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61.
Soubias O Réat V Saurel O Milon A 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,158(1-2):143-148
High resolution 2D NMR MAS spectra of liposomes, in particular 1H-13C chemical shifts correlations have been obtained on fluid lipid bilayers made of pure phospholipids for several years. We have investigated herein the possibility to obtain high resolution 2D MAS spectra of cholesterol embedded in membranes, i.e. on a rigid molecule whose dynamics is characterized mainly by axial diffusion without internal segmental mobility. The efficiency of various pulse sequences for heteronuclear HETCOR has been compared in terms of resolution, sensitivity and selectivity, using either cross polarization or INEPT for coherence transfer, and with or without MREV-8 homonuclear decoupling during t1. At moderately high spinning speed (9 kHz), a similar resolution is obtained in all cases (0.2 ppm for 1H(3,4), 0.15 ppm for 13C(3,4) cholesterol resonances), while sensitivity increases in the order: INEPT < CP(x4) < CP + MREV. At reduced spinning speed (5 kHz), the homonuclear dipolar coupling between the two geminal protons attached to C(4) gives rise to spinning sidebands from which one can estimate a H-H dipolar coupling of 10 kHz which is in good agreement with the known dynamics of cholesterol in membranes. 相似文献
62.
Derivatives of Tr?ger's base (TB) have played important roles in receptor construction due to their rigid V-shape. A new class of these compounds are the oligo-TBs, which can function as cavitands. Herein, we describe both stepwise and one-step (oligomerization) methods suitable for the preparation of linear oligo-TBs. 相似文献
63.
Abdallah R Meille V Shaw J Wenn D de Bellefon C 《Chemical communications (Cambridge, England)》2004,(4):372-373
A microstructured mesh contactor that can offer residence time of more than minutes is used for gas-liquid-solid hydrogenations and gas-liquid asymmetric hydrogenations. Applications for catalyst/chiral inductor screening and for kinetic data acquisition are demonstrated. 相似文献
64.
It is demonstrated that the inclusion of long-range intersite interactions qualitatively modifies the dependence of a superconducting gap on quasimomentum for both s-and d-symmetry types. In particular, the order parameter of a superconducting phase with $d_{x^2 - y^2 } $ the symmetry type depends on two amplitudes and has the form Δ(k)=Δ1(cosk x ?cosk y )+Δ2(cos2k x ?cos2k y ). In this case, the theoretical dependence of the critical temperature on the degree of doping agrees with the experimental dependence. 相似文献
65.
Structural isomers of [UO(2)(oxalate)(3)](4-), [UO(2)(oxalate)F(3)](3-), [UO(2)(oxalate)(2)F](3-), and [UO(2)(oxalate)(2)(H(2)O)](2-) have been studied by using EXAFS and quantum chemical ab initio methods. Theoretical structures and their relative energies were determined in the gas phase and in water using the CPCM model. The most stable isomers according to the quantum chemical calculations have geometries consistent with the EXAFS data, and the difference between measured and calculated bond distances is generally less than 0.05 A. The complex [UO(2)(oxalate)(3)](4-) contains two oxalate ligands forming five-membered chelate rings, while the third is bonded end-on to a single carboxylate oxygen. The most stable isomer of the other two complexes also contains the same type of chelate-bonded oxalate ligands. The activation energy for ring opening in [UO(2)(oxalate)F(3)](3-), deltaU++ = 63 kJ/mol, is in fair agreement with the experimental activation enthalpy, deltaH++ = 45 +/- 5 kJ/mol, for different [UO(2)(picolinate)F(3)](2-) complexes, indicating similar ring-opening mechanisms. No direct experimental information is available on intramolecular exchange in [UO(3)(oxalate)(3)](4-). The theoretical results indicate that it takes place via the tris-chelated intermediate with an activation energy of deltaU++ = 38 kJ/mol; the other pathways involve multiple steps and have much higher activation energies. The geometries and energies of dioxouranium(VI) complexes in the gas phase and solvent models differ slightly, with differences in bond distance and energy of typically less than 0.06 A and 10 kJ/mol, respectively. However, there might be a significant difference in the distance between uranium and the leaving/entering group in the transition state, resulting in a systematic error when the gas-phase geometry is used to estimate the activation energy in solution. This systematic error is about 10 kJ/mol and tends to cancel when comparing different pathways. 相似文献
66.
Magnetic field effect on the structure of the ground state of a two-dimensional quantum Heisenberg magnet is analyzed. A plaquette representation is used to solve the self-consistent problem and calculate the collective excitation spectrum in a magnetic field. Conditions are found for quantum transition between non-magnetic and oblique antiferromagnetic phases. The change in the ground state of the system is associated with disappearance of the gap in the spin excitation spectrum. Effects of frustration and magnetic field on the spectrum are analyzed. A phase diagram of stable singlet and magnetically ordered phases is presented. 相似文献
67.
Floraine Collette Régis Delatouche Christophe Blanquart Fabien Gueugnon Marc Grégoire Philippe Bertrand Valérie Héroguez 《Journal of polymer science. Part A, Polymer chemistry》2013,51(1):176-189
In this contribution, a versatile approach for the synthesis of functionalized particles for drug delivery is presented, using two nonaggressive standardized procedures. The first procedure considered is the functionalization of an azido‐terminated α‐norbornenyl poly(ethylene oxide) (PEO) macromonomer with an alkyne‐containing active molecule via the copper catalyzed azide alkyne cycloaddition, click type reaction. The functionalized macromonomer is then polymerized by Ring‐Opening Metathesis Polymerization (ROMP) in dispersion to form functionalized particles. The second procedure consists in synthesizing particles by ROMP in dispersed media of norbornene with azido‐terminated α‐norbornenyl PEO macromonomer. The ROMP was initiated by the first generation Grubbs catalyst. Such functionalized core‐shell particles have stealthy properties due to their PEO shell and can be viewed as universal nanocarriers on which any alkyne‐modified active molecule can be grafted by click chemistry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
68.
Minh Ngoc Nguyen Sébastien‐Jun Mougnier Emmanuel Ibarboure Valérie Heroguez 《Journal of polymer science. Part A, Polymer chemistry》2011,49(6):1471-1482
Composite latex particles based on homopolymers and graft‐copolymers composed of polynorbornene (PNB) and poly(tert‐butyl acrylate) (PtBA) were synthesized in microemulsion conditions by simultaneous combination of two distinct methods of polymerization: Ring‐opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). Only one commercial compound (first generation Grubbs catalyst) was used to initiate the ROMP of norbornene (NB) and activate the ATRP of tert‐butyl acrylate (tBA). Well‐defined nanoparticles with hydrodynamic diameters smaller than 50 nm were prepared with original morphologies depending on the monomer compositions, the type of combination (polymer blend or graft‐copolymer), and the conditions of microemulsion polymerizations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
69.
P. M. Carreira D. Nunes P. Valério M. F. Araújo 《Journal of Radioanalytical and Nuclear Chemistry》2009,281(1):153-156
The Nuclear and Technological Institute (Instituto Tecnológico e Nuclear—ITN) in cooperation with the International Atomic
Energy Agency (IAEA) has been conducting a nationwide survey of hydrogen (2H/1H) and oxygen (18O/16O) isotopic composition of monthly precipitation since 1988. This paper focuses on basic features of spatial and temporal
distribution of δ18O and δ2H in the precipitation over Continental Portugal derived from ITN database. Phenomenological relationships between stable
isotopes composition of precipitation and various climate-related parameters (local air temperature, distance to the Atlantic
coast, altitude, amount of precipitation) are established and discussed. 相似文献
70.