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121.
Small-angle X-ray scattering (SAXS) measurements on V2O5·nH2O sols and gels, prepared by dissolving V2O5 glass into water at room temperature, show that there are V2O5 polymeric fibers entangled like random coils in the sol of n 5000, while the deviation from the random coil behavior occurs in the dilute sol of n 6000.
A Bragg peak appears at the scattering vector h 0.02 Å−1 to be superimposed on an asymptotic h−2-course in the SAXS curve of the concentrated sol of n 680. This means that the spatial correlation between V2O5 polymeric fibers takes place even in the fluid state.
V2O5·nH2O sols completely lose fluidity at n 250 to transfer to the gel state, where V2O5 polymeric fibers begin to pile up in the parallel with a substrate surface. Such a layer structure is preserved up to the gel of n 4. However, V2O5 polymeric fibers are randomly oriented within each layer. 相似文献
122.
Kawaguchi M Ito R Honda H Endo N Okanouchi N Saito K Seto Y Nakazawa H 《Journal of chromatography. A》2008,1206(2):196-199
A simple and highly sensitive method called stir bar sorptive extraction (SBSE) and thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS), which is used for the determination of trace amounts of 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan) in river water samples, is described. A stir bar coated with polydimethylsiloxane (PDMS) is added to a 10mL water sample and stirring is carried out for 120min at room temperature (25 degrees C) in a vial. Then, the PDMS stir bar is subjected to TD-GC-MS. The detection limit of triclosan is 5ngL(-1) (ppt). The method shows linearity over the calibration range (0.02-20mugL(-1)) and the correlation coefficient is higher than 0.997 for triclosan standard solution. The recovery of triclosan in river water samples ranges from 91.9 to 108.3% (RSD: 4.0-7.0%). This simple, accurate, sensitive, and selective analytical method may be used in the determination of trace amounts of triclosan in river water samples. 相似文献
123.
A theoretical investigation of the X(2)A" and A(2)A' electronic states of the HO(2) radical is reported. Both electronic states have nonlinear equilibrium geometries and they correlate with a (2)Pi state at linear geometries so that they exhibit the Renner effect. In highly excited bending states, there is tunneling between two equivalent minima (with geometries where the H nucleus is bound to one, or the other, of the two O nuclei), and the two linear geometries H-O-O and O-O-H become accessible to the molecule. Thus, HO(2) affords an example of the so-called double Renner effect. Three-dimensional potential energy surfaces for the X(2)A" and A(2)A' electronic states of HO(2) have been calculated ab initio and the global potential energy surfaces for the states have been constructed. These surfaces have been used, in conjunction with the computer program DR [Odaka et al., J. Mol. Structure 795, 14 (2006); Odaka et al., J. Chem. Phys. 126, 094301 (2007)], for calculating HO(2) rovibronic energies in the "double-Renner"-degenerate electronic states X(2)A" and A(2)A'. The results of the ab initio calculations, the rovibronic energies obtained, and analyses of the wavefunctions for selected states are presented. 相似文献
124.
Kawaguchi M Ito R Honda H Endo N Okanouchi N Saito K Seto Y Nakazawa H 《Journal of chromatography. A》2008,1200(2):260-263
A method for the simultaneous measurement of benzophenone (BP) sunscreen compounds, its derivatives 2,4-dihydroxybenzophenone (BP-1), 2-hydroxy-4-methoxybenzophenone (BP-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone (BP-10), 2-hydroxybenzophenone (2OH-BP), 3-hydroxybenzophenone (3OH-BP) and 4-hydroxybenzophenone (4OH-BP), in water samples was developed using stir bar sorptive extraction (SBSE) with in situ derivatization followed by thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS). The detection limit is 0.5-2 ng L(-1) (ppt) for the seven BPs. The method shows good linearity and the correlation coefficients are equal to or higher than 0.990 for all the analyte. The average recoveries of BPs range from 102.0 to 128.1% (RSD<15.4%, n=6). Trace amounts of BPs in river water samples were determined by the present method. 相似文献
125.
Direct observation of the convectional dissipative patterns was successful during the course of dryness of colloidal crystals
of poly (methyl methacrylate) spheres on a cover glass. Formation processes of the convectional patterns of spoke-like lines
were observed as a function of sphere size and also sphere concentration. During dryness of the suspensions, the brilliant
iridescent colors changed beautifully. Macro- and microscopic drying patterns and thickness profiles of the dried film were
observed. Sharp broad rings were observed especially at low sphere concentrations. The water evaporation accompanied with
the convectional flow of water and the colloidal spheres played an important role for these dissipative structure formation. 相似文献
126.
Negishi M Seto H Hase M Yoshikawa K 《Langmuir : the ACS journal of surfaces and colloids》2008,24(16):8431-8434
The mobility of phospholipid molecules at a water/oil interface on cell-sized phospholipid-coated microdroplets was investigated through the measurement of diffusion constants by fluorescence recovery after photobleaching. It is found that the diffusion constant of phospholipids showed the relation D approximately (eta water + eta oil) -0.85, where D is the diffusion constant, eta water is the viscosity of water, and eta oil is the viscosity of oil. This observation indicates that the viscosity of the surrounding oil is the primary factor that determines the diffusibility of phospholipids at a water/oil interface. 相似文献
127.
Hirao I Mitsui T Kimoto M Yokoyama S 《Journal of the American Chemical Society》2007,129(50):15549-15555
Expansion of the genetic alphabet by an unnatural base pair system provides a powerful tool for modern biotechnology. As an alternative to previous unnatural base pairs, we have developed a new pair between 7-(2-thienyl)imidazo[4,5-b]pyridine (Ds) and 2-nitropyrrole (Pn), which functions in DNA amplification. Pn more selectively pairs with Ds in replication than another previously reported pairing partner, pyrrole-2-carbaldehyde (Pa). The nitro group of Pn efficiently prevented the mispairing with A. High efficiency and selectivity of the Ds-Pn pair in PCR amplification were achieved by using a substrate mixture of the gamma-amidotriphosphate of Ds and the usual triphosphates of Pn and the natural bases, with Vent DNA polymerase as a 3' to 5' exonuclease-proficient polymerase. After 20 cycles of PCR, the total mutation rate of the Ds-Pn site in an amplified DNA fragment was approximately 1%. PCR amplification of DNA fragments containing the unnatural Ds-Pn pair would be useful for expanded genetic systems in DNA-based biotechnology. 相似文献
128.
Odaka TE Melnikov VV Jensen P Hirano T Lang B Langer P 《The Journal of chemical physics》2007,126(9):094301
The authors report here the implementation of a newly developed, highly efficient matrix diagonalization routine in the DR program [T. E. Odaka et al., J. Mol. Struct. 795, 14 (2006)]. The DR program solves the rovibronic Schrodinger equation for a triatomic molecule with a double Renner effect, i.e., with two accessible linear arrangements of the nuclei at which the electronic energy is doubly degenerate. With the new routines, the authors can extend the DR calculations of rovibronic energies for A 2Pi MgNC/MgCN by considering a much larger set of rovibronic states, in particular, states at higher J values, than the authors were able to access previously. 相似文献
129.
The ground and low-lying excited states of CoCN have been studied by ab initio multireference single and double excitation configuration interaction (MR-SDCI) calculations with Davidson's correction Q and Cowan-Griffin's relativistic corrections. The electronic ground state of CoCN is (3)Phi(i) and the equilibrium geometry is linear with bond lengths of r(e)(Co-C)=1.8540 A and r(e)(C-N)=1.1677 A, substantially different from the experimentally derived values of r(0)(Co-C)=1.8827(7) A and r(0)(C-N)=1.1313(10) A. The first excited state is (3)Delta(i), separated from the ground state by 727 cm(-1). Larger dynamical electron correlation energy for the low-spin (3)Phi state than for the high-spin (5)Phi state makes the (3)Phi state to be the ground state, which is discussed in terms of the differences in natural orbitals. A new spin-orbit interaction scheme between the X (3)Phi(i) and 1 (3)Delta(i) states is proposed. 相似文献
130.
Colloidal crystals of core-shell type spheres with poly(styrene) core and poly(ethylene oxide) shell
Okamoto J Kimura H Tsuchida A Okubo T Ito K 《Colloids and surfaces. B, Biointerfaces》2007,56(1-2):231-Optics
Elastic modulus and crystal growth kinetics have been studied for colloidal crystals of core–shell type colloidal spheres (diameter = 160–200 nm) in aqueous suspension. Crystallization properties of three kinds of spheres, which have poly(styrene) core and poly(ethylene oxide) shell with different oxyethylene chain length (n = 50, 80 and 150), were examined by reflection spectroscopy. The suspensions were deionized exhaustively for more than 1 year using mixed bed of ion-exchange resins. The rigidities of the crystals range from 0.11 to 120 Pa and from 0.56 to 76 Pa for the spheres of n = 50 and 80, respectively, and increase sharply as the sphere volume fraction increase. The g factor, parameter for crystal stability, range from 0.029 to 0.13 and from 0.040 to 0.11 for the spheres of n = 50 and 80, respectively. These g values indicate the formation of stable crystals, and the values were decreased as the sphere volume fraction increased. Two components of crystal growth rate coefficients, fast and slow, were observed in the order from 10−3 to 101 s−1. This is due to the secondary process in the colloidal crystallization mechanism, corresponding to reorientation from metastable crystals formed in the primary process and/or Ostwald-ripening process. There are no distinct differences in the structural, kinetic and elastic properties among the colloidal crystals of the different core–shell size spheres, nor difference between those of core–shell spheres and silica or poly(styrene) spheres. The results are very reasonably interpreted by the fact that colloidal crystals are formed in a closed container owing to long-range repulsive forces and the Brownian movement of colloidal spheres surrounded by extended electrical double layers, and their formation is not influenced by the rigidity and internal structure of the spheres. 相似文献