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61.
Thomas F Schulz S Nieger M Nättinen K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(8):1915-1924
Bimetallic, pentel-bridged complexes of the type [(dmap)Me2M-E(SiMe3)2-M'(CO)n] (M=Al, Ga; E=P, As, Sb; M'=Cr, Fe, Ni; DMAP=4-(dimethylamino)pyridine) are formed by reactions of DMAP-coordinated monomeric Group 13/15 compounds [(dmap)Me2M-E(SiMe3)2] with the transition metal complexes [(Me3N)Cr(CO)5], [Fe3(CO)12], and [Ni(CO)4]. For the first time, this reaction offers a general pathway to compounds containing a Group 13 metal and a transition metal bridged by a pentel atom. Complexes prepared in this way were characterized by IR and multinuclear NMR spectroscopy and by single-crystal X-ray structure analysis. Their electronic and structural properties are discussed in detail. The Group 13/15 ligands are very weak acceptors, which is likely to be due to the electropositive Group 13 metal, and the complexes feature comparatively long pentel-transition metal bonds. In addition, the synthesis and structural characterization of the parent DMAP-coordinated gallanes [(dmap)Me2Ga-E(SiMe3)2] (E=P, As) are reported. 相似文献
62.
63.
64.
The triangular phase diagram of the system dodecyltri-methylammonium hydroxide (DTAOH)–dodecanephosphonic acid (H2DP)–water was studied by several techniques. The DTAOH-rich zone could not be studied because DTAOH decomposed when it was
dried. Pure H2DP only forms lamellar mesophases with water. The inclusion of DTAOH in the system produces the appearance of cubic and hexagonal
mesophases. The gradual increase in DTAOH proportion lead to the gradual reduction in the existence of the lamellar mesophase
domain, and increase of the hexagonal liquid crystal domain. At high DTAOH content, the lamellar mesophase disappeared. This
behavior was explained by the gradual destruction of the hydrogen-bonded structure in the polar headgroup layer of liquid
crystal aggregates. H2DP-rich anhydrous crystals were triclinic.
Received: 8 September 1997 Accepted: 17 February 1998 相似文献
65.
The influence of the surfactant charge on micellization was studied on sodium n-dodecane-phosphonates, varying the charge of the surfactant ion from 0 to 2. The effects on the cmc, hydrolysis, micelle
composition, and micelle ionization degree were studied. The increase of one e unit in the charge of the surfactant species reduces the cmc by about one order of magnitude.
Received: 18 November 1996 Accepted: 5 March 1997 相似文献
66.
Preparation and Spectroscopic Investigations of Highly Branched Functional Siloxanes The preparation of the siloxanes [(Me3SiO)3SiO]n(Me3SiO)3?nSiX and (Me3SiO)3Si[OSi(OSiMe3)2]2X (n = 1?3, X = H, Cl, OC2H5, OH) is described. The hydride-siloxanes and the siloxanoles have been investigated by i.r. and 29Si-n.m.r. spectroscopy. The frequencies of the Si? H stretching vibration, the 29Si? 1H coupling constants and the 29Si-chemical shifts of the Si(H) signal for the hydride-siloxanes as well as the frequencies of the (Si)O? H stretching vibration, the relative (Si)O? H acidity, and the 29Si-chemical shifts of the Si(OH) signal for the siloxanoles show a dependence on the number of the (Me3SiO)3SiO groups. The spectroscopic data are discussed with respect to the silicate environment of the Si(H) and Si(OH) atom, respectively. In the siloxanoles intramolecular hydrogen bondings were observed. 相似文献
67.
Cao C Dahal S Shang M Beatty AM Hibbs W Schulz CE Scheidt WR 《Inorganic chemistry》2003,42(17):5202-5210
The effect of a sixth ligand in a series of low-spin thiocarbonyl-ligated iron(II)octaethylporphyrinates has been investigated. Six-coordinate complexes have been synthesized and characterized by M?ssbauer and infrared spectroscopy and single-crystal X-ray structure determinations. The results are compared with the five-coordinate parent complex. The crystal structures of [Fe(OEP)(CS)(1-MeIm)] and [Fe(OEP)(CS)(Py)] are reported and discussed. The 1-methylimidazole and pyridine derivatives exhibit Fe-C(CS) bond distances of 1.703(4) and 1.706(2) A that are significantly longer than the 1.662(3) A reported for five-coordinate [Fe(OEP)(CS)] (Scheidt, W. R.; Geiger, D. K. Inorg. Chem. 1982, 21, 1208). The trans Fe-N(ligand) distances of 2.112(3) and 2.1550(15) A observed for the 1-methylimidazole and pyridine complex are approximately 0.13 A longer than those observed for analogous bis-ligated complexes and are consistent with a significant structural trans effect for the CS ligand. M?ssbauer investigations carried out for five- and six-coordinate thiocarbonyl derivatives with several different sixth axial ligands reveal interesting features. All derivatives exhibit very small isomer shift values, consistent with a very strong interaction between iron and CS. The five-coordinate derivative has delta(Fe) = 0.08 mm/s, and the six-coordinate complexes exhibit delta(Fe) = 0.14 to 0.19 mm/s at 4.2 K. The five-coordinate complex shows a large quadrupole splitting (DeltaE(q) = 1.93 mm/s at 4.2 K) which is reduced on coordination of the sixth ligand (DeltaE(q) = 0.42-0.80 mm/s at 4.2 K). Addition of a sixth ligand also leads to a small decrease in the value of nu(CS). Correlations in structural, IR, and M?ssbauer results suggest that the sixth ligand effect is primarily induced by changes in sigma-bonding. The structure of [Fe(OEP)(CS)(CH(3)OH)] is briefly reported. Crystal data: [Fe(OEP)(CS)(1-MeIm)] crystallizes in the monoclinic system, space group P2(1)/n, Z = 4, a = 9.5906(5) A, b = 16.704(4) A, c = 23.1417(6) A, beta = 100.453(7) degrees. [Fe(OEP)(CS)(Py)] crystallizes in the triclinic system, space group P1, Z = 5, a = 13.9073(6) A, b = 16.2624(7) A, c = 22.0709(9) A, alpha = 70.586(1) degrees, beta = 77.242(1) degrees, gamma = 77.959(1) degrees. [Fe(OEP)(CS)(CH(3)OH)] crystallizes in the triclinic system, space group P1, Z = 1, a = 9.0599(5) A, b = 9.4389(5) A, c = 11.0676(6) A, alpha = 90.261(1) degrees, beta = 100.362(1) degrees, gamma = 114.664(1) degrees. 相似文献
68.
P. Svoboda J. Hetflej W. Schulz H. Pracejus 《Reaction Kinetics and Catalysis Letters》1986,32(1):39-44
Supported Ziegler catalysts prepared by the reaction of a Ni(II) 1-butylsalicylaldiminate or Ni(II) 2-ethylhexanoate with Al2O3/SiO2 treated with AlEt3 or NaAlH2 (OCH2CH2OCH3)2 are efficient catalysts for hydrogenation of simple alkenes. The factors influencing their activity are reported.
, qp - Ni(II) - Ni(II) 2- Al2O3/SiO2, AlEt3 NaAlH2 (OCH2CH2OCH3)2, . , .相似文献
69.
Spectroscopic Investigations on Substituent Effects in Silylmethylsilanes The silanes Me3?n(Me3SiCH2)nSiH (n = 1–3), (RMe2SiCH2)3SiH (R = n-Bu, n-Pr, Et, PhCH2, Ph) and Me3ElCH2SiMe2H (El = Ge, Sn) were prepared. The frequencies of the Si? H stretching vibration, the 29Si? 1H coupling constants and the 29Si n.m.r. chemical shifts were measured. The ?(SiH) and J(29Si? 1H) values in the silanes Me3?n(Me3SiCH2)nSiH depend on the number of trimethylsilymethyl groups. There is hardly an influence of the substituents R on these values in the silanes (RMe2SiCH2)3SiH. The frequencies of the Si? H stretching vibrations in the silanes Me3ElCH2SiMe2H (El = Si, Ge, Sn) show the order Si?Ge > Sn. The 29Si n.m.r. chemical shifts of the Si(H) signals are approximately equal in the silanes Me3?n(Me3SiCH2)nSiH and (RMe2SiCH2)3SiH. 相似文献
70.
Karlsson NG Schulz BL Packer NH 《Journal of the American Society for Mass Spectrometry》2004,15(5):659-672
Neutral O-linked oligosaccharides released from the salivary mucin MUC5B were separated and detected by negative ion LC-MS and LC-MS(2). The resolution of the chromatography and the information obtained from collision induced dissociation of detected [M - H](-) ions were usually sufficient to identify the sequence of individual oligosaccharides, illustrated by the fact that 50 different oligosaccharides ranging from disaccharides to nonasaccharides could be assigned from the sample. Fragmentation was shown to yield mostly reducing end sequence fragments (Z(i) and Y(i)), enabling primary sequence assignment. Specific fragmentation pathways or patterns were also detected giving specific linkage information. The reducing end core (Gal/GlcNAcbeta1-3GalNAcol or Gal/GlcNAcbeta1-3(GlcNAcbeta1-6)GalNAcol) could be deduced from the pronounced glycosidic C-3 cleavage and A(i) type cleavages of the reducing end GalNAcol, together with the non reducing end fragment from the loss of a single substituted GalNAcol. Substitution patterns on GlcNAc residues were also found, indicative for C-4 substitution ((0,2)A(i) - H(2)O cleavage) and disubstitution of C-3 and C-4 (Z(i)/Z(i) cleavages). This kind of fragmentation can be used for assigning the mode of chain elongation (Galbeta1-3/4GlcNAcbeta1-) and identification of Lewis type antigens like Lewis a/x and Lewis b/y on O-linked oligosaccharides. In essence, negative ion LC-MS(2) was able to generate extensive data for understanding the overall glycosylation pattern of a sample, especially when only a limited amount of material is available. 相似文献