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61.
Takezawa Y Tanaka K Yori M Tashiro S Shiro M Shionoya M 《The Journal of organic chemistry》2008,73(16):6092-6098
Metal-mediated base pairing with artificial ligand-bearing nucleosides allows site-selective metal incorporation inside DNA duplexes. In particular, this strategy has provided a general way of discrete, heterogeneous metal arrays in a programmable manner. To increase the kind of metallo-building blocks, we have newly synthesized two artificial nucleosides which have an O, S-donor ligand as the nucleobase moiety, mercaptopyridone ( M) and hydroxypyridinethione ( S). These nucleosides were found to efficiently form metal-mediated base pairs with soft transition metal ions such as Pd (2+) and Pt (2+). 相似文献
62.
Nakamura S Kobayashi L Tanaka R Isoda-Yamashita T Motomura K Moroi Y 《Langmuir : the ACS journal of surfaces and colloids》2008,24(1):15-18
Solubilization of benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, n-pentylbenzene, and n-hexylbenzene into micelles of decanoyl-N-methylglucamide (Mega-10) was studied, where equilibrium concentrations of the above solubilizates were determined spectrophotometrically at 303.2 K. The concentration of the above solubilizates remained constant below the critical micelle concentration (cmc) and increased linearly with an increase in Mega-10 concentration above the cmc. The Gibbs free energy change of the solubilizates from the aqueous bulk to the liquid solubilizate phase was evaluated from the dependence of their aqueous solubility on the alkyl chain length of the solubilizates, which leads to -3.46 kJ mol-1 for DeltaG(0)(CH), the energy change per CH2 group of the alkyl chain. The first stepwise solubilization constant (K(overline)1 ) was evaluated from the slope of the change of solubilizate concentration versus Mega-10 concentration. The Gibbs free energy change (DeltaG(0,s)) for the solubilization decreased linearly with the carbon number of the alkyl chain of the solubilizates, from which DeltaG(0,s)(CH2) as evaluated to be -2.71 kJ mol-1. The similar values above clearly indicate that the location of the alkyl chain is a hydrophobic micellar core, which is also supported by the absorption spectrum of the solubilized molecules. 相似文献
63.
Taki M Desaki M Ojida A Iyoshi S Hirayama T Hamachi I Yamamoto Y 《Journal of the American Chemical Society》2008,130(38):12564-12565
We described here a coumarin-based dual-excitation ratiometric probe for cadmium, CadMQ. This fluorescence sensor has high quantum yields of 0.59 and 0.70 in the metal-free and Cd2+-bound forms, respectively, and has a dissociation constant of 0.16 nM for Cd2+. CadMQ is cell permeable and locates within the acidic compartments of the cells. We further show that CadMQ is a useful tool to ratiometrically probe the change in the intracellular Cd2+ levels with the use of two excited wavelengths. 相似文献
64.
Recent studies suggest the dominant role of main-chain H-bond formation in specifying beta-sheet topology. Its essentially sequence-independent nature implies a large degree of freedom in designing beta-sheet-based nanomaterials. Here we show rational design of beta-sheet face inversions by incremental deletions of beta-strands from the single-layer beta-sheet of Borrelia outer surface protein A. We show that a beta-sheet structure can be maintained when a large number of native contacts are removed and that one can design large-scale conformational transitions of a beta-sheet such as face inversion by exploiting the promiscuity of strand-strand interactions. High-resolution X-ray crystal structures confirmed the success of the design and supported the importance of main-chain H-bonds in determining beta-sheet topology. This work suggests a simple but effective strategy for designing and controlling nanomaterials based on beta-rich peptide self-assemblies. 相似文献
65.
Rosamine-based fluorescent chemosensor for selective detection of silver(I) in an aqueous solution 总被引:1,自引:0,他引:1
The synthesis and photophysical properties of a rosamine-based fluorescent chemosensor, RosAg, for detecting Ag ion in an aqueous solution are described. This fluorescent sensor has a negligible quantum yield (<0.005) in the absence of Ag(+), whereas a significant increase in fluorescence is observed upon complexation with Ag(+) under physiological conditions. The crystal structure of the silver complex with the chelator moiety of RosAg reveals a trigonal-planar coordination geometry in which three S atoms occupy the metal center. Although a strong coordinative interaction of Ag-N is not observed in the crystal structure, the (1)H NMR experiments suggest that aniline nitrogen is likely to be associated with the Ag(+) center in the solution state. This may inhibit the photoinduced electron transfer process and result in the enhancement of fluorescence. 相似文献
66.
A Soluble Dynamic Complex Strategy for the Solution‐Processed Fabrication of Organic Thin‐Film Transistors of a Boron‐Containing Polycyclic Aromatic Hydrocarbon
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Kyohei Matsuo Dr. Shohei Saito Prof. Dr. Shigehiro Yamaguchi 《Angewandte Chemie (International ed. in English)》2016,55(39):11984-11988
The solution‐processed fabrication of thin films of organic semiconductors enables the production of cost‐effective, large‐area organic electronic devices under mild conditions. The formation/dissociation of a dynamic B?N coordination bond can be used for the solution‐processed fabrication of semiconducting films of polycyclic aromatic hydrocarbon (PAH) materials. The poor solubility of a boron‐containing PAH in chloroform, toluene, and chlorobenzene was significantly improved by addition of minor amounts (1 wt % of solvent) of pyridine derivatives, as their coordination to the boron atom suppresses the inherent propensity of the PAHs to form π‐stacks. Spin‐coating solutions of the thus formed Lewis acid–base complexes resulted in the formation of amorphous thin films, which could be converted into polycrystalline films of the boron‐containing PAH upon thermal annealing. Organic thin‐film transistors prepared by this solution process displayed typical p‐type characteristics. 相似文献
67.
68.
New triazine-type dehydrocondensing reagents, such as ROMP-Trz-Cl and ROMP(OH)-Trz-Cl, were synthesized by a ring opening metathesis polymerization (ROMP) method, and these showed higher loading than conventional polymer-supported condensing reagents. These polymers effect the formation of amides in good yields by addition of a mixture of carboxylic acid, amine and NMM. ROMP(OH)-Trz-Cl, which contains hydroxyl groups in the polymer chain, gave amides in good yields even in MeOH. 相似文献
69.
Shohei Inoue 《Journal of polymer science. Part A, Polymer chemistry》2000,38(16):2861-2871
The story of the outset of the concept of immortal polymerization is presented. Immortal polymerization is the polymerization that gives polymers with a narrow molecular distribution, even in the presence of a chain transfer reaction, because of its reversibility, which leads to the revival of the polymers once dead, that is, the immortal nature of the polymers. As a result, immortal polymerization can afford polymers with a controlled molecular weight, the number of polymer molecules being more than that of the initiator. The compound that plays a leading role is metalloporphyrin, in which the metal‐axial ligand bond has an unusually high reactivity. Immortal polymerization can be carried out in the ring‐opening polymerizations of epoxides, episulfides, and lactones by the selection of an appropriate metalloporphyrin as the initiator and a protic compound as the chain transfer agent. Immortal polymerization is an effective method for synthesizing end‐functional polymers and oligomers with narrow molecular weight distributions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2861–2871, 2000 相似文献
70.
Nakahata T Fujimura S Kuwahara S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(17):4584-4593
Pteridic acid A (1) is a spirocyclic octaketide produced by the phytoepiphytic actinomycete Streptomyces hygroscopicus TP-A0451 and possesses potent plant-growth-promoting activity comparable to that of indole-3-acetic acid. The enantioselective total synthesis of this natural product was achieved by employing the Sn(OTf)(2)-mediated Evans aldol reaction and the Fukuyama acetylenic coupling reaction as the key C--C bond-forming steps producing 1 through a 14-step sequence in 22 % overall yield from a known oxazolidinone derivative. MgBr(2)-mediated equilibration of an anomerically favored spirocyclic intermediate used for the synthesis of 1 brought about partial epimerization of the spirocenter to give the corresponding anomerically disfavored epimer, which was converted into pteridic acid B (11-epi-1), another plant-growth promoter of the same microbial origin. 相似文献