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21.
Synthesis and Isolation of the Titanium–Scandium Endohedral Fullerenes—Sc2TiC@Ih‐C80, Sc2TiC@D5h‐C80 and Sc2TiC2@Ih‐C80: Metal Size Tuning of the TiIV/TiIII Redox Potentials
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Katrin Junghans Dr. Kamran B. Ghiassi Nataliya A. Samoylova Qingming Deng Marco Rosenkranz Prof. Marilyn M. Olmstead Prof. Alan L. Balch Dr. Alexey A. Popov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13098-13107
The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed‐metal Sc–Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4 system are Sc4C2@C80 (the most abundant EMF from this synthesis), Sc3C2@C80, isomers of Sc2C2@C82, and the family Sc2C2 n (2 n=74, 76, 82, 86, 90, etc.), as well as Sc3CH@C80. The Sc–Ti/CH4 system produces the mixed‐metal Sc2TiC@C2 n (2 n=68, 78, 80) and Sc2TiC2@C2 n (2 n=80) clusterfullerene families. The molecular structures of the new, transition‐metal‐containing endohedral fullerenes, Sc2TiC@Ih‐C80, Sc2TiC@D5h‐C80, and Sc2TiC2@Ih‐C80, were characterized by NMR spectroscopy. The structure of Sc2TiC@Ih‐C80 was also determined by single‐crystal X‐ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2TiC‐ and Sc2TiC2‐containing clusterfullerenes have Ti‐localized LUMOs. Encapsulation of the redox‐active Ti ion inside the fullerene cage enables analysis of the cluster–cage strain in the endohedral fullerenes through electrochemical measurements. 相似文献
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23.
Lubov' V. Snegur Yury S. Nekrasov Nataliya S. Sergeeva Zhanna V. Zhilina Vera V Gumenyuk Zoya A. Starikova Alexander A. Simenel Nataliya B. Morozova Irina K. Sviridova Valery N. Babin 《应用有机金属化学》2008,22(2):139-147
The toxicity of ferrocenylethyl benzotriazole ( 1 ) and other ferrocene compounds including ferrocenylmethyl benzimidazoles ( 4,5,6,11 ), ferricenium salts ( 3,9,10 ) and ferrocenylmethyl adenine ( 7 ), was studied. All ferrocene complexes under investigation showed low or medium toxicities. On the basis of an earlier model of chemical carcinogenesis, the antitumor activity of ferrocenylalkyl azoles 1, 8 and ferricenium salts 9, 10 was studied in vivo in the so‐called sub‐capsular test on human tumors. This effectiveness was compared with that of cisplatin. A series of ferrocenylalkyl azoles were synthesized by interacting azoles either with α‐hydroxyalkyl ferrocenes FcC(OH)R1R2 in organic solvent in the presence of aqueous HBF4 in quantitative yields or with trimethyl(aminomethyl)ferrocene iodide in an aqueous‐basic medium in good yields. The X‐ray determinations of molecular and crystal structures of α‐(1‐benzotriazolyl)ethylferrocene ( 1 ) and α‐(1‐naphthatriazolyl)ethylferrocene ( 12 ) were performed. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
24.
Eric M. Galimov Vyacheslav S. Sevastyanov Nataliya E. Babulevich Ekaterina N. Tyurina 《Rapid communications in mass spectrometry : RCM》2009,23(16):2461-2466
The application of a high‐temperature electrochemical reactor based on stabilized zirconium dioxide (0.9 ZrO20.1 Y2O3) for organic gas sampling in continuous‐flow isotope‐ratio mass spectrometry (CF‐IRMS) has been found to be efficient. This solid electrolyte reactor (SER) can also be used as a chromatographic detector for the quantitative measurements of organic gases. A three‐electrode SER system was studied. Complete stoichiometric oxidation of organic gases has been achieved at 900–950°C due to the large catalytic surface area of the porous platinum coating. At this temperature, the oxygen ions formed from the oxygen of ambient air on the outer surface of the reactor migrate through the solid electrolyte under the action of the applied electric field and allow combustion of gases being analyzed to be effected. It should be noted that oxygen gas was not introduced into the gas‐carrier flow. Similar results for the measurements of carbon isotope ratios were obtained at the oxidation of hydrocarbon gases in both the standard and the solid electrolyte reactors. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
25.
Gladis G. Zakirova Dmitrii Yu. Mladentsev Nataliya E. Borisova 《Tetrahedron letters》2017,58(35):3415-3417
Bis(diphenylphosphine oxides) and bis(tert-butyl(phenyl)phosphine oxides) of 1,10-phenanthroline, 2,2′-bipyridine and pyridine were synthesised in good yields via the Pd(OAc)2/dppf mediated cross-coupling reactions between 6,6′-dichloro-2,2′-bipyridine, 2,9-dichloro-1,10-phenanthroline, or 2,6-dichloropyridine and the corresponding secondary phosphine oxides. These compounds represent potential tetradentate chelating ligands for ions of f-block elements. 相似文献
26.
Ardanova LI Get'man EI Loboda SN Prisedsky VV Tkachenko TV Marchenko VI Antonovich VP Chivireva NA Chebishev KA Lyashenko AS 《Inorganic chemistry》2010,49(22):10687-10693
Polycrystalline hydroxyapatites Ca(10-x)REE(x)(PO(4))(6)(OH)(2-x)O(x) were synthesized and studied by X-ray powder diffraction, infrared absorption, diffuse-reflectance spectroscopy, and thermogravimetry. The solubility limits x(max) of rare earth elements (REE) in Ca hydroxyapatites decreases with an increasing REE atomic number from x(max) = 2.00 for La, Pr, and Nd to x(max) = 0.20 for Yb at 1100 °C. Refinements of X-ray diffraction patterns by the Rietveld method show that REE atoms substitute for Ca preferentially at the Ca(2) sites of the apatite structure. The substitution decreases the Ca(2)-O(4) atomic distances in the calcium coordination polyhedra and increases the Ca(2)-O(1,2,3) distances. This observation shows that interatomic distances depend not only on radii of the ions involved in the substitution but also on their charges. 相似文献
27.
Franz Weitzer Masaaki Naka Nataliya Krendelsberger Frank Stein Cuiyun He Yong Du Julius C. Schuster Prof. Dr. 《无机化学与普通化学杂志》2010,636(6):982-990
The constitution of the ternary system Ni/Si/Ti is investigated over the entire composition range using X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDS), differential thermal analysis (DTA), and metallography. The solid state phase equilibria are determined for 900 °C. Eight ternary phases are found to be stable. The crystal structures for the phases τ1NiSiTi, τ2Ni4Si7Ti4, τ3Ni40Si31Ti13, τ4Ni17Si7Ti6, and τ5Ni3SiTi2 are corroborated. For the remaining phases the compositions are determined as Ni6Si41Ti53 (τ6), Ni16Si42Ti42(τ7), and Ni12Si45Ti43 (τ8). The reaction scheme linking the solid state equilibria with the liquidus surface is amended to account for these newly observed phases. The discrepancies between previous experimental conclusions and modeling results are addressed. The liquidus surface is dominated by the primary crystallisation field of τ1NiSiTi, the only congruently melting phase. 相似文献
28.
Nataliya Chumalo Galyna P. Nychyporuk Rainer Pöttgen Dariusz Kaczorowski 《Journal of solid state chemistry》2010,183(12):2963-2967
The indides Ce7Ni5±xGe3±xIn6 and Pr7Ni5±xGe3±xIn6 were synthesized from the elements by arc-melting of the components. Single crystals were grown via special annealing sequences. Both structures were solved from X-ray single crystal diffraction data: new structure type, P6/m, Z=1, a=11.385(2), c=4.212(1) Å, wR2=0.0640, 634F2 values, 25 variables for Ce7Ni4.73Ge3.27In6 and a=11.355(6), c=4.183(2) Å, wR2=0.0539, 563F2 values, 25 variables for Pr7Ni4.96Ge3.04In6. Both indides show homogeneity ranges through Ni/Ge mixing (M sites). This new structure type can be derived from the AlB2 structure type by a substitution of the Al and B atoms by CeM12 and NiIn6Ce3 polyhedra (tricapped trigonal prism). Magnetic susceptibility measurements on a polycrystalline sample of Ce7Ni5Ge3In6 indicated Curie-Weiss like paramagnetic behavior down to 1.71 K with the effective magnetic moment slightly reduced in relation to the value expected for trivalent cerium ions. No magnetic ordering is evident. 相似文献
29.
Navida Nasir Nataliya Melnychenko-Koblyuk Ingeborg Bednar 《Journal of solid state chemistry》2010,183(10):2329-2342
Three series of vacancy-free quaternary clathrates of type I, Ba8ZnxGe46−x−ySiy, Ba8(Zn,Cu)xGe46−x, and Ba8(Zn,Pd)xGe46−x, have been prepared by reactions of elemental ingots in vacuum sealed quartz at 800 °C. In all cases cubic primitive symmetry (space group Pm3?n, a∼1.1 nm) was confirmed for the clathrate phase by X-ray powder diffraction and X-ray single crystal analyses. The lattice parameters show a linear increase with increase in Ge for Ba8ZnxGe46−x−ySiy. M atoms (Zn, Pd, Cu) preferably occupy the 6d site in random mixtures. No defects were observed for the 6d site. Site preference of Ge and Si in Ba8ZnxGe46−x−ySiy has been elucidated from X-ray refinement: Ge atoms linearly substitute Si in the 24k site whilst a significant deviation from linearity is observed for occupation of the 16i site. A connectivity scheme for the phase equilibria in the “Ba8Ge46” corner at 800 °C has been derived and a three-dimensional isothermal section at 800 °C is presented for the Ba-Pd-Zn-Ge system. Studies of transport properties carried out for Ba8{Cu,Pd,Zn}xGe46−x and Ba8ZnxSiyGe46−x−y evidenced predominantly electrons as charge carriers and the closeness of the systems to a metal-to-insulator transition, fine-tuned by substitution and mechanical processing of starting material Ba8Ge43. A promising figure of merit, ZT ∼0.45 at 750 K, has been derived for Ba8Zn7.4Ge19.8Si18.8, where pricey germanium is exchanged by reasonably cheap silicon. 相似文献
30.
Nataliya Yu. Strutynska Vyacheslav N. Baumer Igor V. Zatovsky Artem A. Babaryk Nikolay S. Slobodyanik 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(4):i39-i41
The complex phosphate tricaesium calcium iron bis(diphosphate), Cs3CaFe(P2O7)2, has been prepared by the flux method. Isolated [FeO5] and [CaO6] polyhedra are linked by two types of P2O7 groups into a three‐dimensional framework. The latter is penetrated by hexagonal channels along the a axis where three Cs atoms are located. Calculations of caesium Voronoi–Dirichlet polyhedra give coordination schemes for the three Cs atoms as [8 + 3], [9 + 1] and [9 + 4]. The structure includes features of both two‐ and three‐dimensional frameworks of caesium double pyrophosphates. 相似文献