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Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):87
Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H–1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10−4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10−4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo 1H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids. 相似文献
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Kerstin Paech Adrian Dumitru Jürgen Schaffner-Bielich Stefan Schramm Horst Stöcker Gebhard Zeeb Detlef Zschiesche 《Acta Physica Hungarica A》2004,21(2-4):151-156
The measured particle ratios in central heavy-ion collisions are investigated within a chemical and thermal equilibrium chiral SU(3) σ?ω approach. Contrary to the commonly adopted non-interacting gas calculations, the chiral SU(3) model predicts modified effective hadron masses and effective chemical potentials in the medium and a transition to a chirally restored phase at high temperatures or chemical potentials. the influence of three different types of phase transitions is investigated. We show that the deduced freeze-out values considerably depend on the underlying model while the quality of the fit is approximately the same. 相似文献
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Phase modulation in dipolar-coupled A2 spin systems: effect of maximum state mixing in H NMR in vivo
Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):69
Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (An system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time. 相似文献
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The control of piecewise-deterministic processes is studied where only local boundedness of the data is assumed. Moreover the discount rate may be zero. The value function is shown to be solution to the Bellman equation in a weak sense; however the solution concept is strong enough to generate optimal policies. Continuity and compactness conditions are given for the existence of nonrelaxed optimal feedback controls. 相似文献
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Guy Schmitz 《国际化学动力学杂志》2007,39(1):17-21
At bromide concentrations higher than 0.1 M, a second term must be added to the classical rate law of the bromate–bromide reaction that becomes ?d[BrO3?]/dt = [BrO3?][H+]2(k1[Br?] + k2[Br?]2). In perchloric solutions at 25°C, k1 = 2.18 dm3 mol?3 s?1 and k2 = 0.65 dm4 mol?4 s?1 at 1 M ionic strength and k1 = 2.60 dm3 mol3 s?1and k2 = 1.05 dm4 mol?4 s?1 at 2 M ionic strength. A mechanism explaining this rate law, with Br2O2 as key intermediate species, is proposed. Errors that may occur when using the Guggenheim method are discussed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 17–21, 2007 相似文献
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