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351.
The standard oxidation states of central metal atoms in C
4v
nitrido ([M(N)(L)5]
z
) complexes are four units higher than those in corresponding nitrosyls ([M(NO)(L)5]
z
) (L=CN: z = 3−, M = Mn, Tc, Re; z = 2−, M = Fe, Ru, Os; L = NH3: z = 2+, M = Mn, Tc, Re; z = 3+, M = Fe, Ru, Os). Recent work has suggested that [Mn(NO)(CN)5]3− behaves electronically much closer to Mn(V)[b
2(xy)]2, the ground state of [Mn(N)(CN)5]3−, than to Mn(I)[b
2(xy)]2[e(xz,yz)]4. We have employed density functional theory and time-dependent density functional theory to calculate the properties of the
ground states and lowest-lying excitations of [M(N)(L)5]
z
and [M(NO)(L)5]
z
. Our results show that [M(N)(L)5]
z
and [M(NO)(L)5]
z
complexes with the same z value have strikingly similar electronic structures. 相似文献
352.
353.
Money VA Cartmell A Guerreiro CI Ducros VM Fontes CM Gilbert HJ Davies GJ 《Organic & biomolecular chemistry》2008,6(5):851-853
The substrate binding regions of a beta-1,3:1,4 glucanase are revealed through structural analysis with a thio-oligosaccharide and kinetics of enzyme variants. 相似文献
354.
The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories. 相似文献
355.
Variability of UV irradiance in Europe 总被引:1,自引:1,他引:0
Seckmeyer G Pissulla D Glandorf M Henriques D Johnsen B Webb A Siani AM Bais A Kjeldstad B Brogniez C Lenoble J Gardiner B Kirsch P Koskela T Kaurola J Uhlmann B Slaper H den Outer P Janouch M Werle P Gröbner J Mayer B de la Casiniere A Simic S Carvalho F 《Photochemistry and photobiology》2008,84(1):172-179
356.
Hassan Keypour Reza Azadbakht Hamid Khanmohammadi Harry Adams 《Journal of organometallic chemistry》2008,693(13):2237-2243
Three Cd(II) macroacyclic Schiff base complexes [CdL4(NO3)2] (4), [CdL5(NO3)2] (5), [CdL6(NO3)2] (6) were prepared by template condensation of 2-pyridinecarboxaldehyde with N1-(2-nitrobenzyl)-N1-(2-aminoethyl)ethane-1,2-diamine (L1), N1-(2-nitrobenzyl)-N1-(2-aminoethyl)propane-1,3-diamine (L2) or N1-(2-nitrobenzyl)-N1-(3-aminopropyl)propane-1,3-diamine (L3), in the presence of cadmium metal ion, respectively. Three Cd(II) complexes with L1, L2 and L3 were also synthesized. All complexes have been studied with IR, 1H NMR, 13C NMR, DEPT, COSY, HMQC and microanalysis. Two of these complexes, [CdL4(NO3)2] (4) and [CdL1(NO3)2] (1) have been characterized through X-ray crystallography. In complex 4, the Cd is in a six-coordinate environment comprised of the ligand N4-donor set and two oxygen atoms of two nitrate groups. In the polyamine complexes (1, 2 and 3) Cd and ligand are in a ratio of 1:1. Supporting ab initio HF-MO calculations have been undertaken using the standard 3-21G∗ and 6-31G∗ basis sets. 相似文献
357.
Dibutylmagnesium (contaminated with Al(n-Bu)3; nMg:nAl ca. 1:0.2) was found to react with MeOCH2CH2OH followed by the addition of PhSCH(Me)Ph in the presence of 0.2 equiv n-butyllithium yielding [Mg7(μ3-OCH2CH2OMe)6(μ-OCH2CH2OMe)6][Al(n-Bu)4]2 (1) as the principal product (yield 40–45% referred to MeOCH2CH2OH). The single-crystal X-ray diffraction analysis revealed that the centrosymmetric cationic heptamagnesium complex is built up from seven edge-shared MgO6 octahedra. The [Al(n-Bu)4]− anions adopt approximately a tetrahedral AlC4 symmetry. 1H, 13C and 27Al NMR spectroscopic measurements showed that in THF solution the structures both of the heptamagnesium complex and the tetrabutylaluminate anion are preserved and that there are no cation–anion interactions reducing the symmetry. The 27Al resonance (151.6 ppm) was found to be very sharp (w1/2 = 5 Hz), the coupling constant 1J(27Al,13C) amounts to 72.3 Hz. 相似文献
358.
He Zhu Dr. Qiang Chen Dr. Igor Rončević Dr. Kirsten E. Christensen Prof. Harry L. Anderson 《Angewandte Chemie (International ed. in English)》2023,62(31):e202307035
π-Conjugated nanoribbons attract interest because of their unusual electronic structures and charge-transport behavior. Here, we report the synthesis of a series of fully edge-fused porphyrin-anthracene oligomeric ribbons (dimer and trimer), together with a computational study of the corresponding infinite polymer. The porphyrin dimer and trimer were synthesized in high yield, via oxidative cyclodehydrogenation of singly linked precursors, using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and trifluoromethanesulfonic acid (TfOH). The crystal structure of the dimer shows that the central π-system is flat, with a slight S-shaped wave distortion at each porphyrin terminal. The extended π-conjugation causes a dramatic red-shift in the absorption spectra: the absorption maxima of the fused dimer and trimer appear at 1188 nm and 1642 nm, respectively (for the nickel complexes dissolved in toluene). The coordinated metal in the dimer was changed from Ni to Mg, using p-tolylmagnesium bromide, providing access to free-base and Zn complexes. These results open a versatile avenue to longer π-conjugated nanoribbons with integrated metalloporphyrin units. 相似文献
359.
360.
Palmer JH Day MW Wilson AD Henling LM Gross Z Gray HB 《Journal of the American Chemical Society》2008,130(25):7786-7787
This work reports the synthesis and full characterization of 5,10,15-tris-pentafluorophenylcorrolato-iridium(III) bis-trimethylamine 1 and its octabromo derivative 2. The corrole is planar in both cases (the mean deviation from the plane is as low as 0.0371 A for 1 and 0.0325 A for 2), the UV-vis spectra display a split Soret band with a shoulder attributable to an MLCT transition, and cyclic voltammetry reveals that the iridium(II) oxidation state cannot be accessed, while the oxidation to formal iridium(IV) complexes is achieved at much lower potentials than in other coordination environments. 相似文献