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101.
The reactions of the half‐sandwich iron(II) complex [FeCl(Cp*)(tmeda)] ( 1 ; Cp*=η5‐C5Me5, TMEDA=N,N,N′,N′‐tetramethylethylenediamine) with potassium naphthalenide or potassium anthracenide gave the diamagnetic complexes [(Cp*)Fe(μ‐polyarene)Fe(Cp*)] (polyarene=naphthalene ( 2 ), anthracene ( 3a )), which have two {(Cp*)Fe} units bound to opposite faces of the polyarene. One of two {(Cp*)Fe} units in 3a is located over the central ring of anthracene while the other is positioned over an outer ring. The {(Cp*)Fe} unit bound to the central ring of 3a migrates to the outer ring upon heating in the solid state to give the isomer 3b . The electrochemical potential separations between successive one‐electron redox events for complexes 2 and 3b are large. The mixed valence complexes [ [2]+ ]+ and [ [3b]+ ]+ were synthesized by chemical oxidation. The mixed‐valence complex [ [3b]+ ]+ is charge delocalized on the Mössbauer timescale at 78 K, and its absorption spectrum shows an intervalence charge‐transfer band. Complex [ [2]+ ]+ exhibits two absorption bands in the near‐IR region and a slightly broadened doublet in the Mössbauer spectrum. DFT calculations were carried out to examine the electronic structures of these dinuclear iron(I) complexes to elucidate the factors responsible for their diamagnetism and to determine the degree of charge delocalization in the mixed‐valence complexes.  相似文献   
102.
Circularly polarized luminescence (CPL) of chiral Eu(III) complexes with nona- and octa-coordinated structures, [Eu(R/S-iPr-Pybox)(D-facam)(3)] (1-R/1-S; R/S-iPr-Pybox, 2,6-bis(4R/4S-isopropyl-2-oxazolin-2-yl)pyridine; D-facam, 3-trifluoroacetyl-d-camphor), [Eu(S,S-Me-Ph-Pybox)(D-facam)(3)] (2-SS; S,S-Me-Ph-Pybox, 2,6-bis(4S-methyl-5S-phenyl-2-oxazolin-2-yl)pyridine), and [Eu(Phen)(D-facam)(3)] (3; Phen, 1,10-phenanthroline) are reported, and their structural features are discussed on the basis of X-ray crystallographic analyses. These chiral Eu(III) complexes showed relatively intense photoluminescence due to their (5)D(0) → (7)F(1) (magnetic-dipole) and (5)D(0) → (7)F(2) (electric-dipole) transition. The dissymmetry factors of CPL (g(CPL)) at the former band of 1-R and 1-S were as large as -1.0 and -0.8, respectively, while the g(CPL) of 3 at the (5)D(0) → (7)F(1) transition was relatively small (g(CPL) = -0.46). X-ray crystallographic data indicated specific ligand-ligand hydrogen bonding in these compounds which was expected to stabilize their chiral structures even in solution phase. CPL properties of 1-R and 1-S were discussed in terms of transition nature of lanthanide luminescence.  相似文献   
103.
Structural stability of GaN(0 0 0 1) under Ga-rich conditions is systematically investigated by using our ab initio-based approach. The surface phase diagram for GaN(0 0 0 1) including (2×2) and pseudo-(1×1) is obtained as functions of temperature and Ga beam equivalent pressure by comparing chemical potentials of Ga atom in the gas phase with that on the surface. The calculated results reveal that the pseudo-(1×1) appearing below 684–973 K changes its structure to the (2×2) with Ga adatom at higher temperatures beyond 767–1078 K via the newly found (1×1) with two adlayers of Ga. These results are consistent with the stable temperature range of both the pseudo-(1×1) and (2×2) with Ga adatom obtained experimentally. Furthermore, it should be noted that the structure with another coverage of Ga adatoms between the (1×1) and (2×2)-Ga does not appear as a stable structure of GaN(0 0 0 1). Furthermore, ghost island formation observed by scanning tunneling microscopy is discussed on the basis of the phase diagram.  相似文献   
104.
105.
Flow of a spontaneously formed optical pattern in a nonlinear optical feedback system consisting of a liquid crystal optically addressable spatial light modulator with feedback is induced by a lateral wave-front shift of the feedback light. We demonstrate the dependency of the flow speed on the wave-front shift by tilting an optical flat inserted in the feedback loop. We also demonstrate the application to real-time, high-sensitivity detection of small tilt angles of optical components.  相似文献   
106.
As the first systematic study dealing with the adsorption of estrogens by granular activated carbon (GAC), the removal behavior of 17β-estradiol (E2) and its biotransformation product of estrone (E1) in fixed GAC columns was examined using four biological activated carbon (BAC) columns (BAC-1~BAC-4) generated by coating four GAC columns with detached microorganisms from the riverbed sediment of a representative drinking river water source containing lower content of natural organic matter (NOM). For comparison, parallel adsorption experiments were also performed using another four GAC columns (GAC-1~ GAC-4) packed by strictly following the configurations of four BAC columns. Adsorption experimental results obtained by intermittently spiking E2 over a total running period about 350 days into the river water mixed with or without a peaty water containing higher content of NOM showed that E2 was readily removed by adsorption and the combined adsorption/biodegradation. The vertical profiles of E2 and E1, which have great significance for better understanding and optimization of the adsorption process for removal of human estrogens, were also obtained.  相似文献   
107.
The surface of a TiO2 film electrode, about 1 μm thick, prepared by the sol-gel method, was modified by being additionally coated with about 0.1 μm thick TiO2---SiO2, TiO2---ZrO2 or TiO2---Al2O3 films. The effect of the additional coating on the photoelectrochemical properties of a TiO2 film electrode was investigated in detail. On addition of the second additive to TiO2, the flat band potential was shifted toward negative potential for SiO2 and positive potential for ZrO2 and Al2O3, which is attributed to the change in the point of zero zeta potential (pzzp), not in the electron affinity (EA). However, enhancement in photocurrent was not observed for all the cases.  相似文献   
108.
The surface of a gold (Au) disk electrode was modified with a self-assembled monolayer consisting of phenylboronic acid moiety to fabricate a voltammetric sensor sensitive to sugars. The modified Au electrode exhibited a voltammetric response to sugars in the presence of Fe(CN)6(3-) ion in the sample solution at neutral pH. The peak current of the cyclic voltammograms decreased depending on the type and concentration of sugars. The dynamic range of the electrode is 3 - 100 mM for glucose and mannose and 1 - 30 mM for fructose. The sugar sensor can be used repeatedly after rinsing in 10 mM acetate buffer (pH 4.5).  相似文献   
109.
Surface-modified polyethylene (PE) membrane sheets were prepared by the radiation-induced graft polymerization (RIGP) of an epoxy-group-containing monomer, glycidyl methacrylate (GMA). The epoxy ring of GMA was opened by introducing diethylamine (DEA) or sodium sulfite (SS). We examined the properties of these sheets by measuring the amount of grafting polymer, surface roughness and membrane potential, and also investigated the adhesion of five Gram-negative bacteria, Escherichia coli, Pseudomonas aeruginosa, Pseudomonas putida, Pseudomonas fluorescens and Paracoccus denitrificans, onto the prepared sheet surfaces. A linear relationship between the degree of grafting (dg) and surface roughness was observed. Moreover, membrane potential was dependent on the amount of DEA or SS as the ionizable group. These results indicate that RIGP enables the control of the physicochemical properties of such a sheet surface by adjusting dg and the subsequent conversion of functional groups. A batch test on bacterial adhesion onto the sheets clarified that the DEA-containing sheet (DEA sheet) exhibited an adhesion rate constant, k, significantly greater than those of other types of sheet. Clearly, the adhesion rate constant of the DEA sheet increased with dg, indicating that electrostatic interaction is the most decisive factor for bacterial adhesion when it works as an attractive force. Furthermore, the densities of bacteria adhering onto the GMA-containing sheet (GMA sheet) and the SS-containing sheet (SS sheet) were almost the same as that onto a PE sheet, whereas that onto a DEA sheet significantly increased. Thus, the introduction of the GMA- and SS-containing graft chain did not have much influence on bacterial adhesion onto the surfaces, supporting the conclusion that the promotion of bacterial adhesion onto the GMA and SS sheets was due to an increase in surface area resulting from RIGP. Moreover, the scanning electron microscopy images of the sheet surfaces indicate that the conditions and morphologies of initial bacterial adhesion are dependent on surface properties, particularly membrane potential.  相似文献   
110.
We have developed a practical crossed Claisen condensation between ketene silyl acetals and methyl esters using catalytic NaOH to obtain alpha-monoalkylated beta-keto esters and inaccessible alpha,alpha-dialkylated beta-keto esters.  相似文献   
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