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81.
The negative ion mass spectra of sulphur, dinitriles and their mixtures were studied. The abundance of negative ions of sulphur was almost comparable to that of positive ions. In the negative ion mass spectrum of a mixture of sulphur and dinitrile, intense and characteristic peaks of [M + Sn]? (n = 2, 3, 4, etc.) were observed resulting from ion–molecule association of dinitrile with the Sn? anions. As a standard sample of a negative ion mass spectrum, sulphur itself has proved useful in the lower mass region (below m/e 256: S8?). 相似文献
82.
Kozo Arai Yoshio Nakamura H. E. Edwards G. O. Phillips 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1497-1503
Three different commercial heparins were trinitophenylated with 2,4,6-trinitrobenzenesulfonic acid (TNBS) under aqueous conditions. The reaction kinetics of amino groups in heparin with TNBS showed that the reactivities of amino groups were significantly different for free amino groups on heparin, compared to reactivities in peptides and amino acid residues attached to heparin molecules. With TNBS, unreactive amino groups were always present during the reaction. 相似文献
83.
An air- and moisture-stable (pi-allyl)palladium complex bearing a unique diphosphinidenecyclobutene ligand effectively catalyzes amination reactions of aryl bromides with amines, where the reactions proceed under mild conditions without solvent, with 2 mol % of catalyst and 1 equiv of t-BuOK at room temperature. Under these conditions the amination products were obtained in good to excellent isolated yields. 相似文献
84.
[reaction: see text] Sterically protected 3,4-diphosphinidenecyclobutenes, having ring-fused structures, were prepared. Structures of 8,9-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]bicyclo[5.2.0]non-1(7)-ene and its dichloropalladium(II) complex were analyzed by X-ray crystallography. A geometrical change induced by the complex formation was exhibited by X-ray crystallographic analysis. The geometrical change in solution was also suggested by (1)H NMR spectroscopy in CDCl(3). 相似文献
85.
Kozo Arai Shigeo Komine Michiharu Negishi 《Journal of polymer science. Part A, Polymer chemistry》1970,8(4):917-927
In order to elucidate the termination mechanism in the graft copolymerization of methyl methacrylate to unreduced and reduced wool fibers, graft copolymers were prepared by means of the LiBr–K2S2O8 redox sytem without homopolymer or with K2S2O8 only with homopolymer at 30°C. The graft polymers (PMMA) were isolated almost completely from the wool trunk by an HCI-digestion method, leaving a few amino acid residues on the end of the graft polymers. Dinitrophenylation of the isolated polymer was carried out by various methods. The spectral features were almost the same as for dinitrophenylated amino acids of the usual type such as valine, leucine, and methionine, with a maximum in ultraviolet light at 340–345 mμ. From colorimetric analysis of the number of dinitrophenylated amino acid endgroups and the measurement of the average molecular weight of the isolated polymers, the number of amino acid endgroups linked to the graft polymers was calculated to be about one and two per polymer chain in reduced and unreduced wool, respectively, independent of the reaction system, graft-on, and molecular weight of graft polymers. From these facts, it was suggested that the most of isolated polymers are the truly grafted polymers. Also, the termination reactions have been explained as follows. In the unreduced wool, the restriction of mobility of the radical end might be expected, for the confinement of growing chains in wool fibers. This would be favorable to termination by recombination rather than by the disproportionation, since the former has a lower activation energy than the latter. Thus, the formation of intra- or intermolecular crosslinks might be considered between polypeptide chains. On the other hand, in the reduced wool, the mobility of graft polymers might be considered to be greater than that of unreduced wool because of its open structure. Therefore, termination would be principally by disproportionation between graft polymer radicals. 相似文献
86.
Kaewsaiha P Matsumoto K Matsuoka H 《Langmuir : the ACS journal of surfaces and colloids》2007,23(1):20-24
The strong polyelectrolyte layer in the monolayer of ionic amphiphilic diblock copolymers at the air/water interface consists of carpet and brush layers when the brush density is satisfactorily high like that of the weak acid polymer. Also, a drastic structural change was induced by the addition of salt to the brush layer. In this study, the critical brush density for the transition between "carpet-only" and "carpet + brush" structures for the strongly ionic amphiphilic diblock copolymer, poly(hydrogenated isoprepene)-b-poly(styrene sulfonic acid) sodium salt, monolayer was measured by an in situ X-ray reflectivity technique. The critical brush density was found to be about 0.12 nm-2, which is lower than that observed for a weak acid polymer and, unlike the weak acid polymer, is independent of the hydrophilic chain length. This difference might be attributed to the strong ionic nature of the brush chain. In addition, the reversibility of the transition was confirmed. The effect of salt addition to the nanostructure of the carpet layer was examined in detail. No structural change was found, indicating that most of the ionic groups in the carpet layer do not show an ionic nature because of counterion condensation. 相似文献
87.
Kozo Matsumoto Shuji Kage Hideki Matsuoka 《Journal of polymer science. Part A, Polymer chemistry》2007,45(7):1316-1323
Fluorinated polymer particles with grafting sulfonate chains, which showed high dispersion stability in aqueous media, were synthesized by the crosslinking of block copolymer micelles. A crosslinkable block copolymer, poly[(2,3,4,5,6‐pentafluorostyrene)‐co‐4‐(1‐methylsilacyclobutyl)styrene]‐b‐poly(neopentyl 4‐styrenesulfonate), composed of a statistical copolymer segment of 2,3,4,5,6‐pentafluorostyrene with 4‐(1‐methylsilacyclobutyl)styrene and a neopentyl 4‐styrenesulfonate segment, was prepared by the nitroxy‐mediated living radical polymerization of a 2,3,4,5,6‐pentafluorostyrene/4‐(1‐methylsilacyclobutyl)styrene mixture and neopentyl 4‐styrenesulfonate. The block copolymer formed micelles with a poly[(2,3,4,5,6‐pentafluorostyrene)‐co‐4‐(1‐methylsilacyclobutyl)styrene] core in acetonitrile, which were crosslinked via the ring‐opening reaction of silacyclobutyl groups in the core by a treatment with a platinum catalyst. The deprotection of sulfonate groups in the micelle corona by exposure to trimethylsilyl iodide and a treatment with aqueous HCl, followed by neutralization with aqueous NaOH, provided a polymer particle with polymer chains of sodium 4‐styrenesulfonate grafted on its surface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1316–1323, 2007 相似文献
88.
ZrO2酸碱性质的TPD表征 I. 单组分吸附研究 总被引:2,自引:3,他引:2
以NH_3、吡啶、Et_3N、CO_2和苯酚为探针,用TPD-MS方法对ZrO_2催化剂的酸碱性质进行了表征.ZrO_2上碱性探针(NH_3、吡啶和Et_3N)的脱附温度远低于在强酸性SiO_2-Al_2O_3上;而酸性探针CO_2的脱附温度远低于在强碱性MgO上的结果.为ZrO_2的弱酸弱碱性质提供了证明.NH_3吸附IR结果表明ZrO_2表面配位不饱合Zr~(4+)为酸(Lewis酸)中心.NH_3、吡啶和Et_3N与这些酸中心作用的方式和能量分布相似.NH_3和CO_2的TPD谱图均存在三个脱附峰,且相应脱附峰的温度范围相近.表明ZrO_2的酸中心和碱中心具有匹配相当的酸、碱强度,ZrO_2为典型的酸-碱双功能催化剂,在苯酚的TPD过程中,ZrO_2的特征表现为对苯酚的强吸附和对苯酚分解的高活性.文中结合IR结果,对与NH_3和CO_2的脱附相联系的表面吸附物种分别进行了讨论. 相似文献
89.
Horinouchi Y Tsuchiya K Taoka C Tajima S Kihira Y Matsuda Y Shishido K Yoshida M Hamano S Kawazoe K Ikeda Y Ishizawa K Tomita S Tamaki T 《Chemical & pharmaceutical bulletin》2011,59(2):208-214
Recently, increasing evidence suggests that the antihypertensive drug nifedipine acts as a protective agent for endothelial cells, and that the activity is unrelated to its calcium channel blocking. Nifedipine is unstable under light and reportedly decomposes to a stable nitrosonifedipine (NO-NIF). NO-NIF has no antihypertensive effect, and it has been recognized as a contaminant of nifedipine. The present study for the first time demonstrated that NO-NIF changed to a NO-NIF radical in a time-dependent manner when it interacted with human umbilical vein endothelial cells (HUVECs). The electron paramagnetic resonance (EPR) signal of NO-NIF radicals in HUVECs showed an asymmetric pattern suggesting that the radicals were located in the membrane. The NO-NIF radicals had radical scavenging activity for 1,1-diphenyl-2-picrylhydrazyl, whereas neither NO-NIF nor nifedipine did. In addition, the NO-NIF radical more effectively quenched lipid peroxides than NO-NIF or nifedipine. Furthermore, NO-NIF attenuated the superoxide-derived free radicals in HUVECs stimulated with LY83583, and suppressed iron-nitrilotriacetic acid (Fe-NTA)-induced cytotoxicity in rat pheochromocytoma (PC12) cells. Our findings suggest that NO-NIF is a candidate for a new class of antioxidative drugs that protect cells against oxidative stress. 相似文献
90.
Kozo Arai Masamichi Shimizu Machiko Shimada 《Journal of polymer science. Part A, Polymer chemistry》1973,11(12):3271-3281
In order to study the termination reaction of polymer radicals in the viscous media of wool fibers, reduced, methylated, and S-carboxymethylated wool fibers were used for graft copolymerization of methyl methacrylate and styrene. With termination of poly(methyl methacrylate) radicals, two different termination reactions, recombination and disproportionation, were together involved in the grafting systems studied. The occurrences of two termination reactions in the system could be correlated with the mobility of the wool chain controlling the radical end mobility. With decreasing disulfide content in the fibers, disproportionation predominantly takes place among the mobilized chains. At a constant disulfide, the thiol content or the concentration of thiol anions becomes the determining factor for the termination reaction. A possible explanation for these phenomena in terms of the thiol and disulfide interchange reaction is presented. On the grafting of styrene, additional evidence was obtained that prevention and retardation of the interchange reactions followed mechanochemical bond scission of the disulfide and other covalent bonds and produced new free radicals which could initiate chain reactions. 相似文献