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21.
The chain conformation and molecular packing of isotactic poly(p-fluorostyrene) have been examined using calculations made with semiempirical potential energy functions. Isolated chain conformational energies indicate no difference in conformation for the fluoropolymer from the conformation for isotactic polystyrene. The energy for packing poly(p-fluorostyrene) chains into a crystalline array as 31 or 41 helices was also compared with the energies for packing polystyrene in both of these helical forms. While not being the lowest energy mode of packing for poly(p-fluorostyrene), the packing of 41-helices does yield a local energy minimum. Such packing of 41 helical polystrene chains is considerably less energetically feasible. The results indicate the causes for the experimentally observed difference in the crystalline conformations of the two isotactic polymers as being due to intermolecular influences. 相似文献
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The reaction of NO-Fe(TPP) with low pressures of NO gas proceeds through three distinct transformations, the first of which we suggest is the formation of an N--N-coupled, (NO)(2) adduct intermediate. The subsequent formation of NO(NO(2))Fe(TPP), which under these conditions readily loses NO, suggests that it is formed by addition of free NO(2) to the starting nitrosyl. A mechanism is proposed which implies that the addition of a competitive O atom acceptor would lead to catalytic production of N(2)O. In agreement with the proposed mechanism, the formation of N(2)O is decoupled from the formation of the nitrite by using PPh(3) as the competitive acceptor. The mechanism of O atom transfer was examined by cross-labeling experiments, which show that both O atoms in the intermediate are equivalent, even under catalytic conditions. The formation of an intermediate was confirmed by IR spectroscopy of the heterogeneous reaction of an NO-Fe(TPP) film with gaseous NO, in which transient, isotope-sensitive nu(NO) bands are seen prior to NO(NO(2))Fe(TPP) formation. Mixed (14)N/(15)N label experiments demonstrate coupling between the two bound nitrosyls in the transient species. 相似文献
24.
E Bailey P B Farmer J A Peal S A Hotchkiss J Caldwell 《Journal of chromatography. A》1987,416(1):81-89
A method is described for the simultaneous determination of [1,3-15N] theophylline and unlabelled theophylline in human plasma using gas chromatography-mass spectrometry. Plasma samples were subjected to extractive alkylation and the stable isotopically labelled and unlabelled forms of the drug were analysed as their N-pentafluorobenzyl derivatives on an SE-52 fused-silica capillary column. Quantitation was made by selected-ion monitoring employing as the internal standard 3-isobutyl-1-methylxanthine. The method has been used to study the absorption kinetics and bioavailability of a sustained release formulation of the drug when co-administered to human volunteers with a conventional formulation of the drug labelled with the stable isotope. 相似文献
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26.
A substantial quantity of experimental data on rewetting, much of which has not been previously reported, is analysed using the results of calculations of the two-dimensional conduction processes taking place in the walls of tubes, which have been used to simulate the cladding of nuclear fuel elements. Correlations giving the quenching heat-transfer coefficient and sputtering temperature are proposed as a result of the analysis. These correlations may be combined with the previously reported conduction analysis to predict rewetting rates under a wide range of conditions. The new data include falling film rewetting rates measured for a range of system pressures (1–15 bars), initial wall temperatures (200–650°C), coolant mass flowrates (3–50 g sec?1) and subcoolings (0–90°C). Measurements have also been made of rewetting rates by bottom flooding of both saturated and subcooled water at atmospheric pressure. 相似文献
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28.
Sharp JS Farmer DJ Kelly J 《Langmuir : the ACS journal of surfaces and colloids》2011,27(15):9367-9371
The resonant vibrations of small (microliter) sessile water droplets supported on solid substrates were monitored using a simple optical detection technique. A small puff of air was used to apply an impulse to the droplets and their time dependent oscillations were monitored by passing a laser beam through the droplet and measuring the variations of the intensity of the scattered light using a simple photodiode arrangement. The resulting time dependent intensity changes were then Fourier transformed to obtain information about the vibrational frequencies of the droplets. The resonant frequencies of droplets with masses in the range 0.005-0.03 g were obtained on surfaces with water contact angles ranging from 12 ± 4° to 160 ± 5°. The contact angle dependence of the resonant frequency of the droplets was found to be in good agreement with a simple theory which considers standing wave states along the meridian profile length of the droplets. 相似文献
29.
Potassium cyanide was used as a model toxicant to determine the feasibility of using anionic impurities as a forensic signature for matching cyanide salts back to their source. In this study, portions of eight KCN stocks originating from four countries were separately dissolved in water and analyzed by high performance ion chromatography (HPIC) using an anion exchange column and conductivity detection. Sixty KCN aqueous samples were produced from the eight stocks and analyzed for 11 anionic impurities. Hierarchal cluster analysis and principal component analysis were used to demonstrate that KCN samples cluster according to source based on the concentrations of their anionic impurities. The Fisher-ratio method and degree-of-class separation (DCS) were used for feature selection on a training set of KCN samples in order to optimize sample clustering. The optimal subset of anions needed for sample classification was determined to be sulfate, oxalate, phosphate, and an unknown anion named unk5. Using K-nearest neighbors (KNN) and the optimal subset of anions, KCN test samples from different KCN stocks were correctly determined to be manufactured in the United States. In addition, KCN samples from stocks manufactured in Belgium, Germany, and the Czech Republic were all correctly matched back to their original stocks because each stock had a unique anionic impurity profile. The application of the Fisher-ratio method and DCS for feature selection improved the accuracy and confidence of sample classification by KNN. 相似文献
30.
Kim SN Kuang Z Slocik JM Jones SE Cui Y Farmer BL McAlpine MC Naik RR 《Journal of the American Chemical Society》2011,133(37):14480-14483
Peptides identified from combinatorial peptide libraries have been shown to bind to a variety of abiotic surfaces. Biotic-abiotic interactions can be exploited to create hybrid materials with interesting electronic, optical, or catalytic properties. Here we show that peptides identified from a combinatorial phage display peptide library assemble preferentially to the edge or planar surface of graphene and can affect the electronic properties of graphene. Molecular dynamics simulations and experiments provide insight into the mechanism of peptide binding to the graphene edge. 相似文献