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41.
Synthesis and Properties of Di-molybdenum-μ-nitrido-heptachloride, Mo2NCl7 Mo2NCl7 was prepared by the reaction of molybdenum pentachloride with the bromide of Millon's base, [Hg2N]Br, in boiling CCl4. It forms a moisture sensitive, dark green crystal powder, the magnetic moment at 20°C (μeff = 0.95 B.M.) being strongly reduced. With acetonitrile the μ-nitrido complex Mo2NCl7 · 3CH3CN is formed, with phosphoryl chloride the donor acceptor complex Mo2NCl7 · 2POCl3, respectively. Partial oxidation of the latter complex with chlorine leads to very unstable Mo2NCl8 · 2POCl3, from which (PPh4)3[Mo3NCl10] can be obtained by the reaction with PPh4Cl. For the complex (PPh4)3[Mo2NCl10] is also found a reduced paramagnetism of μeff = 1.47 B.M. at 20°C. All complexes are characterized by i.r. spectroscopy. 相似文献
42.
The basic obstacles for the general use of laser-ablation(LA)-ICP-MS in analytical laboratories are connected with its reproducibility and calibration. A mathematical relation deduced from the correlation function of the analytical signals allows the estimation of the number of craters needed for representative analyses. The procedure was applied to different samples such as manganese crusts and soils. The ion intensities of the major elements in the manganese crusts and nodules were used as internal standards, improving relative standard deviations by factors between 2 and 3. Selected samples of wood and manganese crusts were analyzed by LA-ICP-MS and the results compared with those obtained by solution ICP-MS. The agreement of the values is within the 95% confidence limits. Powdered reference materials and, in the case of wood analysis, cellulose doped with standard solutions were used for the calibration. 相似文献
43.
Kurt Rüfenacht 《Helvetica chimica acta》1975,58(6):1521-1527
Aza-analogues of the known pesticidal dithiophosphates 2, 4 and 5 have been prepared by replacing the phthalimide, benzotriazole and 1,2,3-benzotriazin-4(3H)-one moieties resp. in 2 by those of quinolinic acid imide (6), cinchomeronic acid imide (7) and pyrazine-2,3-dicarboxylic acid imide (12), in 4 by 1H-v-triazolo[4,5-b]pyridine (15) and in 5 by pyrido[2,3-e]1,2,3-triazin-4(3H)-one (21). Compared to the known compounds the new esters are less or at best equally pesticidal with an equal or even higher mammalian toxicity. 相似文献
44.
45.
Depending on the N-protecting group of pyroglutamates, the reactivity can be directed to the formation of 6-azabicyclo[3.2.1]octanes or 4-azabicyclo[3.3.0]octanes, which are conformationally restricted glutamate analogues. 相似文献
46.
Kuno Wagner Kurt Findeisen Walter Schfer Werner Dietrich 《Angewandte Chemie (International ed. in English)》1981,20(10):819-830
Research in the field of low-molecular weight, oligomeric and polymeric α,ω-diisocyanatocarbodiimides and -polycarbodiimides has been fruitful, not only in connection with these compounds themselves, but also—as so often happens in chemistry—with quite different problems. Novel synthetic methods, discoveries concerning the properties of low-molecular weight carbodiimides and phosphane imide derivatives, as well as results on the fragmentation reactions of four-membered heterocyclic compounds containing oxygen, phosphorus, and nitrogen, and a better understanding of the diisocyanate polyaddition process are among the many by-products of this research. The “high- and low-temperature formation” of polycarbodiimides and the homogeneous and heterogeneous catalysis of this process are described, and the fundamental importance of four-membered ring fragmentation mechanisms resulting in the formation of phosphane imide derivatives is outlined. Interesting building blocks for the diisocyanate polyaddition and polycondensation processes can be synthesized by many derivatization reactions of oligomeric and high-molecular weight polycarbodiimides and polyuretonimines. The in situ production of polycarbodiimides via matrix reactions in flexible polyurethane foams leads to a cellular arrangement of the material due to the pronounced symmetrical growth processes. Combination-foams with increased carbonation tendencies are formed in this way. Attention is drawn to several industrial applications of α,ω-diisocyanatopolycarbodiimides, of high-molecular weight cross-linked polyuretonimines, and of polycarbodiimide foams. 相似文献
47.
[(Mes3Sn)2MoO4], a Monomeric Triorganotin Molybdate Mes3SnBr (Mes = 1, 3, 5‐trimethylphenyl) reacts with (NBu4)2[Mo6O19] in the presence of (NBu4)OH (in CH3CN as solvent) to form [(Mes3Sn)2MoO4]. Alternatively the title compound can be obtained from the reaction of [MoO2(acac)2] (acac = 2, 4‐pentadionate) with Mes3SnOH in isopropanol. [(Mes3Sn)2MoO4] forms monoclinic crystals, space group C2/c, with a = 2271.6(3) pm, b = 825.2(1) pm, c = 2739.9(5) pm, β = 90.96(2)°. The crystal structure consists of isolated molecules in which a tetrahedral MoO4 unit is connected to two terminal Mes3Sn groups. The Mo‐O distances range from 169.6(4) to 181.1(3) pm and the Sn‐O distance is 204.8(3) pm. 相似文献
48.
N(SCl)2⊕ [MoCl5(NSCl)]?, a Chlorothionitrene Complex of Molybdenum (VI) . The title compound is formed together with MoCl3(N3S2) by the reaction of MoCl4 or MoCl5 with (NSCl)3 in CH2Cl2. The black, crystalline compound was characterized by its i.r. spectrum and an X-ray crystal structure determination. N(SCl)2⊕[MoCl5(NSCl)]? crystallizes in the monoclinic space group P21/n with four formula units per unit cell. The lattice constants are a = 716.3, b = 1627.4, c = 1178.9 pm and β = 100.90°. The [MoCl5(NSCl)]? ion posseses an almost linear Mo = N = S grouping with bond lengths that can be interpreted as double bonds. Crystal data for AsPh4[MoCl5(NSCl)] are reported. 相似文献
49.
A new synthetic route for the preparation of the betain-like compound (CH3N)6P4F8 from (CH3NPF3)2,N-methyl-hexamethyldisilazane andN,N-dimethyl-urea has been found. The steps of this multi-stage reaction could be rationalized to a far extent.
10. Mitteilung:Kubjacek M., Utvary K., Mh. Chem.112, 305 (1981). 相似文献
50.
A series of enantiomerically pure 8-oxabicyclo[3.2.1]oct-6-en-3-ones functionalized in the unsaturated two-carbon bridge has been prepared by the title reaction. Carbocation reactivity has been fined-tuned at -95 degrees C and adjusted to diene nucleophilicity. Conventional electrophilic substitution of 3-silylated and 3-stannylated furan is suppressed in favor of the rapid 4 + 3 cycloaddition mode. In the case of cycloadduct 13A, stereoselectivity (17:1) is perfectly matched to regioselectivity (17:1). High stereoselection as well as unprecedented regioselection and chemoselection is attributed to the low-temperature cycloaddition protocol and the design of chiral auxiliary and tether. 相似文献