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121.
Fundamental questions in the study of interesting dynamics of planar diffeomorphisms like the Hénon map involve homoclinic phenomena, topological entropy and strange attractors. Inherently, answering these questions requires knowledge about the stable and unstable manifolds, which in the typical case in the plane are smooth curves. We present a method to find highly accurate Taylor Model enclosures of the invariant curves near hyperbolic fixed points. Successive iteration of these local enclosures yields similarly accurate enclosures of pieces of the global manifold tangle. Applications presented include the automatic computation of rigorous enclosures of all homoclinic points up to finite iterates. This allows to find symbolic dynamics in the original system and consequently compute rigorous lower bounds for its topological entropy. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
122.
Structure Determination of an AgI‐Mediated Cytosine–Cytosine Base Pair within DNA Duplex in Solution with 1H/15N/109Ag NMR Spectroscopy
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Dr. Takenori Dairaku Dr. Kyoko Furuita Dr. Hajime Sato Dr. Jakub Šebera Dr. Katsuyuki Nakashima Dr. Jiro Kondo Daichi Yamanaka Prof. Yoshinori Kondo Dr. Itaru Okamoto Prof. Akira Ono Dr. Vladimír Sychrovský Dr. Chojiro Kojima Prof. Yoshiyuki Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13028-13031
The structure of an AgI‐mediated cytosine–cytosine base pair, C–AgI–C, was determined with NMR spectroscopy in solution. The observation of 1‐bond 15N‐109Ag J‐coupling (1J(15N,109Ag): 83 and 84 Hz) recorded within the C–AgI–C base pair evidenced the N3–AgI–N3 linkage in C–AgI–C. The triplet resonances of the N4 atoms in C–AgI–C demonstrated that each exocyclic N4 atom exists as an amino group (?NH2), and any isomerization and/or N4–AgI bonding can be excluded. The 3D structure of AgI–DNA complex determined with NOEs was classified as a B‐form conformation with a notable propeller twist of C–AgI–C (?18.3±3.0°). The 109Ag NMR chemical shift of C‐AgI‐C was recorded for cytidine/AgI complex (δ(109Ag): 442 ppm) to completed full NMR characterization of the metal linkage. The structural interpretation of NMR data with quantum mechanical calculations corroborated the structure of the C–AgI–C base pair. 相似文献
123.
124.
The CO2 TEA laser irradiation of CBr2F2 in the presence of Cl2 yielded 13C-enriched CBrClF2 and 13C-enriched CCl2F2 under selected experimental conditions. As the photolysis proceeded, the 13C concentration of CBrClF2 decreased gradually and that of CCl2F2 increased up to 90% or higher. These results can be explained by the mechanism involving the secondary 13C-selective IRMPD of the primary product CBrClF2. On the other hand, the carbon-containing product for a CCl2F2/Br2 system was only CBrClF2; the further IRMPD of which probably regenerated CBrClF2 in the presence of Br2. The decomposition probabilities of 12C- and 13C-containing molecules in both systems were measured as functions of laser line, laser fluence, and reactant pressures. 相似文献
125.
Recently, a relatively simple scheme for the construction of isotropic intermolecular potentials has been proposed and tested for the like species interactions involving He, Ne, Ar, Kr and H2. The model potential has an adjustable parameter which controls the balance between its exchange and Coulomb energy components. The representation of the Coulomb energy contains a damped multipolar dispersion energy series (which is truncated through O(R?10) and provides additional flexibility through adjustment of the dispersion energy coefficients, particularly C8 and C10, within conservative error estimates. In this paper the scheme is tested further by application to interactions involving unlike noble gas atoms where the parameters in the potential model are determined by fitting mixed second virial coefficient data as a function of temperature. Generally the approach leads to potential of accuracy comparable to the best available literature potentials which are usually determined using a large base of experimental and theoretical input data. Our results also strongly indicate the need of high quality virial data. 相似文献
126.
Efficient routes for the syntheses of optically pure and hitherto unknown l-chiro- and d-allo-inositol derivatives, azido- and aminocyclitols of l-chiro-configuration, diazido- and diaminocyclitols of d-allo-configuration from economically viable myo-inositol are described. These routes provide access to synthetically flexible 1,2:4,5-di-O-isopropylidene-chiro-inositol and 1,6:3,4-di-O-isopropylidene-allo-inositol, which are otherwise difficult to synthesize directly from their parent inositols. A one pot methodology that allows rapid access to both chiro- and allo-inositol derivatives has also been developed. Investigations on the glycosidase inhibitory properties of these novel azido- and amino-inositols unraveled the potentials of these classes of compounds as novel class of glycosidase inhibitors. Both d and l forms of these cyclitols could be synthesized from myo-inositol in gram scales and hence by exploiting the difference in reactivities of cis- and trans-ketals, a variety of protected derivatives, which are useful for the synthesis of unnatural phosphoinositols and natural products, can be synthesized. 相似文献
127.
Segawa Y Suzuki Y Yamashita M Nozaki K 《Journal of the American Chemical Society》2008,130(47):16069-16079
A series of lithium salts of boryl anion, boryllithiums, were synthesized and characterized by NMR spectroscopy and crystallographic analysis. In addition to the parent boryllithium compound 35a, structural modification of boryllithium, using saturated C-C and benzannulated C=C backbones in the five-membered ring and mesityl groups on the nitrogen atoms, also allowed generation of the corresponding boryllithium. The solid state structures of boryllithium showed that the boron-lithium bond is polarized where the boron atom is anionic in all (35a x DME)(2), 35a x (THF)(2), 35b x (THF)(2), and 35c x (THF)(2) when compared to the structures of hydroborane 38a-c and optimized free boryl anion opt-46a-c. Dissolution of the isolated single crystals of (35a x DME)(2) and 35a x (THF)(2) in THF-d(8) showed that the boron-lithium bond remained in solution and free DME or THF molecules were observed. Temperature-dependent (11)B NMR chemical shift changes of 35a were observed in THF-d(8) or methylcyclohexane-d(14), suggesting a change of chemical shift anisotropy around the boron center. The HOMO of opt-35a x (THF)(2) had a lone pair character on the boron atom, as observed for phenyllithium, whereas the HOMO of hydroborane 38a corresponds to the pi-orbital of the boron-containing five-membered heterocycle. The polarity of the B-Li bond, estimated by AIM analysis, was similar to that of alkyllithium. Boryllithiums 35a and 35b behave as a base or a boron nucleophile in reaction with organic electrophiles via deprotonation, S(N)2-type substitution, halogen-metal exchange or electron-transfer, 1,2-addition to a carbonyl group, and S(N)Ar reaction. In the case of the reaction with CO(2), intramolecular cyclization followed by CO elimination from borylcarboxylate anion and subsequent protonation gave hydroxyboranes 64a and 64b. The characters of the carbonyl groups in the borylcarbonyl compounds 60a, 60b, 61, 62, and 63a, which were obtained from the reaction of boryllithiums 35a and 35b, were investigated by X-ray crystallography, IR, and (13)C NMR spectroscopy to show that the boryl substituent weakened the C=O bond when compared to carbon substituted analogues. 相似文献
128.
Tsujioka T Sesumi Y Takagi R Masui K Yokojima S Uchida K Nakamura S 《Journal of the American Chemical Society》2008,130(32):10740-10747
We report here a novel phenomenon: selective metal deposition on photoswitchable diarylethene (DAE) surfaces. Magnesium vapor was deposited by vacuum evaporation on the colored DAE but not on the uncolored surface. The selective deposition originates in the change of the glass transition temperature of the amorphous DAE film resulting from photoisomerization and therefore from changes of surface molecular motion. We clarified that Mg atoms on the uncolored surface actively migrated on the surface and were desorbed from the surface. The possibility of depositing other metals is also discussed. Light-controllable metal-integrated deposition was demonstrated as a new function of the photoswitchable molecular surfaces. This study reveals new features of the photoswitchable molecular surfaces, and their potential suggests bright prospects for future applications in organic electronics. 相似文献
129.
Shono T Nagasawa T Tsubouchi A Noguchi K Takeda T 《Chemical communications (Cambridge, England)》2008,(30):3537-3539
The reaction of titanium cyclopropylidene complexes, prepared by the reductive titanation of 7,7-dichlorobicyclo[4.1.0]heptanes, with alkynes produced air and moisture stable titanacyclobutenes with a spiro-bonded cyclopropane. 相似文献
130.
Mohammad Ghazizadeh Yoshihiro Sasaki Tatsuo Oguro Shigeru Sato Seiko Egawa Kyoko Inoue Akiko Adachi Hajime Shimizu Oichi Kawanami 《Microscopy and microanalysis》2008,14(4):357-361
Observation of the internal ultrastructure of human chromosomes by transmission electron microscopy (TEM) has frequently been attempted in spite of the difficulties in detaching metaphase chromosome spreads from the glass slide for further processing. In this study we have used a method in which metaphase chromosome spreads were prepared on a flexible thermoplastic membrane (ACLAR) film. To assess chromosome identity, a diamidino-phenylindole staining and karyotying was first done using a conventional cytogenetic system. The chromosome spreads were then fixed with 1% osmium tetroxide, stained with freshly prepared 2% tannic acid, dehydrated, and flat-embedded in epoxy resin. The resin sheet was easily detachable and carried whole chromosome spreads. By this method, TEM observation of chromosomes from normal human lymphocytes allowed a thorough examination of the ultrastructure of centromeres, telomeres, fragile sites, and other chromosomal regions. Various ultrastructural patterns including thick electron dense boundaries, less dense internal regions, and extended chromatin loops at the periphery of the chromosomes were discernible. Application of the present method to chromosome research is expected to provide comprehensive information on the internal ultrastructure of different chromosomal regions in relation to function. 相似文献