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101.
The design and synthesis of a porphyrin-appended terpyridine, 5-(4-([2,2′:6′,2″]-terpyridin-4-yl-carboxyamidyl)phenyl)-10,15,20-triphenylporphyrin (H2TPPTPy) and its application as potential fluoroionophore for recognition of metal ions are reported. For preparation of the fluoroionophore, a novel simple strategy with improved total yield has been applied for the synthesis of 2,2′:6′,2″-terpyridine-4′-carboxylic acid as a ligand. H2TPPTPy shows chelation-enhanced fluorescence effect with cadmium ion via the interruption of photoinduced electron transfer (PET) process, which has been utilized as the basis of the fabrication of the Cd(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Cd(II)-sensitive chemosensor were investigated. It shows a linear response toward Cd(II) in the concentration range of 3.2 × 10−6 to 3.2 × 10−4 M with a limit of detection of 1.2 × 10−6 M. The chemosensor shows good selectivity for Cd(II) over a large number of cations, such as alkali, alkali earth and transitional metal ions except Cu(II) and Zn(II). The sensor has been used for determination of Cd(II) in water samples with satisfactory recoveries. 相似文献
102.
The preliminary results described here show the complete transfer of Hg(II) ions, in the absence of a chelating agent in 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids; the lag time required to gain the quantitative metal ion partition turned out to be strongly dependent both on alkyl chain length on the imidazolium ring and on the working temperature. 相似文献
103.
104.
Conformational stability of G-quartets found in telomeric DNA quadruplex structures requires the coordination of monovalent ions. Here, an extensive Hartree-Fock and density functional theory analysis of the energetically favored position of Li+, Na+, and K+ ions is presented. The calculations show that at quartet-quartet distances observed in DNA quadruplex structures (3.3 A), the Li+ and Na+ ions favor positions of 0.55 and 0.95 A outside the plane of the G-quartet, respectively. The larger K+ ion prefers a central position between successive G-quartets. The energy barrier separating the minima in the quartet-ion-quartet model are much smaller for the Li+ and Na+ ions compared with the K+ ion; this suggests that K+ ions will not move as freely through the central channel of the DNA quadruplex. Spin-spin coupling constants and isotropic chemical shifts in G-quartets extracted from crystal structures of K+- and Na+-coordinated DNA quadruplexes were calculated with B3LYP/6-311G(d). The results show that the sizes of the trans-hydrogen-bond couplings are influenced primarily by the hydrogen bond geometry and only slightly by the presence of the ion. The calculations show that the R(N2N7) distance of the N2-H2...N7 hydrogen bond is characterized by strong correlations to both the chemical shifts of the donor group atoms and the (h2)J(N2N7) couplings. In contrast, weaker correlations between the (h3)J(N1C6') couplings and single geometric factors related to the N1-H1...O6=C6 hydrogen bond are observed. As such, deriving geometric information on the hydrogen bond through the use of trans-hydrogen-bond couplings and chemical shifts is more complex for the N1-H1...O6=C6 hydrogen bond than for the N2-H2...N7 moiety. The computed trans-hydrogen-bond couplings are shown to correlate with the experimentally determined couplings. However, the experimental values do not show such strong geometric dependencies. 相似文献
105.
《Electroanalysis》2006,18(11):1081-1089
This paper describes the voltammetric behavior of As(III) at the hanging mercury drop electrode (HMDE) in the presence of sodium diethyl dithiocarbamate (SDDC) and a new voltammetric method for the determination of As(III) at trace levels. The method is based on the adsorptive deposition of a As(III) complex with SDDC at ?0.45 V (vs. Ag/AgCl) on the HMDE in acidic medium of 0.01 mol L?1 HCl (pH 2.0) and its cathodic stripping during the potential scan (100 mV s?1). The linear range for the determination of As(III) in the presence of SDDC (4 μmol L?1) in water samples was between 1 and 10 μg L?1 for a deposition time of 300 s (r=0.994) and between 10 and 100 μg L?1 for a deposition time of 60 s (r=0.999). For the determination of As(III) in dialysis concentrate samples, the linear range was between 5 and 25 μg L?1 for a deposition time of 180 s (r=0.992) and between 10 and 100 μg L?1 for a deposition time of 60 s (r=0.996). Detection limits of 0.3 and 2.2 μg L?1 in water and dialysis concentrate samples were calculated for the method using a deposition time of 300 and 180 s, respectively. Recovery values between 93.0 and 110.0% for As(III) added to deionized, mineral, seawater (synthetic and real) and dialysis concentrate samples prove the satisfactory accuracy and applicability of the procedure. 相似文献
106.
Ion Association and Hydration in Aqueous Solutions of Nickel(II) and Cobalt(II) Sulfate 总被引:1,自引:0,他引:1
Ting?Chen Glenn?HefterEmail author Richard?Buchner 《Journal of solution chemistry》2005,34(9):1045-1066
Aqueous solutions of nickel(II) and cobalt(II) sulfate have been investigated at 25 ∘C by dielectric relaxation spectroscopy (DRS) over a wide range of frequencies (0.2 ≤ ν (GHz) ≤ 89) and salt concentrations
(0.025 ≤ c(mol-L−1) ≤ 1.4). The spectra indicate, as for MgSO4(aq) studied previously, the simultaneous presence of double solvent-separated, solvent-shared and contact ion pairs in both
NiSO4(aq) and CoSO4(aq). The stepwise formation constants for each ion-pair type and the overall association constant, obtained from the data
are in good agreement with ultrasonic relaxation and other estimates. The DR spectra at higher concentrations (c ≥ 0.5 mol-L−1) suggest the existence of a nonlinear triple ion M2SO42+(aq). Consistent with the very strong hydration of the salts, which have ‘effective’ hydration numbers approaching 27 at infinite
dilution, there are no significant differences in any of the relaxation or thermodynamic parameters for NiSO4(aq) and CoSO4(aq), except that the triple ion appears to be somewhat more stable for the latter. 相似文献
107.
H. Pongratz K. K. Mayer W. Wiegrebe 《Monatshefte für Chemie / Chemical Monthly》1997,128(6-7):659-673
Summary N-Butoxy- and N-propoxy-imines derived fromo-,m-, andp-substituted benzaldehydes (X = F, Cl, Br, I) decompose upon electron impact to the respective aldoximes by loss of C
n
H2n
and competitivelyvia 1,5-distonic radical cations by loss of CH2O to 1,3-distonic ions which eliminate H and/or a halogen atom in the course of homolytic aromatic substitution, giving rise to cyclic (M-CH2O-H)+ or (M-CH2O-X
)+ ions.Dedicated with warm regards to Prof. Dr.D. Seebach, Zürich, on the occasion of his 60th birthday 相似文献
108.
A. A. Vedenyapin M. D. Baturova G. I. Ioseliani G. Kh. Areshidze 《Russian Chemical Bulletin》1997,46(1):76-80
The anodic oxidation of the carbon felt Carbonetcalon results in the formation of surface defects which serve as centers of
strong adsorption of PdII, NiII, and CuII ions. The electrochemical reduction of adsorbed ions makes it possible to obtain metallic catalysts, which undergo multiple
redox cycles without loss of metal. The catalysts are characterized by high dispersity of the reduced phase, high adsorption
capacity with respect to hydrogen, and 100% selectivity in hydrogenation of acetophenone.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 81–85, January 1997 相似文献
109.
G. Papanastasiou A. Papoutsis M. Tsirtou I. Ziogas 《Journal of solution chemistry》1996,25(2):203-217
The kinetics of the reaction between sodium ethoxide and methyl iodide has been studied at 25°C in various cyclohexane-ethanol solvent mixtures with a cyclohexane content of 10 to 50% per volume. The determination of the rate constants att=0 were carried out by a new iterative method proposed in this investigation. The obtained results show that the reaction rate decreases with the increasing cyclohexane content. This behavior can be attributed to various solute-solvent interactions of electrostatic nature. On the other hand, the variation of ion and ion pairs rate constants with solvent composition permits the various solvation effects to be taken into account. 相似文献
110.
研究了在聚乙二醇2000(PEG)-硫酸钠(Na2SO4)-邻苯二酚紫(PV)体系中铍(Ⅱ)、铁(Ⅲ)、铁(Ⅱ)、铝(Ⅲ)、铬(Ⅲ)、锰(Ⅱ)的萃取行为。试验结果表明,铍(Ⅱ)在pH 3.5-7.0及铁(Ⅲ)在pH 4.0-7.0范围内可以被PEG相几乎完全萃取,而铝(Ⅲ)、铬(Ⅲ)在pH 1.0-7.0、锰(Ⅱ)在pH 1.0-4.5、铁(Ⅱ)在pH 1.0-4.5则不被萃取。从而实现了将铍(Ⅱ)(pH 3.5)、铁(Ⅲ)(pH 5.0)与铝(Ⅲ)、铬(Ⅲ)、锰(Ⅱ)、铁(Ⅱ)混合离子的定量分离。同时探讨了PEG相的萃取机理。 相似文献