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11.
12.
Matsumoto T Kamada Y Sugimoto T Tada T Noguchi S Nakazumi H Shiro M Yoshino H Murata K 《Inorganic chemistry》2003,42(17):5192-5201
Two donor molecules newly synthesized, dimethylthio- and ethylenedithio-tetrathiafulvalenothioquinone-1,3-diselenolemethides (1 and 2), were used to prepare their charge-transfer (CT) salts with a magnetic FeBr(4)(-) counteranion. For 1, a low electrical conducting 1:1 salt (1.FeBr(4)) was obtained, in which molecules of 1 are tightly dimerized in a one-dimensional (1D) stacking column. On the other hand, 2 gave a 2:1 salt (2(2).FeBr(4)) as two different kinds of plate crystals (I and II). Both I and II possess similar stacking structures of molecules of 2 in each 1D column with a half-cut pipelike structure along the c axis. However, for I, the stacking columns are aligned in the same direction along the a and b axes, while for II they are in the same direction along the a axis, but in the reverse direction along the b axis, resulting in the difference in the relative arrangement of molecules of 2 and FeBr(4)(-) ions between the two crystals. The room-temperature electrical conductivities of the single crystals of I and II were 13.6 and 12.7 S cm(-)(1), respectively. The electrical conducting behavior in I was metallic above 170 K but changed to be semiconducting with a very small activation energy of 7.0 meV in the temperature range 4-170 K. In contrast, II showed the semiconducting behavior in the whole temperature range 77-285 K. The corresponding nonmagnetic GaBr(4)(-) salts with almost the same crystal structure as I and II showed definitively different electrical conducting properties in the metal to semiconductor transition temperature in I as well as in the magnitude of activation energy in the semiconducting region of I and II. The interaction between the d spins of FeBr(4)(-) ions was weak and antiferromagnetic in both I and II, but the magnitude of the spin interaction was unexpectedly larger compared with that in the FeBr(4)(-) salt of the corresponding sulfur derivative of 2 with closer contact between the neighboring FeBr(4)(-) ions. These electrical conducting and magnetic results suggest a significant interaction between the conducting pi electrons and the d spins of FeBr(4)(-) ions located near the columns or layers. 相似文献
13.
Third-order nonlinear optical properties of a disazo dye attached polymer (3R) were evaluated and compared with that of a monoazo (Disperse Red 1) dye attached polymer (2R). The third-order nonlinear optical coefficient (ξ(3)) of the 3R is more than three times higher than that of the 2R over the fundamental wavelengths between 1.5 and 2.0 μm. This is explained by π-conjugation elongation. For both polymers, the ξ(3) dependence on the fundamental wavelength corresponds to their absorption spectra. This is attributable to a three-photon resonance effect. At the 1.50 μm resonant wavelength, the maximum ξ(3) of 4.8 × 10-11 esu is obtained for 3R at a dye content of 17 mol%. 相似文献
14.
Jadranka Vuković Shiro Matsuoka Kazuhisa Yoshimura Vladimir Grdinić Renata Jurišić Grubešić 《Mikrochimica acta》2007,159(3-4):277-285
A simple, sensitive and rapid solid-phase spectrophotometric procedure was developed for the determination of traces of phenol
with 4-aminoantipyrine as a reagent (AAP-SPS), and the optimal experimental conditions were established. This method was performed by sorption and direct absorbance measurements
of the product phenol-AAP sorbed on the anion-exchanger Dowex 1-X4 (0.2 g) at 495 nm (absorption maximum) and 700 nm (non-absorption wavelength). The
sensitivity offered by the AAP-SPS procedure was higher by a factor of 40 compared with the respective conventional spectrophotometric method. Metrological
characteristics were established using a prevalidation strategy. The AAP-SPS procedure is characterized by a linear calibration function in the working range of 0.05–0.50 μmol, low standard deviation
of procedure (±0.012), low limit of determination (0.021 μmol), and favorable random (±0.85 to ±11.27%) and systematic deviations
(−4.55 to +11.50%). Moreover, the accuracy of the system investigated by the recovery test is acceptable (99–102%). Favorable
working and performance characteristics make the new SPS method ideal for phenol monitoring in pharmaceutical preparations
as well as other matrices. 相似文献
15.
Tamura O Shiro T Ogasawara M Toyao A Ishibashi H 《The Journal of organic chemistry》2005,70(12):4569-4577
The 4-hydroxy 4-substituted glutamic acid moiety is a common substructure of biologically important natural products such as monatin [(2S,4S)-2], lycoperdic acid (3), and dysiherbaine (4). To develop methodology for syntheses of these natural products, cycloadditions of nitrone 5 with 2-substituted 2-propen-1-ols 6 and 2-substituted acrylates 8 were investigated. Reactions of nitrone 5 with alcohols 6 in the presence of MgBr2OEt2 gave cycloadducts 7 in a highly stereoselective manner, whereas noncatalyzed reactions of 5 with acrylates 8 afforded adducts 9. Using the former reaction, syntheses of monatin [(2S,4S)-2], monatin derivative 18, and lycoperdic acid (3) were accomplished. The C4-epimer of monatin [(2S,4R)-2)] was also synthesized by employing the latter cycloaddition. 相似文献
16.
Yoshiyasu Ichikawa Yohei Matsukawa Mari Tamura Fumiyo Ohara Minoru Isobe Hiyoshizo Kotsuki 《化学:亚洲杂志》2006,1(5):717-723
A new method for the synthesis of urea‐linked disaccharides in aqueous media has been developed. The key feature of our approach is two strained Steyermark‐type gluco‐ and galactopyranosyl oxazolidinones. Each oxazolidinone is attached to a pyranose ring in a di‐equatorial trans‐annulation framework. Reaction of these oxazolidinones with 4‐aminohexopyranose in water proceeded smoothly to afford the urea‐tethered cellobiose and lactose analogues. The galactose‐type oxazolidinone proved to be more reactive than the glucose‐type, which is explained by the presence of an axial hydroxy group at C4 in the former. 相似文献
17.
Chemical conversion of various celluloses to glucose and its derivatives in supercritical water 总被引:16,自引:0,他引:16
The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105s) under the conditions of a tin bath temperature of 500°C and pressure of 35MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10s supercritical treatment, while that from starch for 3–5s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques. 相似文献
18.
Some organogermanium oligomers with different side groups were synthesized via li-gand substitution polymerization from 1, 4-dioxane complex of germanium dichloride withdifferent organolithitum compounds. The oligomers were isolated through either precipi-tation from methanol or extraction using toluene with a yield of no less than 50%. Theweiglit average molecular weight (M_w) of the oligomers is ranging from 1.4×10~3 to 5.9×10~3depending on the type and alkyl length of the organolithium compounds used. 相似文献
19.
20.
Two-step preparation for catalyst-free biodiesel fuel production 总被引:10,自引:0,他引:10
Biodiesel fuel was prepared by a two-step reaction: hydrolysis and methyl esterification. Hydrolysis was carried out at a
subcritical state of water to obtain fatty acids from triglycerides of rapeseed oil, while the methyl esterification of the
hydrolyzed products of triglycerides was treated near the supercritical methanol condition to achieve fatty acid methyl esters.
Consequently, the two-step preparation was found to convert rapessed oil to fatty acid methyl esters in considerably shorter
reaction time and milder reaction condition than the direct supercritical methanol treatment. The optimum reaction condition
in this two-step preparation was 270°C and 20 min for hydrolysis and methyl esterification, respectively. Variables affecting
the yields in hydrolysis and methyl esterification are discussed. 相似文献