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791.
Kubo K Nakao A Ishii Y Yamamoto T Tamura M Kato R Yakushi K Matsubayashi GE 《Inorganic chemistry》2008,47(12):5495-5502
The electronic properties of cation radical salts derived from organometallic mixed-ligand complexes [(ppy)Au(S-S)](ppy- = C-dehydro-2-phenylpyridine(-); S-S(2-) = dithiolene ligand) with Au(III)-C sigma-bond were investigated. A 2:1 salt complex [(ppy)Au(C8H4S8)]2[PF6] (C8H4S8(2-) = 2-((4,5-ethylenedithio)-1,3-dithiole-2-ylidene)-1,3-dithiole-4,5-dithiolate(2-)) exhibited semiconductive behavior under ambient pressure (rho rt = 2.6 Omega cm, Ea = 0.03 eV). Magnetic measurements show that it is a Mott insulator close to the metal-insulator boundary. Raman and infrared spectra have revealed that the complex has a quasi-one-dimensional dimeric structure consisting of uniformly charged donor molecules. The complex exhibits metallic behavior at pressures above 0.8 GPa. In contrast, a similar compound [(ppy)Au(C8H4S6O2)]2[BF4] (C8H4S6O2(2-) = 2-((4,5-ethylenedioxy)-1,3-dithiole-2-ylidene)-1,3-dithiole-4,5-dithiolate(2-)) is a band insulator. 相似文献
792.
Katagiri T Fujiwara Y Takahashi S Ozaki N Uneyama K 《Chemical communications (Cambridge, England)》2002,(9):986-987
Chiral induction in the reaction of Et2Zn with PhCHO by fluorinated chiral amino alcohols was correlated to the extent of aggregation of Et2Zn species, which was estimated by manometric study. 相似文献
793.
Kiya Y Hutchison GR Henderson JC Sarukawa T Hatozaki O Oyama N Abruña HD 《Langmuir : the ACS journal of surfaces and colloids》2006,22(25):10554-10563
The redox reactions of DMcT at PEDOT-modified glassy carbon electrodes (GCEs) in acetonitrile (AN) have been investigated via cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM) in order to elucidate the redox reaction mechanism. A redox couple at -0.29 V versus Ag/Ag+ was assigned to the dimerization process of singly protonated DMcT (DMcT-1H), and a second couple observed at +0.42 V was assigned to the polymerization process of the protonated DMcT dimer. Our investigations revealed further that the anodic current response at +0.55 V (polymerization process) has a shoulder at +0.38 V ascribed to the dimerization process of doubly protonated DMcT (DMcT-2H), indicating that the redox couple at +0.42 V is the overlapping response of the polymerization of the protonated DMcT dimer and the dimerization of the DMcT-2H monomer. It was also confirmed that the dimerization process of DMcT-1H at -0.29 V proceeded not only at the surface of a PEDOT film but also inside the film as previously suggested. Moreover, the thermodynamics of these redox reactions at PEDOT-modified GCEs are dependent on the basicity (or acidity) of the solution, as anticipated and previously shown at unmodified GCEs. The oxidation of DMcT occurs at less positive potentials and the reduction occurs at more negative potentials in the presence of base. On the basis of the results obtained, the full redox reaction scheme for DMcT at a PEDOT-modified GCE is proposed. 相似文献
794.
Yasuyuki Tezuka Chisato Hoshino 《Journal of polymer science. Part A, Polymer chemistry》1994,32(5):897-907
Poly(ethylene oxide) [poly(EO)], with number-average molecular weights (Mns) of 1000 and 2000, and poly(tetrahydrofuran) [poly(THF)] with Mns of 1000 and 2000, possessing dichloroacetic acid ester end groups ( 1 , and 2 , respectively) were prepared from precursor diols by esterification with dichloroacetyl chloride in the presence of pyridine. 1 and 2 were subjected to the reaction with copper metal in DMSO to produce the corresponding segmented polyethers containing fumarate/maleate groups within the main chain ( 3 and 4 , respectively), through a polycondensation of carbalkoxy carbenoid intermedlates generated via α, α-dichloro elimination from the end groups of 1 and 2 . The radical polymerization of styrene in the presence of 3 and 4 produced network copolymers consisting of poly (EO) or poly(THF) and polystyrene segments. © 1994 John Wiley & Sons, Inc. 相似文献
795.
The coupling of a high-power nitrogen (N2) microwave-induced plasma (MIP) mass spectrometry--(MS) (1.3 kW) with high-performance liquid chromatography, connected with concentric nebulizer (CN), ultrasonic nebulizer (USN) and a hydride generation (HG) systems, for the optimization and determination of selenium compounds, has been carried out. The MIP-MS system fulfils the ideal requirement being an on-line real-time chromatographic detector for Se speciation analysis. Interchanging of MIP-MS system fabricated nebulizer (concentric) with an ultrasonic nebulizer increases about 3.4-12 (peak height) and 6.5-10 (peak area) times ion signals for the selenium compounds. The detection limits for selenate, selenite, trimethylselenonium ion (TmSe), selenomethionine (Semet) and selenoethionine (Seet) (in Milli-Q-water) obtained with the optimized HPLC-USN-N2MIP-MS system are 0.11, 0.14, 0.09, 0.14 and 0.10 microg L(-1), respectively, about 12-48 times lower than the HPLC-CN-MIP-MS and 1.5-4.4 (peak height) times lower compared to the HPLC-CN-inductively coupled plasma (ICP)-MS coupling. Considering peak area, the repeatability (R.S.D. for three successive analyses) and intermediate precision (R.S.D. for three successive analyses performed on three different days), achieved for five Se compounds are 0.8-5.6, and 1.1-5.9%, comparable with the HPLC-CN-ICP-MS, HPLC-HG-MIP-MS and HPLC-CN-MIP-MS systems. The combined HPLC-USN-N2MIP-MS has been adequately applied for the determination of Se compounds in certified National Institute for Environmental studies human urine CRM No. 18. The results reasonably agree with the HPLC-CN-ICP-MS values. This encouraging combination may be an alternative ion source of mass spectrometry for coming generation in regard to the selenium speciation analysis. 相似文献
796.
Delgado JL de la Cruz P López-Arza V Langa F Kimball DB Haley MM Araki Y Ito O 《The Journal of organic chemistry》2004,69(8):2661-2668
A series of isoindazole-C(60) dyads 4a-c based on pyrazolino[60]fullerene have been prepared by 1,3-dipolar cycloadditions of the nitrile imines, generated in situ from hydrazones 3a-c, to C(60). Molecular orbital calculations for 4b revealed that the electron distribution of the HOMO is located on the isoindazole moiety, while the electron distribution of the LUMO is located on the C(60) moiety. Electrochemical properties of the new dyads 4a-c show a similar electron affinity with respect to C(60). Charge-transfer interactions in the ground state between the isoindazole ring and the fullerene cage are predicted by the molecular orbital calculations and confirmed by electrochemical studies in 4a,b. Steady-state fluorescence emission spectra of dyads 4a-c show that fluorescence intensities in polar benzonitrile solvent decrease with increasing electron-donating ability of the substituent attached on the isoindazole group. This was confirmed by the shortening of fluorescence lifetimes, from which intramolecular charge-separation rates and efficiencies via the excited singlet states of the fullerene moiety were evaluated. The yields of the triplet states in polar solvent decrease with the electron-donating ability, supporting the competitive formation of the charge-separated state with the intersystem crossing from the excited states. Thus, isoindazole[60]fullerene 4b can be considered a molecular switch with an AND logic gate. 相似文献
797.
Shoichi Katsuta Takuya Ishitani Mika Suzuki Yuki Ishii Yoshihiro Kudo Yasuyuki Takeda 《Journal of solution chemistry》2004,33(5):437-451
The 1:1 ion-pair formation constants (K
IP) of tetraalkylammonium (Me4N+, Et4N+, Pr4N+, Bu4N+, and Bu3MeN+) picrates in water were determined by capillary electrophoresis at 25°C. The ion-pair extraction constants (K
ex,ip) of the picrates from water to m-xylene were determined by a batch-extraction method at 25°C, and the distribution constants (K
D) of the neutral ion-pairs were calculated from the relationship K
D = Kex,ip/K
IP. The tetraalkylammonium ion having more methylene groups generally forms a slightly more stable ion-pair with the picrate ion in water, which is attributed to the lower hydration of the cation. For Me4N+, Et4N+, Pr4N+, and Bu4N+, the distribution of the ion pair into m-xylene increases in that order, and a linear relationship was found between log K
D and the number of methylene groups in the cation. This is consistently explained by the regular solution theory. It was also revealed that the ion pairs have a strong specific interaction with water. The ion pair of Bu3MeN+ has a higher distribution constant than that expected from the relationship between log K
D and the number of methylene groups for the symmetrical tetraalkylammonium ions. The cation dependence of the ion pair extractability is mostly governed by that of the distribution of the ion pair. 相似文献
798.
An asymmetric synthesis of chiral 1,4- and 1,5-diols has been developed from the ene acetals 1a and 1c, prepared from the corresponding aldehydes and chiral C(2)-symmetric diols, involving remote asymmetric induction as a key step. In the first step, treatment of 1 with I(coll)(2)ClO(4) in the presence of an alcohol afforded the macrocyclic acetals (3-5 and 7) in a highly stereoselective manner. Subsequent nucleophilic substitution of iodide followed by a Grignard reaction with complete retention of stereochemistry and a final deprotection of the diphenylethylene or diphenylpropylene unit successfully gave optically active 1,4- and 1,5-diols in good yields. 相似文献
799.
We investigated the triboluminescence (TL) of sugars using an innovative experimental approach: the laser-induced shock wave (LISW) technique. We found that the LISW could induce very bright TL in crystalline sugars, the intensity of which was shown to be 10(5) times higher than that obtained by conventional manual hand rubbing. We also applied the LISW technique to amorphous sugar samples. Although it was supposed that TL could not be excited in amorphous solids of sugars having isotropic structures, we revealed that LISW could induce bright TL in amorphous sugars similar to that induced in crystalline sugars. On the basis of the experimental results showing the dynamic behavior of the sample fracture combined with those of the TL, we discuss these novel TL mechanisms in sugars. We believe that the shock wave technique opens a new channel for investigating the nature of TL. 相似文献
800.
Presence of inhomogeneous layered structures of ionic liquid (IL) molecules at IL/HOPG and IL/mica interfaces was directly detected and imaged by using frequency-modulation atomic force microscopy. High stability of the layered structures may disturb their interface applications to catalysis and electrochemistry. 相似文献