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21.
Rinta Sato Dr. Kosuke Suzuki Midori Sugawa Prof. Dr. Noritaka Mizuno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):12982-12990
Polyoxometalates (POMs) with heterodinuclear lanthanoid cores, TBA8H4[{Ln(μ2‐OH)2Ln′}(γ‐SiW10O36)2] ( LnLn′ ; Ln=Gd, Dy; Ln′=Eu, Yb, Lu; TBA=tetra‐n‐butylammonium), were successfully synthesized through the stepwise incorporation of two types of lanthanoid cations into the vacant sites of lacunary [γ‐SiW10O36]8? units without the use of templating cations. The incorporation of a Ln3+ ion into the vacant site between two [γ‐SiW10O36]8? units afforded mononuclear Ln3+‐containing sandwich‐type POMs with vacant sites ( Ln1 ; TBA8H5[{Ln(H2O)4}(γ‐SiW10O36)2]; Ln=Dy, Gd, La). The vacant sites in Ln1 were surrounded by coordinating W? O and Ln? O oxygen atoms. On the addition of one equivalent of [Ln′(acac)3] to solutions of Dy1 or Gd1 in 1,2‐dichloroethane (DCE), heterodinuclear lanthanoid cores with bis(μ2‐OH) bridging ligands, [Dy(μ2‐OH)2Ln′]4+, were selectively synthesized ( LnLn′ ; Ln=Dy, Gd; Ln′=Eu, Yb, Lu). On the other hand, La1 , which contained the largest lanthanoid cation, could not accommodate a second Ln′3+ ion. DyLn′ showed single‐molecule magnet behavior and their energy barriers for magnetization reversal (ΔE/kB) could be manipulated by adjusting the coordination geometry and anisotropy of the Dy3+ ion by tuning the adjacent Ln′3+ ion in the heterodinuclear [Dy(μ2‐OH)2Ln′]4+ cores. The energy barriers increased in the order: DyLu (ΔE/kB=48 K)< DyYb (53 K)< DyDy (66 K)< DyEu (73 K), with an increase in the ionic radii of Ln′3+; DyEu showed the highest energy barrier. 相似文献
22.
Masahide Tominaga Hiroyuki Ukai Kosuke Katagiri Kazuaki Ohara Kentaro Yamaguchi Isao Azumaya 《Tetrahedron》2014
Five macrocyclic molecules (1–5) were efficiently synthesized from the dimerization and trimerization of di-substituted adamantane derivatives, which were composed of three different aromatic units and two different linker groups. Three single-crystals were obtained from these macrocyclic molecules, including a set of pseudopolymorphs (3a and 3b) of macrocycle 3 and another macrocycle 5 (5a). Single crystal X-ray analysis revealed that the three monocyclic compounds were rectangular or square in shape with solvent molecules in the cavity. Macrocycle 3 in 3a formed stacks to produce tubular structures with channels that assembled into three-dimensional networks through CH/π interactions. 相似文献
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Siti Masturah binti Fakhruddin Kosuke Ino Kumi Y. Inoue Yuji Nashimoto Hitoshi Shiku 《Electroanalysis》2022,34(2):212-226
Bipolar electrode-based (BPE-based) electrochromic devices have garnered increasing attention in the past decade. These BPE-based electrochromic devices have been used for analytical health monitoring, point-of-care (POC) diagnostics, and chemical sensing. In this review, we highlight recent progress made regarding BPE-based electrochromic devices constructed for these analytical applications. Various, available electrochromic materials are summarized in the first section, after which the different device types (e. g., paper-based and self-powered) are discussed. Biological- and chemical-based analytical demonstrations of these devices are then reviewed. Finally, we conclude this review with a perspective on the future developments of BPE-based electrochromic devices in analytical applications. 相似文献
25.
Synthesis of α‐Dawson‐Type Silicotungstate [α‐Si2W18O62]8− and Protonation and Deprotonation Inside the Aperture through Intramolecular Hydrogen Bonds
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Takuo Minato Dr. Kosuke Suzuki Dr. Keigo Kamata Prof. Dr. Noritaka Mizuno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5946-5952
The design of structurally well‐defined anionic molecular metal–oxygen clusters, polyoxometalates (POMs), leads to inorganic receptors with unique and tunable properties. Herein, an α‐Dawson‐type silicotungstate, TBA8[α‐Si2W18O62] ? 3 H2O ( II ) that possesses a ?8 charge was successfully synthesized by dimerization of a trivacant lacunary α‐Keggin‐type silicotungstate TBA4H6[α‐SiW9O34] ? 2 H2O ( I ) in an organic solvent. POM II could be reversibly protonated (in the presence of acid) and deprotonated (in the presence of base) inside the aperture by means of intramolecular hydrogen bonds with retention of the POM structure. In contrast, the aperture of phosphorus‐centered POM TBA6[α‐P2W18O62]?H2O ( III ) was not protonated inside the aperture. The density functional theory (DFT) calculations revealed that the basicities and charges of internal μ3‐oxygen atoms were increased by changing the central heteroatoms from P5+ to Si4+, thereby supporting the protonation of II . Additionally, II showed much higher catalytic performance for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde than I and III . 相似文献
26.
Mesoporous Silica Particles as Topologically Crosslinking Fillers for Poly(N‐isopropylacrylamide) Hydrogels
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Prof. Nobuyoshi Miyamoto Kotaro Shimasaki Kosuke Yamamoto Morio Shintate Yuichiro Kamachi Dr. Bishnu Prasad Bastakoti Dr. Norihiro Suzuki Dr. Ryuhei Motokawa Prof. Yusuke Yamauchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):14955-14958
Here it is demonstrated that mesoporous silicas (MPSs) can be used as effective “topological crosslinkers” for poly(N‐isopropylacrylamide) (PNIPA) hydrogels to improve the mechanical property. Three‐dimensional bicontinuous mesporous silica is found to effectively reinforce the PNIPA hydrogels, as compared to nonporous silica and two‐dimensional hexagonally ordered mesoporous silica. 相似文献
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28.
Kentaro Yonesato Hiroyasu Ito Daisuke Yokogawa Kazuya Yamaguchi Kosuke Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(38):16361-16365
Small Agn nanoclusters (n<10) have been emerging as promising materials as sensing, biolabeling, and catalysis because of their unique electronic states and optical properties. However, studying synthesis, structure determination, and exploration of their properties remain major challenges as a result of the low stability of small Ag nanoclusters. Herein, we synthesized an atomically precise face‐centered‐cubic‐type small {Ag7}5+ nanocluster supported by a novel triangular hollow polyoxometalate (POM) framework [Si3W27O96]18?. The cluster showed unique {Ag7}5+‐to‐POM charge transfer bands in both visible and UV light regions. Furthermore, this small {Ag7}5+ nanocluster exhibited an unprecedented ultrastability in solution, despite having exposed Ag sites that can be accessed by small molecules, such as O2, water, and solvents. 相似文献
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Water‐ and Temperature‐Triggered Reversible Structural Transformation of Tetranuclear Cobalt(II) Cores Sandwiched by Polyoxometalates
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Yosuke Kuriyama Dr. Yuji Kikukawa Dr. Kosuke Suzuki Dr. Kazuya Yamaguchi Prof. Dr. Noritaka Mizuno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):3962-3966
Although stimuli‐responsive structural transformations of inorganic materials have attracted considerable attention because of their potential use as functional switchable materials, multinuclear metal cores frequently suffer from unexpected dissociation of metal cations and/or irreversible transformations into infinite structures. In this study, we describe the successful demonstration of the water‐ and temperature‐triggered reversible structural transformation between cubane‐ and planar‐type tetranuclear CoII cores sandwiched by polyoxometalates. The arrangements and coordination geometries of the CoII cations were interconverted by simple hydration and dehydration, resulting in the manipulation of the magnetic and optical properties of these compounds. Moreover, this system showed unique thermochromism through temperature‐dependent reversible structural interconversion. 相似文献