysis shows that there are significant differences in thermodynamic function of the trans- and cis-PUFAs. The trans-cis isomerization energy values reinforce the consistency and the relative accuracy of theoretical model calculations. The observed flexibility of naturally cis PUFAs could be explained by a very special "smooth basin" PES of the motif of sp(2)-sp(3)-sp(2) hybrid states as reported previously (J. Phys. Chem. A 2005, 109, 520-533). We assumed that intrinsic thermodynamic functions may describe this flexible folding process. The folding enthalpy as well as the folding entropy suggests that there is a new role of the cis-PUFAs in membranes: these cis isomers may have a strong influence on membrane stability and permeability. The average length of the cis helix and beta PUFA was approximated. The difference between the lengths of these two structures is approximately 10 A. 相似文献
25.
Sahai MA Fejer SN Viskolcz B Pai EF Csizmadia IG 《The journal of physical chemistry. A》2006,110(40):11527-11536
First-principle computations were carried out on the conformational space of trans and cis peptide bond isomers of HCO-Thr-NH2. Using the concept of multidimensional conformational analysis (MDCA), geometry optimizations were performed at the B3LYP/6-31G(d) level of theory, and single-point energies as well as thermodynamic functions were calculated at the G3MP2B3 level of theory for the corresponding optimized structures. Two backbone Ramachandran-type potential energy surfaces (PESs) were computed, one each for the cis and trans isomers, keeping the side chain at the fully extended orientation (chi1=chi2=anti). Similarly, two side chain PESs for the cis and trans isomers were generated for the (phi=psi=anti) orientation corresponding to approximately the betaL backbone conformation. Besides correlating the relative Gibbs free energy of the various stable conformations with the number of stabilizing hydrogen bonds, the process of trans-->cis isomerization is discussed in terms of intrinsic stabilities as measured by the computed thermodynamic functions. 相似文献
26.
Mériguet G Cousin F Dubois E Boué F Cebers A Farago B Perzynski R 《The journal of physical chemistry. B》2006,110(9):4378-4386
In the present study, the structure of monophasic ionic magnetic fluids under a static magnetic field is explored. In these aqueous electrostatically stabilized ferrofluids, we vary both the isotropic interparticle interactions and the anisotropic dipolar magnetic interaction by tuning the ionic strength and the size of the nanoparticles. Small angle neutron scattering measurements carried out on nanoparticles dispersed in light water exhibit miscellaneous 2D nuclear patterns under a magnetic field with various q-dependent anisotropies. In this nondeuterated solvent where the magnetic scattering is negligible, this anisotropy originates from an anisotropy of the structure of the dispersions. Both the low q region and the peak of the structure factor can be anisotropic. On the scale of the interparticle distance, the structure is better defined in the direction perpendicular to the field. In the thermodynamic limit (q-->0), the model previously described in ref 10 matches the data without any fitting parameters: the interparticle interaction is more repulsive in the direction parallel to the magnetic field. At low q, the amplitude of the anisotropy of the pattern is governed by the ratio of two interaction parameters: the reduced parameter of the anisotropic magnetic dipolar interaction, gamma/Phi, over the isotropic interaction parameter, , in zero field, which is proportional to the second virial coefficient. 相似文献
27.
Alon Noga; Bollobas Bela; Kim Jeong Han; Vu Van H. 《Proceedings London Mathematical Society》2003,86(2):273-301
A cover of a hypergraph is a collection of edges whose unioncontains all vertices. Let H = (V, E) be a k-uniform, D-regularhypergraph on n vertices, in which no two vertices are containedin more than o(D/e2k log D) edges as D tends to infinity. Ourresults include the fact that if k = o(log D), then there isa cover of (1 + o(1))n/k edges, extending the known result thatthis holds for fixed k. On the other hand, if k 4 log D thenthere are k-uniform, D-regular hypergraphs on n vertices inwhich no two vertices are contained in more than one edge, andyet the smallest cover has at least (nk) log (k log D)) edges.Several extensions and variants are also obtained, as well asthe following geometric application. The minimum number of linesrequired to separate n random points in the unit square is,almost surely, (n2/3 / (log n)1/3). 2000 Mathematical SubjectClassification: 05C65, 05D15, 60D05. 相似文献
28.
The structure-function and materials paradigms drive research on the understanding of structures and structural heterogeneity of molecules and solids from materials science to structural biology. Functional insights into complex architectures are often gained from a suite of complementary physicochemical methods. In the context of biomacromolecular structures, the use of pulse dipolar electron paramagnetic resonance spectroscopy (PDS) has become increasingly popular. The main interest in PDS is providing long-range nanometre distance distributions that allow for identifying macromolecular topologies, validating structural models and conformational transitions as well as docking of quaternary complexes. Most commonly, cysteines are introduced into protein structures by site-directed mutagenesis and modified site-specifically to a spin-labelled side-chain such as a stable nitroxide radical. In this contribution, we investigate labelling by four different commercial labelling agents that react through different sulfur-specific reactions. Further, the distance distributions obtained are between spin-bearing moieties and need to be related to the protein structure via modelling approaches. Here, we compare two different approaches to modelling these distributions for all four side-chains. The results indicate that there are significant differences in the optimum labelling procedure. All four spin-labels show differences in the ease of labelling and purification. Further challenges arise from the different tether lengths and rotamers of spin-labelled side-chains; both influence the modelling and translation into structures. Our comparison indicates that the spin-label with the shortest tether in the spin-labelled side-group, (bis-(2,2,5,5-Tetramethyl-3-imidazoline-1-oxyl-4-yl) disulfide, may be underappreciated and could increase the resolution of structural studies by PDS if labelling conditions are optimised accordingly. 相似文献
29.
Ana Bela Cruzeiro 《Journal of Functional Analysis》1984,58(3):335-347
Unicity of the flow associated to a good vector field on the Wiener space. 相似文献
30.
Let G be a compact Lie group, L(G) the associated loop group, ω the canonical symplectic form on L(G). Set H the Hamiltonian function for which the associated ω-Hamiltonian vector field is the infinitesimal rotation. Then H generates a canonical semi-definite Riemannian structure on L(G), which induces a Riemannian structure on the free loop groupL(G)/G=L0(G). This metric corresponds to the Sobolev norm H1. Using orthonormal frame methodology the positivity and finiteness of the Ricci curvature of L0(G) is proved. By studying the dissipation towards high modes of a unitary group valued SDE it is proved that the loop group does not have any infinitesimally invariant measure. 相似文献