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31.
The determination of fluoridation rate provides a relatively inexpensive time-average surveillance method for monitoring atmospheric fluorides in specific areas. The fluoride is collected by the reaction with calcium oxide coating on a filter paper strip during the exposure of the candle to ambient air. The collected fluorides are then extracted from the exposed filter paper into a buffer solution and subsequently determined by ion selective electrode. 相似文献
32.
Wong CY Che CM Chan MC Han J Leung KH Phillips DL Wong KY Zhu N 《Journal of the American Chemical Society》2005,127(40):13997-14007
The synthesis and spectroscopic properties of trans-[RuL4(C[triple bond]CAr)2] (L4 = two 1,2-bis(dimethylphosphino)ethane, (dmpe)2; 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane, 16-TMC; 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane, N2O2) are described. Investigations into the effects of varying the [RuL4] core, acetylide ligands, and acetylide chain length for the [(-)C[triple bond]C(C6H4C[triple bond]C)(n-1)Ph] and [(-)C[triple bond]C(C6H4)(n-1)Ph] (n = 1-3) series upon the electronic and electrochemical characteristics of trans-[RuL4(C[triple bond]CAr)2](0/+) are presented. DFT and TD-DFT calculations have been performed on trans-[Ru(L')4(C[triple bond]CAr)2](0/+) (L' = PH3 and NH3) to examine the metal-acetylide pi-interaction and the nature of the associated electronic transition(s). It was observed that (1) the relationship between the transition energy and 1/n for trans-[Ru(dmpe)2{C[triple bond]C(C6H4C[triple bond]C)(n-1)Ph}2] (n = 1-3) is linear, and (2) the sum of the d(pi)(Ru(II)) --> pi*(C[triple bond]CAr) MLCT energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2] and the pi(C[triple bond]CAr) --> d(pi)(Ru(III)) LMCT energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2]+ corresponds to the intraligand pi pi* absorption energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2]. The crystal structure of trans-[Ru(dmpe)2{C[triple bond]C(C6H4C[triple bond]C)2Ph}2] shows that the two edges of the molecule are separated by 41.7 A. The electrochemical and spectroscopic properties of these complexes can be systematically tuned by modifying L4 and Ar to give E(1/2) values for oxidation of trans-[RuL4(C[triple bond]CAr)2] that span over 870 mV and lambda(max) values of trans-[RuL4(C[triple bond]CAr)2] that range from 19,230 to 31,750 cm(-1). The overall experimental findings suggest that the pi-back-bonding interaction in trans-[RuL4(C[triple bond]CAr)2] is weak and the [RuL4] moiety in these molecules may be considered to be playing a "dopant" role in a linear rigid pi-conjugated rod. 相似文献
33.
Assay of free ferulic acid and total ferulic acid for quality assessment of Angelica sinensis 总被引:4,自引:0,他引:4
Activity of Chinese Danggui (DG), the processed root of Angelica sinensis (Oliv.) Diels, is linked to the ferulic acid content but the stability of ferulic acid during extraction for medicinal use is not known. The stabilities of ferulic acid and coniferyl ferulate were evaluated in the extracts of DG using a variety of extraction solvents. These included various combinations and proportions of methanol, water, formic acid, 1 M aqueous hydrochloric acid and 2% sodium hydrogen carbonate (NaHCO3) in water. Coniferyl ferulate was found liable to hydrolyze into ferulic acid in neutral, strongly acidic and basic solvents, where heat and water could facilitate this hydrolysis. However, the hydrolysis was relatively resisted in weakly organic acid. Based on the stability evaluation, two new terms, namely: free ferulic acid and total ferulic acid, were suggested and defined. Free ferulic acid refers to the natural content of ferulic acid in herbs. Total ferulic acid means the sum of free ferulic acid plus the amount of related hydrolyzed components. Meanwhile, the high-performance liquid chromatographic (HPLC) method was developed to assay free ferulic acid and total ferulic acid in DG using methanol-formic acid (95:5) and methanol-2% NaHCO3 in water (95:5) as extraction solvents, respectively. Ten DG samples were investigated on their contents of free and total ferulic acid. The results indicated that the amount variety of free ferulic acid was larger than that of their counterparts, and the ratio of total ferulic acid to free ferulic acid was 4.07 +/- 2.73 (mean +/- SD, n = 10). The chemical assay of DG using total ferulic acid content would be a better choice to assess the herbal quality and was recommended. 相似文献
34.
New methods are suggested for the determination of the charge density of acrylamide/acrylate copolymers.13C nuclear magnetic resonance spectroscopy was used to determine the comonomer ratio by comparing the peak intensities of the methine carbon in acrylamide and acrylate monomers. Results were compared with those obtained by conductometric and potentiometric titration and were found to be in good agreement. Differential scanning calorimetry was employed to determine the glass transition temperatures (T
g) of the copolymers. A master curve was established by plottingT
g versus charge density of the copolymers previously determined by NMR and conductometric titration. Compositions of poly(acrylamide-co-acrylate) samples can thus be determined by measuring theT
g and reading the percent composition directly from the master curve. 相似文献
35.
Samuel C. Perry Pui-ki Leung Ling Wang Carlos Ponce de León 《Current Opinion in Electrochemistry》2020
CO2 reduction processes continue to be developed for electrosynthesis, energy storage applications, and environmental remediation. A number of promising materials have shown high activity and selectivity to target reduction products. However, the progress has been mainly at a small laboratory scale, and the technical challenges of large scale CO2 reduction have not been considered adequately. This review covers recent advancements in catalyst materials and cell designs. The leading materials for CO2 reduction to a number of useful products are presented with their corresponding cell and reactor designs. The latest efforts to progress to industrially relevant scales are discussed, along with the challenges that must be met for carbon dioxide reduction to be a viable route for mass scale production. 相似文献
36.
The microwave spectra of six isotopomers of HCl-N(2)O have been obtained in the 7-19 GHz region with a pulsed molecular beam, Fourier transform microwave spectrometer. The nuclear quadrupole hyperfine structure due to all quadrupolar nuclei is resolved and the spectra are analyzed using the Watson S-reduced Hamiltonian with the inclusion of nuclear quadrupole coupling interactions. The spectroscopic constants determined include rotational constants, quartic and sextic centrifugal distortion constants, and nuclear quadrupole coupling constants for each quadrupolar nucleus. Due to correlations of the structural parameters, the effective structure of the complex cannot be obtained by fitting to the spectroscopic constants of the six isotopomers. Instead, the parameters for each isotopomer are calculated from the A and C rotational constants and the chlorine nuclear quadrupole coupling constant along the a-axis, chi(aa). There are two possible structures; the one in which hydrogen of HCl interacts with the more electronegative oxygen of N(2)O is taken to represent the complex. The two subunits are approximately slipped parallel. For H (35)Cl-(14)N(2)O, the distance between the central nitrogen and chlorine is 3.5153 A and the N(2)O and HCl subunits form angles of 72.30 degrees and 119.44 degrees with this N-Cl axis, respectively. The chlorine and oxygen atoms occupy the opposite, obtuse vertices of the quadrilateral formed by O, central N, Cl, and H. Nuclear quadrupole coupling constants show that while the electric field gradient of the HCl subunit remains essentially unchanged upon complexation, there is electronic rearrangement about the two nitrogen nuclei in N(2)O. 相似文献
37.
Summary High molecular weight poly 2- and 4-vinyl pyridines were synthesized by ionic polymerisation and their flocculation efficiency tested against kaolin and silica dispersions at pH 3. Low additions of the polymers, around 3 parts per 103 parts solid, destabilize the dispersions and clarify silica dispersions to a remarkable extent; however, over-addition of polymer leads to partial restabilization. The flocculation efficiency improves with increase of solids content, especially with clay dispersions. Flocculation efficiency increases with polymer molecular weight, especially over the lower part of the range covered, but is relatively independent of pH in the range 2–4. Quaternization of poly(4-vinyl pyridine) with bromobutane produces a good flocculant for aqueous silica dispersions in which the degree of restabilization on over-dosing depends on the KCI content. TheN-oxide derivatives of the vinyl pyridine polymers do not affect the colloidal stability of silica dispersions. The observations are interpreted in terms of bridging flocculation by the cationic polymer molecules between anionic surface sites on the solid particles. 相似文献
38.
In a continuing effort to predict the physicochemical properties of seawater from the properties of single aqueous electrolyte solutions, the pairwise heats of mixing at constant molal ionic strength,I=1.0 ional, have been determined for the six possible pairs of salts from the set (NaCl, Na2SO4, MgCl2, MgSO4) at 30°C. In addition, heats of dilution for two aqueous solutions formed from these salts and havingI=1.0 ional have been determined at 30°C. In order to present the most thermodynamically consistent results, it was found necessary to apply a correction term to the relative apparent equivalent enthalpies given in the literature at 30°C. These correction terms derived from a consideration of published results on heats of dilution at very low concentrations. Further, in order to make predictions for seawater at 25°C, it was deemed desirable to refit existing heat-capacity data. The heats relative apparent equivalent enthalpies for the two mixtures mentioned as well as for seawater. The estimates are based on the theoretical equation of Reilly and Wood for charge-asymmetric mixtures which derives from the work of Friedman. In the most applicable cases, the estimates agree with experimental relative apparent equivalent enthalpies to within 5%. In general, the results substantiate the theoretical equation.Taken in part from the Ph.D. dissertation of W. H. Leung, University of Miami, Miami, Florida 33149. 相似文献
39.
The enthalpies of dilution of lithium, sodium, potassium, and magnesium chloride and sulfate solutions in the range 0.1 to 1.0 m have been measured at 30°C with a microcalorimeter. The relative apparent enthalpies φL of these solutions have been determined with the aid of an extended form of the Debye-Hückel limiting law $$\phi _L = S_H I^{1/2} [1/(1 + I^{1/2} ) - (\sigma /3)] + {\rm B}{\rm I} + CI^{3/2} $$ whereS H is the limiting-law slope, σ = 3/I3/2 × [(1+I1/2 ? 1/(1+I1/2 ? 2 ln (2+I1/2)], andB andC are empirical constants. This equation fits the experimental results to within a standard deviation of 2 cal-mole?1 for all the salts. The measured φL for the MgSO4 solutions were compared to those calculated using the additivity principle, φL(MgCl2) + φL(Na2SO4) ? 2φL(NaCl), and the extended Debye-Hückel equation. The results of this comparison have been used to calculate the ΔH A o for the formation of MgSO 4 0 . A value of ΔH A o = 1.15 to 1.36 was obtained, depending upon the φL estimates for the free ions Mg2+ and SO 4 2? . The results are briefly discussed and compared to the results obtained by other workers. 相似文献
40.
Determination of in vitro permeability of drug candidates through a caco-2 cell monolayer by liquid chromatography/tandem mass spectrometry 总被引:6,自引:0,他引:6
Studying the permeability of compounds across a Caco-2 cell monolayer is an established in vitro model to screen for oral absorption and to evaluate the mechanism of transport. This assay can also be used to evaluate compounds as potential P-glycoprotein substrates and/or inhibitors. The traditional methods of sample analysis (high-performance liquid chromatography (HPLC) with a UV or fluorescence detector) limit the throughput and sensitivity of this assay. Data are presented here describing the use of liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the analysis of samples derived from the Caco-2 cell studies. During the analysis an automatic switching valve was used to divert the flow from the HPLC column to waste for the first minute, preventing the early eluting salts from entering and contaminating the LC/MS interface. This approach allows the rapid and accurate determination of drug transport across the Caco-2 cell monolayer. The high sensitivity and specificity of LC/MS/MS make this technique an ideal candidate for the low concentration and high throughput routine analysis of Caco-2 cell solutions, especially if multiple compounds are administered and analyzed simultaneously. Thus, the use of LC/MS/MS will increase the value of the Caco-2 cell assay as an in vitro screening tool. 相似文献