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941.
The HfFe6Ge6-type compounds Gd0.8L0.2Mn6Sn6 and Tb0.8L0.2Mn6Sn6 (L = Sc, Y, Lu) have been studied by 119Sn Mössbauer spectroscopy. The values of the apparent quadrupolar splitting clearly evidence the easy plane magnetization of the gadolinium compounds and the easy axis one in the terbium compounds. The three tin sites behave differently with the nature and size of the substituting L element. For a given series, the hyperfine field of the Sn2d site is almost unchanged whatever the size of the L element. The hyperfine field of the Sn2e site strongly varies with the L size in relation with atomic displacements. The hyperfine field of the Sn2c site exhibits a more complicated behavior. The field difference in the easy plane and easy axis compounds confirms the angle-dependent anisotropic contribution of the Mn moment to the hyperfine field. The analysis of the results also suggests the play of angle-dependent contributions arising from the rare earth moment. 相似文献
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Dipl.‐Chem. Alexander Zhdanko Dr. Markus Ströbele Prof. Dr. Martin E. Maier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14732-14744
Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh3, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf??Me2S<2,6‐lutidine<4‐picoline<CF3CO2?≈DMAP<TMTU<PPh3<OH?≈Cl?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)2 and S‐tolBINAP(AuOTf)2 showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh3 causes abstraction of one gold atom to give mononuclear complexes LLAuPPh3+ and (Ph3P)nAu+, but other N and S ligands give ordinary dicationic species LL(AuNu)22+. In reactions with different bases, LAu+ provided new oxonium ions whose chemistry was also studied: (DTBPAu)3O+, (L2Au)2OH+, (L2Au)3O+, (L3Au)2OH+, and (IMesAu)2OH+. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)2OH+, (L2Au)3O+, and L2AuOH are described. Reactions of dppf(AuOTf)2 and S‐tolBINAP(AuOTf)2 with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)2]3O22+, L8(Au)2OH+, and [L8(Au)2]3O22+, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe+ with S2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined. 相似文献
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Christian Logemann Daniel Gunzelmann Prof. Dr. Thorsten Klüner Prof. Dr. Jürgen Senker Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(48):15495-15503
The reactions of group 14 tetrachlorides MCl4 (M=Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures lead to the unique complex ions [M(S2O7)3]2?, which show the central M atoms in coordination with three chelating S2O72? groups. The mean distances M? O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M? O bonds. For the silicon compound (NH4)2[Si(S2O7)3], 29Si solid‐state NMR measurements have been performed, with the results showing a signal at ?215.5 ppm for (NH4)2[Si(S2O7)3], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO6] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S2O7)3]2? ions is achieved by monovalent A+ counter ions (A=NH4, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A+ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S2O7)3]2? ions remain essentially unaffected with the different A+ ions. Furthermore, the nature of the A+ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements. 相似文献
949.
Bhanu P. Mudraboyina Prof. James A. Wisner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(44):14157-14164
The design and syntheses of four self‐complementary oligomers that contain an underlying AADD hydrogen bond sequence are presented, and their self‐association was examined in the solution and solid state. The molecular recognition between the two strands is highly sensitive to substitutions of their component heterocycles. Substitution with electron‐donating and ‐withdrawing groups and the influence of preorganization has a large effect on the overall stabilities of the complexes studied. In particular, a wide range (>105 M ?1) of stabilities with respect to substitutions at various positions in the AADD oligomers was demonstrated. In the most extreme case, the dimerization constant measured (Kdimer≥4.5×107 M ?1) is comparable to the most stable homodimers of neutral AADD arrays reported to date. 相似文献
950.
A miniature mid-infrared (mid-IR) methane (CH4) sensor system was developed by employing a wide-band wire-source and a semi-ellipsoid multi-pass gas cell. A dual-step differential method instead of the traditional one-step differential method was adopted by this sensor to tune measuring range/zero point and to suppress the additive/multiplicative noise. This method included a first subtraction operation between the two output signals (including a detection signal and a reference signal) from the dual-channel detector and a second subtraction operation on the amplitudes of the first-subtraction signal and the reference signal, followed by a ratio operation between the amplitude of the second-subtraction signal and the reference signal. Detailed experiments were performed to assess the performance of the sensor system. The detection range is 0–50 k ppm, and as the concentration gets larger than 12 k ppm, the relative detection error falls into the range of −3% to +3%. The Allan deviation is about 4.65 ppm with an averaging time of 1 s, and such value can be further improved to 0.45 ppm with an averaging time of 124 s. Due to the cost-effective incandescence wire-source, the small-size ellipsoid multi-pass gas cell and the miniature structure of the sensor, the developed standalone device shows potential applications of CH4 detection under coal-mine environment. 相似文献