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91.
Robert E. Pratt William J. Welstead Robert E. Lutz 《Journal of heterocyclic chemistry》1970,7(5):1051-1055
Hydrazoic-sulfuric acid mixture converted cis-α-phenyl-β-benzoylchalcone (trans-dibenzoylstilbene, 4 ) into 2,3-diphenyl-4-benzoylquinoline ( 5 ) the structure of which was proved by debenzoylation to 2,3-diphenylquinoline. α,β-Diphenyl and cis-α,β-dibromochalcones similarly were converted respectively into 2,3,4-triphenylquinoline ( 19 ) and 2-phenyl-3,4-dibromoquinoline ( 20 ). The structure of 19 was shown by difference from the corresponding isoquinoline 21 (synthesized). Smith's mechanism for the analogous conversion of o-phenylbenzophenone into 9-phenylphenanthridine through the 9-fluorenol and the 9-hydroazide with loss of nitrogen and ring expansion, was supported by methyl label experiments using 2-(p-tolyl)benzophenone which gave a 53:47 mixture of 3- and 8-methyl-6-phenylphenanthridines. Applicability of the mechanism to the reactions with disubstituted cis-chalcones was shown by sulfuric acid conversions of two of these into indenol 22 and 2-bromo-3-phenylindenone ( 24 ), respectively. trans-Dibenzoylstilbene underwent resinification in sulfuric acid, giving the quinoline ( 5 ) only when hydrazoic acid was present. 相似文献
92.
Methane, mixed with argon, has been polymerized by means of a hollow-cathode discharge system. Two types of cathodes were studied; one was made of a solid solution of 81% tungsten and 19% platinum, while the other was of pure tungsten. Under identical operating conditions, a higher polymer yield was found in the case of the platinum cathode (90% against 70% for tungsten). The work function of the solid solution was estimated to be 6.3 eV, compared with 4.4 eV for tungsten. In terms of the data available, the thermionic current, which is the main source of energetic electrons, is about one order of magnitude lower for the solid solution cathode when compared with the tungsten cathode thermionic current. However, the polymer yield observed is higher in the former case. The concentration of the CH species in the hollow cathode was found to differ greatly for the cathodes tested and was about 5 times higher in the case of tungsten-platinum cathodes. Since no excited platinum vapor could be detected in the gas phase, the increase in CH concentration was attributed to a catalytic effect of the cathode inside surface. An evaluation of the plasma polymer deposition rate yields 70 nm·s–1 for the platinum-tungsten type hollow cathode and 42 nm·s–1 for the tungsten one. In both cases, the deposition rate is much higher than those obtained from the most widely used methods for plasma polymer deposition (0.10–1.0 nm·s–1) implying methane-argon mixtures, and is comparable to the results obtained with a new type of plasma polymer deposition reactor described in the literature. 相似文献
93.
Teh-Chang Chou Holger Lange Rolf Gleiter Tibor Ggh Miroslav Krí Max H. Pfenninger Marian Valentíny Camille Ganter 《Helvetica chimica acta》1995,78(8):2011-2025
Three 1,4-dimethylidenecyclohexanes, bridged in the 2,6- and 3,5-positions by two ethano ( 4 ), one ethano and one propano ( 5 ), and two propano bridges ( 6 ) have been synthesized. The interaction of the two exocyclic methylidene groups has been investigated by He(I) photoelectron (PE) spectroscopy. It revealed a slightly larger energy difference (0.8 eV) for 4 and 5 as compared to the parent 1,4-dimethylidenecyclohexane ( 7 ) (0.7 eV). The interpretation of the PE spectra was based on the comparison with PE data of related systems and with the results of semiempirical calculations on 4–6 . 相似文献
94.
Zusammenfassung Von den in der vorigen Mitteilung beschriebenen 3,4-Bis-(p-methoxyphenylhexandionen-(2,5) [meso undracem.] wurde diemeso-Verbindung durch Reduktion in zwei (der drei möglichen) entsprechende sekundäre Diole übergeführt und das höherschmelzende Diol durch Entmethylierung in ein 3,4-Bis-(p-hydroxyphenyl)-hexandiol-(2,5) (Dihydroxyhexoestrol) umgewandelt. Versuche, durch Reduktion eine Überführung in ein Hexoestrol zu erreichen und die sterische Anordnung festzulegen, schlugen sämtlich fehl.Eingehender wurde die Gewinnung homologer tertiärer Diole durch Umsetzung der beiden Hexandionderivate (meso undracem.) mit CH3MgX bearbeitet, wobei unter Ätherspaltung die beiden Bis-homologen-dihydroxy-hexoestrole resultierten. Ammesoiden Hexandionderivat wurde auch die Grignardreaktion allein (ohne Entmethylierung) durchgeführt.
6. Mitt.:H. Bretschneider undR. Lutz, Mh. Chem.95, 1702 (1964). 相似文献
Of the two (meso andracemic) 3,4-di(p-methoxyphenyl)-hexanediones-(2,5) described in the previous communication, themeso compound has been converted by reduction into two (of the three possible) corresponding secondary diols. Demethylation of the higher melting isomer yielded 3,4-di(p-hydroxyphenyl)-hexanediol-(2,5) (dihydroxyhexestrol). Attempts to obtain the corresponding hexestrol by reduction and hence to determine its configuration remained unsuccessful.The preparation of homologous tertiary diols by reaction of the two hexanedione derivatives (meso andracemic) with CH3MgX has been investigated more closely; on ether cleavage the two di-homologous dihydroxyhexestrols were formed. The Grignard reaction was also carried out on themeso hexanedione without subsequent demethylation.
6. Mitt.:H. Bretschneider undR. Lutz, Mh. Chem.95, 1702 (1964). 相似文献
95.
Using an adiabatic calorimeter, the heat of transition Sα ? Sβ, the heat of fusion of Sβ and the specific heat of the liquid had been determined on sulfur samples refined by zone melting and samples doped with chlorine, bromine and iodine. The data obtained from pure sulfur (heat of fusion: 1608 ± 8 J/Tom, specific heat of the liquid at 120°C: 29,4 J/Tom.°C) are about 10% lower than comparable values of other authors. Apparently they represent heat of fusion and specific heat of the pure cyclooctasulfur. The measurements on doped samples (δHS = 1736 ± 10 J/Tom) are in agreement with the data reported in literature and include a portion of enthalpy from the transition reaction of cycloocta-sulfur (Sλ) to catenaocta-sulfur (Sπ), requiring extremly long equilibrium times in pure sulfur. The influence of impurity on the caloric properties of the liquid sulfur is also indicated by the increasing width and decreasing highness of the Cp-maximum at 159°C with increasing amount of halogens. For the heat of transition Sα → Sβ, independent of the amount of impurity, the literature data could be confirmed. At the samples doped with iodine there was observed a previously unreported transition near 65,9°C. 相似文献
96.
Lutz Behle Markus Neuburger Margaretha Zehnder Thomas A. Kaden 《Helvetica chimica acta》1995,78(3):693-702
The new bis-macrocycle 1, 1′-[(1H-pyrazol-3], 5-diyl)bis(methylene)bis[1, 4, 7-triazacyclononane] ( 1 ) was synthesized and its complexation with Cu2+ studied. Potentiometric and spectrophotometric titrations indicate that, in addition to the mononuclear species [Cu(LH2)]4+, [Cu(LH)]3+, [CuL]2+, and [Cu(LH?1)]+, binuclear complexes such as [Cu2L]4+, [Cu2(LH?1)]3+, and [Cu2(LH-2)]2+ are also formed in solution. The stability constants and spectral properties of these are reported. The binuclear species [Cu2(LH?1)]3+ specifically reacts with an azide ion to give a ternary complex [Cu2(LH?1)(N3)]2+, the stability and structure of which were determined spectrophotometrically and by X-ray diffraction, respectively. The two Cu2+ ions are in a square-pyramidal coordination geometry. The axial ligand is one of the N-atoms of the 1, 4, 7-triazacyclononane ring, whereas at the base of the square pyramid, one finds the other two N-atoms of the macrocycle, one N-atom of the pyrazolide and one of the azide, both of which are bridging the two metal centres. In [Cu2(LH?1)(N3)]2+, a strong antiferromagnetic coupling is present, thus resulting in a species with a low magnetic moment of 1.36 B.M. at room temperature. 相似文献
97.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemical communications (Cambridge, England)》2005,(40):5115-5117
Chiral C3-symmetric trisoxazolines are highly efficient stereodirecting ligands in enantioselective Cu(II) Lewis acid catalysis which is based on the concept of a stereoelectronic hemilability of the divalent copper; in direct comparison with the analogous bisoxazoline systems they are more efficient in the enantioselective alpha-amination as well as the enantioselective Mannich reaction of prochiral beta-ketoesters. 相似文献
98.
The metal ion distribution on the two metal sites of monoclinic Mn1?xCux(HCOO)2 · 2(H,D)2O mixed crystals are studied by infrared and Raman spectroscopic methods. The spectral regions 3 200–3 400 cm?1 (vOH), 2 875–2 990 cm?1 (vCH), 2 330–2 500 cm?1 (vOD of matrix isolated HDO molecules), 1 350–1 400 cm?1 (symmetric CO2 stretching modes), 570–950 cm?1 (H2O librations), and 490 cm?1 (M? O lattice modes) are mostly sensitive to the metal ions present. The frequency shifts of these bands with increasing content of copper show that Cu2+ prefers the M(1) site, coordinated by HCOO? only. The strengths of the hydrogen bonds increase on going from manganese to copper formate, due to the increased synergetic effect of Cu2+. Solubility and X-ray data of the mixed crystals are included. Irrespective of the same crystal structure, two series of mixed crystals are formed: eutonic area at 0.65 ≥ x ≥ 0.5. 相似文献
99.
The synthesis of a number of nickel(II) complexes containing the didentate phosphane ligand 1,2-bis(di(o-methoxyphenyl)phosphino)ethane (o-MeO-dppe) is reported. Two types of complexes have been synthesized, i.e., the mono(chelate) complex (1) of the general formula [Ni(o-MeO-dppe)X2] (where X = Cl, Br or I) and the bis(chelate) complex (2) of the general formula [Ni(o-MeO-dppe)2]Y2 (where Y = PF6 or trifluoroacetate (TFA)). These complexes have been characterized using electronic absorption and NMR spectroscopy. The structures of the mono(chelate) complex [Ni(o-MeO-dppe)I2] (1c) and of the bis(chelate) complex [Ni(o-MeO-dppe)2](PF6)2 (2e) have been determined by X-ray crystallography. [Ni(o-MeO-dppe)I2] crystallizes in the monoclinic space group P2(1)/c with Z = 4, a = 12.1309(1) A, b = 16.5759(3) A, c = 17.6474(2) A, beta = 119.3250(10) degrees. [Ni(o-MeO-dppe)2](PF6)2 crystallizes in the monoclinic space group C2/c with Z = 4, a = 22.5326(3) A, b = 13.6794(2) A, c = 21.7134(3) A, beta = 107.1745(7) degrees. In both structures the nickel ion is in a square-planar geometry with a NiP2I2 and NiP4 chromophore, respectively. Using 1H and 31P[1H] NMR spectroscopy the behavior of the complexes in various solvents has been studied. It appears that in solution these nickel complexes are involved in an autoionization equilibrium: 2[Ni(o-MeO-dppe)X2] <==>[Ni(o-MeO-dppe)2](2+) + ["NiX(4)"](2-). The ionized complex (3) consists of a cationic unit in which a nickel atom is surrounded by two didentate phosphane ligands, and an anionic unit that stoichiometrically consists of a nickel atom and four anions. The position of the autoionization equilibrium is highly dependent on the anion and the solvent used. In a polar solvent in combination with weakly coordinating anions only the ionized complex is observed, whereas in an apolar solvent in combination with coordinating anions only the mono(chelate) complex occurs. A comparison of the behavior of o-MeO-dppe with its unsubstituted analogue dppe in combination with nickel(II) acetate using 31P[1H] NMR spectroscopy shows that the latter is more readily oxidized. 相似文献
100.
C. Lange 《Journal of mass spectrometry : JMS》1993,28(11):1285-1296
Oxirane chemical ionization (CI) gives numerous ions, including C2H3O+ and C2H5O+. These ions react with organic molecules through various specific ion–molecule reactions such as hydride abstraction, protonation, additions or cycloadditions. Oxirane CI allows discrimination between unsaturated compounds with [M + 43]+ and [M + 57]+ adduct ions and heteroatom functions with [M + 45]+ adduct ion. All are diagnostic ions. Oxirane CI permits selectivity during the ionization process of a mixture and discrimination of isomers. 相似文献