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121.
《Electroanalysis》2006,18(4):391-398
The first study of the voltammetric reduction of cyclooctatetraene (COT) in tetrahydrofuran (THF) in the presence of lithium ion is reported. A single wave is observed at ?2.23 V vs. Ag/0.1 M AgNO3. Density functional calculations have been carried out on a variety of COT/Li/THF species in order to clarify the nature and role of ion pairing in this system. The dominant species in solution are the COT/Li/(THF)2 anion radical and the COT/Li2/(THF)4 dianion. Computer simulations have been carried out to further understand the effects of ion pairing on the reduction. The simulations show that coalescence of two waves into one can occur in the presence of strong ion pairing even when the second reduction potential is negative of the first. 相似文献
122.
Silver(I)‐Selective PVC Membrane Potentiometric Sensor Based on a Recently Synthesized Calix[4]arene
《Electroanalysis》2006,18(10):1019-1027
A new PVC membrane potentiometric sensor for Ag(I) ion based on a recently synthesized calix[4]arene compound of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dihydroxy‐calix[4]arene‐thiacrown‐4 is developed. The electrode exhibits a Nernstian response for Ag(I) ions over a wide concentration range (1.0×10?2?1.0×10?6 M) with a slope of 53.8±1.6 mV per decade. It has a relatively fast response time (5–10 s) and can be used for at least 2 months without any considerable divergence in potentials. The proposed electrode shows high selectivity towards Ag+ ions over Pb2+, Cd2+, Co2+, Zn2+, Cu2+, Ni2+, Sr2+, Mg2+, Ca2+, Li+, K+, Na+, NH4+ ions and can be used in a pH range of 2–6. Only interference of Hg2+ is found. It is successfully used as an indicator electrode in potentiometric titration of a mixture of chloride, bromide and iodide ions. 相似文献
123.
Analysis of selected ionic liquid cations by ion exchange chromatography and reversed-phase high performance liquid chromatography 总被引:1,自引:0,他引:1
The chromatographic behavior of 8 ionic liquids - 7 homologues of 1-alkyl-3-methylimidazolium and 4-methyl-N-butylpyridinium - has been investigated with a strong cation exchange adsorbent. In particular, the dependence of the retention properties of these solutes on mobile phase composition, pH, and buffer concentration was evaluated with the aim of optimizing and improving the selectivity and retention of solute separation. While using the SCX stationary phase, several interactions occurred with varying strengths, depending on the mobile phase composition. Cation exchange, nonspecific hydrophobic interactions, and adsorption chromatography behavior were observed. Reversed phase chromatography occurred at low concentrations of acetonitrile, electrostatic and adsorption interactions at higher organic modifier concentrations. Elevated buffer concentrations lowered the retention factors without affecting the selectivity of ionic liquids. Obtained results were further compared to the chromatographic behaviour of ionic liquids in the reversed phase system. All analyzed ionic liquids follow reversed-phase behavior while being separated. Much lower selectivity in the range of highly hydrophilic compounds is obtained. This suggests preferred use of ion chromatography for separation and analysis of compounds below 4 carbon atoms in the alkyl side chain. 相似文献
124.
Summary A pure silica gel (Pia Seed 5S-60-SIL), synthesized by the hydrolysis of pure tetraethoxysilane [Si(OCH2CH3)4], was applied as a cation-exchange stationary phase in ion chromatography with indirect photometric detection for common
mono-and divalent cations (Li+, Na+, NH4
+, K+, Mg2+, and Ca2+) using various protonated aromatic monoamines (tyramine [4-(2-aminethyl) phenol], benzylamine, phenylethylamine, 2-methylpyridine
and 2,6-dimethylpyridine) as eluet ions. When using 0.75 mM tyramine-0.25 mM oxalic acid-1.5 mM 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane)
at pH 5.0 as the eluent, excellent simultaneous separation and highly sensitive detection at 275 nm for these mono-and divalent
cations were achieved on the Pia Seed 5S-60-SIL column (150×4.6 mm I.D.) in 20 min. 相似文献
125.
W.Franklin Smyth Clare Joyce Venkataraman N. Ramachandran Edmund O’Kane Danny Coulter 《Analytica chimica acta》2004,506(2):203-214
The electrospray ionisation-ion trap mass spectrometry (ESI-MSn) of selected hypnotic drugs, i.e. zopiclone, zolpidem, flunitrazepam and their metabolites have been investigated. Sequential product ion fragmentation experiments (MSn) have been performed in order to elucidate the degradation pathways for the [M+H]+ ions and their predominant fragment ions. These MSn experiments show certain characteristic fragmentations in that functional groups are generally cleaved from the ring systems as neutral molecules such as H2O, CO, CO2, NO2, amines and HF. When an aromatic entity is present in a drug molecule together with a nitrogen-containing saturated ring structure as with zopiclone and its N-desmethyl metabolite fragmentation initially occurs at the latter ring with the former being resistant to fragmentation. The structures of fragment ions proposed for ESI-MSn can be supported by electrospray ionisation-quadrupole time-of-flight mass spectrometry (ESI-QTOF-MS).These molecules can be identified and determined in mixtures at low ng/ml concentrations by the application of liquid chromatography (LC)-ESI-MSn which can be used for their analysis in saliva samples.This paper includes a tabulation of mass losses/signals at low m/z values for these hypnotic drugs and many others in recent publications which will be of value in the characterisation of drug metabolites of unknown structure and also natural product pharmaceuticals isolated from plants, etc. 相似文献
126.
Determination of trichothecenes in cereals by gas chromatography with ion trap detection 总被引:1,自引:0,他引:1
Summary A method for determination of the trichothecene toxins, deoxynivalenol, 3α-acetyl-deoxynivalenol, nivalenol, T-2 toxin, HT-2
toxin and diacetoxyscirpenol in cereals (wheat, barley, oats, corn) is described. Extraction was performed according to Tanaka
et al. (J. Chromatogr.328, 271 (1985)) [33], derivatization by trifluoroacylation with trifluoroacetic acid anhydride. For quantitation and confirmation
a capillary gas chromatograph combined with a selective mass detector (ion trap) working in CI-mode with methanol as reagent
gas was used. The quantitation limit for the complete method is 1–5 μg/kg, depending on the chemical characteristics of each
toxin and cleanness of the extracts. Recoverics from spiked cereals were 78–89%. 相似文献
127.
Ion association in the system Ca(OH)2–H3PO4–KCl–H2O at 37°C has been studied potentiometrically over a range of pH from 3 to 9. The experimental conditions were optimized for the accurate determination of the association constants for the formation of the ion pairs CaH2PO
4
+
, CaHPO4 and CaPO
4
–
which were found to be 27.9±0.1, 591±2, and (1.35±0.02)×106 L-mol–1, respectively. 相似文献
128.
Fe(CN)4?6, Cu(CN)3?4, Co(CN)3?6, Fe(CN)3?6, Ni(CN)2?4 and Cr(CN)3?6 are determined by ion-interaction chromatography using a C18 column and methanol-tetrahydrofuran-10 mM phosphate buffer (pH 7.9) (25 + 1 + 74, v/v/v) containing 5 mM tetrabutylammonium hydroxide as mobile phase, with spectrophotometric detection at 214 nm. Detection limits are in the range 0.01–0.5 mg 1?1. In an alternative approach, an automated on-line sample preconcentration technique is used wherein a 2-ml volume of sample containing metallo-cyanides is loaded onto a C18 precolumn which has been equilibrated with the above mobile phase. The bound solutes are then eluted from the precolumn to a C18 analytical column where they are separated using the same mobile phase as employed to equilibrate the precolumn. Detection limits are in the rate 0.08–1.58 μg 1?1 and calibration graphs are linear up to 200 μg 1?1. The preconcentration step is shown to give quantitative recoveries for all species except Fe(CN)4?6 and (CN)3?4. The iron(II) complex does not bind quantitatively to the precolumn, and extensive studies with the copper complex suggested that low recoveries were due to dissociation and ligand-exchange reactions occurring during the chromatographic separation process. Negative interference effects were observed for Cl? and SO2?4 when present at a level of 250 mg 11?, and UV-absorbing anions such as Br?, SCN?, NO?2 and NO?3 caused positive interference when present at concentrations as low as 1 mg 1?1. The negative interferences could be reduced by diluting the sample and the positive interferences could be eliminated by incorporating an additional step in the preconcentration process, in which UV-absorbing anions bound to the precolumn after sample loading were eluted selectively using an eluent consisting of 10 mM NaCl in phosphate buffer (pH 6.7). 相似文献
129.
This study examines the reagent gas pressure and ion source temperature dependence for dimethyl ether chemical ionization (DME CI) mass spectra recorded with an external source ion trap mass spectrometer (ITMS). Information for better controls of the reagent gas pressure in order to obtain fair CI spectra is provided. The origin of M+? ions observed in DME CIMS is discussed in detail. Furthermore, the ion source temperature effect on the DME CI is also investigated. 相似文献
130.
A study of the mechanisms involved in the separation of metal ions with a mixed-bed stationary phase
Summary The optimization of chromatographic methods for the determination of metal species require an understanding of the mechanisms
involved. In this work, the separation of Cd, Co, Cu, Fe(II/III), Mn, Pb and Zn using a mixed bed column (IonPac CS5A) and
a cation-exchange column (IonPac CS2) is studied as a function of mobile phase composition. The type and concentration of
complexing agent and of ionic strength modificators were evaluated. The charge of analytes were calculated using the classical
ion exchange approach to highlight the effect of eluent composition on retention. The comparative study enabled us to identify
an optimal eluent composition for the separation of the nine metal species. 相似文献