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121.
Christopher M. Barhick John R. Eyler 《Journal of the American Society for Mass Spectrometry》1992,3(2):122-127
A glow discharge (CD) ion source has been coupled to a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer using a four-element electrostatic lens to accelerate and focus ions generated external to the instrument’s high magnetic field into its analyzer cell. Like other CD mass spectrometers, GD-FT-ICR can provide a quantitative measure of bulk analyte concentration with good precision and accuracy. Although detection limits currently attainable are several orders of magnitude higher than the commercially available magnetic sector-based instrument, CD-FT-ICR holds promise for ultrahigh resolving power elemental mass analysis. Several schemes are proposed to lower the detection limits of the technique while still providing high enough resolution to resolve isobaric interferences. 相似文献
122.
Christopher T Burns 《Journal of organometallic chemistry》2003,683(1):240-248
The reaction of (hexyl)HC(mim)2 (1, mim=N-methyl-imidazol-2-yl) with (cod)PdMeCl in C6H6 yields {(hexyl)HC(mim)2}Pd(Me)Cl (3). The photochemical reaction of 3 with CH2Cl2 at 23 °C in ambient room light yields {(hexyl)HC(mim)2}Pd(CHCl2)Cl (4). It is proposed that this reaction proceeds by homolytic scission of the PdMe bond of 3. 相似文献
123.
MNDO calculations have been carried out on the reactions of the electron-rich germylene L2Ge [L=(H3Si)2N] with diazo compounds, as models for the experimentally observed reactions of L2Ge [L=(Me3Si)2N]. The most stable form of the 11 adduct of L2Ge with N2C(COOMe)2 is found to have a cyclic configuration resulting from a strong intramolecular interaction between the oxygen of one of the carbonyl groups and the germanium atom. Protonation of this cyclic adduct occurs at nitrogen, giving an intermediate, addition to which of nucleophiles X– provides acyclic L2Ge(X)NHN(COOMe)2, as observed experimentally. Two similar cyclic adducts are formed between L2Ge and N2C(COCH3)(COOCH3), the most stable of which provides, after a proton shift, the observed 1,3,4,2-oxadiazagermine system
. Adduct formation between Me2Si=NSiMe3 and simple Lewis bases (H2O, NH3, THF, H2CO) is calculated to be strong, but the corresponding adducts of Me2Ge=NSiMe3 are very weak: much stronger adducts are predicted for L2GeNNC(COOMe)2. 相似文献
124.
Wang XB Niu S Yang X Ibrahim SK Pickett CJ Ichiye T Wang LS 《Journal of the American Chemical Society》2003,125(46):14072-14081
The cubane [4Fe-4S] is the most common multinuclear metal center in nature for electron transfer and storage. Using electrospray, we produced a series of gaseous doubly charged cubane-type complexes, [Fe4S4L4]2- (L = -SC2H5, -SH, -Cl, -Br, -I) and the Se-analogues [Fe4Se4L4]2- (L = -SC2H5, -Cl), and probed their electronic structures with photoelectron spectroscopy and density functional calculations. The photoelectron spectral features are similar among all the seven species investigated, revealing a weak threshold feature due to the minority spins on the Fe centers and confirming the low-spin two-layer model for the [4Fe-4S](2+) core and its "inverted level scheme". The measured adiabatic detachment energies, which are sensitive to the terminal ligand substitution, provide the intrinsic oxidation potentials of the [Fe4S4L4]2- complexes. The calculations revealed a simple correlation between the electron donor property of the terminal thiolate as well as the bridging sulfide with the variation of the intrinsic redox potentials. Our data provide intrinsic electronic structure information of the [4Fe-4S] cluster and the molecular basis for understanding the protein and solvent effects on the redox properties of the [4Fe-4S] active sites. 相似文献
125.
A sensitive voltammetric method is presented for the determination of tract levels of Mn (II) using carbon film electrodes fabricated from carbon resistors of 2 Ω. Determination of manganese was made by square wave cathodic stripping voltammetry (CSV), with deposition of manganese as manganese dioxide. Chronoamperometric experiments were made to study MnO2 nucleation and growth. As a result, it was found to be necessary to perform electrode conditioning at a more positive potential to initiate MnO2 nucleation. Under optimised conditions the detection limit obtained was 4 nM and the relative standard deviation for eight measurements of 0.22 nM was 5.3%. Interferences from various metal ions on the response CSV of Mn(II) were investigated, namely Cd(II), Ni(II), Cu(II), Cr(VI), Pb(II), Zn(II) and Fe(II). Application to environmental samples was demonstrated. 相似文献
126.
Aguilar CN Favela-Torres E Viniegra-González G Augur C 《Applied biochemistry and biotechnology》2002,102(1-6):407-414
Undesirable protease production by Aspergillus niger Aa-20 in submerged culture and solid-state culture was evaluated using different concentrations of tannic acid as sole carbon
source in a model system designed for tannase production. Protease production was found to be dependent on the culture system
used (submerged culture or solid-state culture) and on the initial tannic acid concentration. Expression of protease activity
in submerged culture was higher (up to 10 times) than activity obtained in solid-state culture, using identical culture medium
composition. In submerged culture, the lowest final protease activity (0.13 IU) was obtained with the highest tannic acid
concentration, while in solid-state culture protease activity was not affected by changes in initial substrate concentration.
Absence of detectable proteolytic activity in solid-state culture is related to high production of tannase enzyme. Hence,
the use of solid-state culture for fungal enzyme production may allow for higher and more stable enzyme titers present in
culture extracts. 相似文献
127.
128.
Atmospheric pressure ionization has been used to great effect by mass spectrometrists in widely diverse fields. The aim of this brief review is to set down the advantages of API/MS to fundamental and analytical chemists alike through discussion of the basic processes of ionisation and through its application. 相似文献
129.
John M. Kane Christopher R. Dalton Michael A. Staeger Edward W. Huber 《Journal of heterocyclic chemistry》1995,32(1):183-187
Several 1,2,4-triazole derivatives containing a 2-fluorophenyl substituent at either the 3- or 5-position and a methyl group at the 4-position were synthesized. These derivatives exhibit long-range 19F-1H and 19F-13C through-space coupling in their 1H and 13C nmr spectra between the fluorine and the 4-methyl group. The close spatial proximity of these nuclei was confirmed by X-ray analysis and by fluorine irradiated proton observe ({19F}-1H) NOE difference spectroscopy. 相似文献
130.
Collman JP Kaplun M Sunderland CJ Boulatov R 《Journal of the American Chemical Society》2004,126(36):11166-11167
Electrocatalytic reduction of a series of chemical oxidants of different power (tert-butyl hydroperoxide, potassium peroxomonosulfate, peracetic acid, and m-chloroperbenzoic acid) at iron-porphyrin-modified graphite electrodes is studied in buffered aqueous solutions by rotating disk and ring-disk voltammetry. Both ferric and ferrous porphyrins are catalytically active. Turnover of ferric catalysts is slower than that of the ferrous analogues and involves competing catalytic reduction and disproportionation. The kinetic data are consistent with reactant binding being the rate-determining step in catalysis by Fe(III). In catalysis by Fe(II), the turnover is controlled by the first electron transfer. The covalently linked proximal imidazole ligand is found to be crucial for achieving the Fe(III) catalysis. 相似文献