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81.
Trond Erik Havre 《Colloid and polymer science》2004,282(3):270-279
A method for studying the precipitation of calcium naphthenate particles by means of near-IR spectroscopy is presented. Naphthenic or fatty acids were dissolved in water at high pH (11.2–11.5). Upon addition of a Ca2+ solution the nucleation period and particle growth were monitored. The near-IR spectra experience a baseline elevation owing to the formation and growth of calcium naphthenate particles. The resulting change in optical density over time is discussed on the basis of supersaturation, particle sizes, agglomeration, Ca2+-to-carboxylic acid ratio and nucleation process. Solubility products, defined as the ion concentration products where no particle growth was detected, were estimated for the calcium soaps. The method showed some quantitative limitations since the particle sizes changed with supersaturation. Smaller particles will have less influence on the optical density and the larger particle will dominate the resulting scattering contribution. However, it is obvious that the method has qualitative value, for example, to study the efficiency of different calcium naphthenate inhibitors. 相似文献
82.
Starting from eicosapentaenoic acid (EPA) the marine, naturally occurring, pyrrole derivatives, mycalazol 5 and mycalazal 2 have been synthesized. The Stille coupling reaction is a key step in the syntheses. 相似文献
83.
Phenols are converted to salicylaldehydes with paraformaldehyde, MgCl2-Et3N in THF, and when subsequently treated with aqueous NaOH and H2O2 afford the corresponding catechols. The sequence is conveniently carried out as a one-pot procedure. 相似文献
84.
Dahle J Noordhuis P Stokke T Svendsrud DH Kvam E 《Photochemistry and photobiology》2005,81(1):114-119
We previously reported that approximately 10% of V79 Chinese hamster fibroblast populations clonally derived from single cells immediately after irradiation with either ultraviolet B (UV-B, 290-320 nm, mainly 311 nm) or ultraviolet A (UV-A, 320-400 nm, mainly 350-390 nm) radiation exhibit genomic instability. The instability is revealed by relatively high mutation frequencies in the hypoxanthine phosphoribosyl transferase (hprt) gene up to 23 cell generations after irradiation. These delayed mutant clones exhibited higher levels of oxidative stress than normal cells. Therefore, persistently increased oxidative stress has been proposed as a mechanism for UV-induced genomic instability. This study investigates whether this mechanism is reflected in the deletion spectrum of delayed mutant clones. Eighty-eight percent of the delayed mutant clones derived from UV-A-irradiated populations were found to have total deletion of the hprt gene. Correspondingly, 81% of UV-A-induced early mutations (i.e. detected shortly after irradiation) also had total deletions. Among delayed UV-B-induced mutant clones, 23% had total deletions and 8% had deletion of one exon, whereas all early UV-B events were either point mutations or small deletions or insertions. In conclusion, the multiplex polymerase chain reaction deletion screen showed that there were explicit differences in the occurrence of large gene alterations between early and delayed mutations induced by UV-B radiation. For UV-A radiation the deletion spectra were similar for delayed and early mutations. UV-A radiation is, in contrast to UV-B radiation, only weakly absorbed by DNA and probably induces mutation almost solely via production of reactive oxygen species. Therefore, the present results support the hypothesis that persistent increase in oxidative stress is involved in the mechanism of UV-induced genomic instability. 相似文献
85.
Phenols were converted to their magnesium salts with the MgCl2-Et3N base system and subsequently reacted with Eschenmoser's salt, affording N,N-dimethyl substituted benzylamines in high to excellent yields. A series of mono N-substituted benzylamines were prepared in one-pot syntheses by ortho-formylation of phenols to corresponding salicylaldehydes, which in turn reacted with amines to imines. The imines were subsequently reduced to mono N-substituted benzylamines. Some of these benzylamines were further converted, without work-up, to mono N-substituted dihydro-2H-1,3-benzoxazines. 相似文献
86.
Radovan Bast Dr. Andreas Heßelmann Dr. Paweł Sałek Dr. Trygve Helgaker Prof. Dr. Trond Saue Dr. 《Chemphyschem》2008,9(3):445-453
We test the performance of four‐component relativistic density functional theory by calculating the static and frequency‐dependent electric dipole–dipole polarizabilities of all (ground‐state) closed‐shell atoms up to Ra. We consider 12 nonrelativistic functionals, including three asymptotically shape‐corrected functionals, by using two smooth interpolation schemes introduced by the Baerends group: the gradient‐regulated asymptotic connection (GRAC) procedure and the statistical averaging of (model) orbital potentials (SAOP). Basis sets of doubly augmented triple‐zeta quality are used. The results are compared to experimental data or to accurate ab initio results. The reference static electric dipole polarizability of palladium has been obtained by finite‐field calculations using the coupled‐cluster singles, doubles, and perturbative triples method within this work. The best overall performance is obtained using hybrid functionals and their GRAC shape‐corrected versions. The performance of SAOP is among the best for nonhybrid functionals for Group 18 atoms but its precision degrades when considering the full set of atoms. In general, we find that conclusions based on results obtained for the rare‐gas atoms are not necessarily representative of the complete set of atoms. GRAC cannot be used with effective core potentials since the asymptotic correction is switched on in the core region. 相似文献
87.
Trond Digernes 《P-Adic Numbers, Ultrametric Analysis, and Applications》2018,10(4):253-266
We give a review of finite approximations of quantum systems, both in an Archimedean and a non-Archimedean setting. Proofs will generally be omitted. In the Appendix we present some numerical results. 相似文献
88.
Brautaset T Bruheim P Sletta H Hagen L Ellingsen TE Strøm AR Valla S Zotchev SB 《Chemistry & biology》2002,9(3):367-373
Genetic manipulation of the polyketide synthase (PKS) gene nysC involved in the biosynthesis of the tetraene antifungal antibiotic nystatin yielded a recombinant strain producing hexaene nystatin derivatives. Analysis of one such compound, S48HX, by LC-MS/MS suggested that it comprises a 36-membered macrolactone ring completely decorated by the post-PKS modification enzymes. Further characterization by bioassay has shown that S48HX exhibits antifungal activity. Genetic analysis of the hexaene-producing mutant revealed an in-frame deletion within the nysC gene via recombination between two homologous ketoreductase domain-encoding sequences. Apparently, this event resulted in the elimination of one complete module from NysC PKS, subsequently leading to the production of the nystatin derivative with a contracted macrolactone ring. These results represent the first example of manipulation of a PKS gene for the biosynthesis of a polyene antibiotic. 相似文献
89.
The Powell singular function was introduced 1962 by M.J.D. Powell as an unconstrained optimization problem. The function is also used as nonlinear least squares problem and system of nonlinear equations. The function is a classic test function included in collections of test problems in optimization as well as an example problem in text books. In the global optimization literature the function is stated as a difficult test case. The function is convex and the Hessian has a double singularity at the solution. In this paper we consider Newton’s method and methods in Halley class and we discuss the relationship between these methods on the Powell Singular Function. We show that these methods have global but linear rate of convergence. The function is in a subclass of unary functions and results for Newton’s method and methods in the Halley class can be extended to this class. Newton’s method is often made globally convergent by introducing a line search. We show that a full Newton step will satisfy many of standard step length rules and that exact line searches will yield slightly faster linear rate of convergence than Newton’s method. We illustrate some of these properties with numerical experiments. 相似文献
90.
The frequency-dependent dipole polarizability of Hg(2) is calculated using response theory within four-component relativistic density-functional theory [using the local-density approximation (LDA) and the hybrid functional B3LYP] including corrections for the basis-set superposition error. The anisotropic component of the polarizability tensor agrees well with the values obtained from collision-induced Raman spectroscopy carried out at a wavelength of 488 nm. The values obtained from the two density functionals agree closely with the experimentally derived anisotropy component of the dipole polarizability, despite their rather large differences in the dimer potential-energy curves (LDA is strongly overbinding while B3LYP is purely repulsive). The first two refractivity virial coefficients for the generalized Clausius-Mossotti function are derived. 相似文献