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11.
Lattice images of 4H, 5H, and 6H perovskite polytypes have been obtained. With the electron beam parallel to 10
, the images are correlated directly with the projected structures of the polytypes. Stacking faults were found only in the 6H compound, and consisted of additional cubic close-packed AO3 layers. Ordering of cation vacancies in the 5H material was evident in the lattice image as an array of white dots. 相似文献
12.
This paper describes the design, construction and use of a field-cycled proton-electron double-resonance imaging (FC-PEDRI) system for the detection and imaging of free radicals. The unique feature of this imager is its use of a 450-mT detection magnetic field in order to achieve good image quality and sensitivity. The detection magnetic field is provided by a superconducting magnet, giving high stability and homogeneity. Field cycling is implemented by switching on and off the current in an internal, coaxial, resistive secondary magnet that partially cancels the superconducting magnet's field at the sample; the secondary magnet is actively shielded to avoid eddy currents. EPR irradiation takes place at approximately 5 mT, following which the field is switched to 450 mT in 40 ms for NMR signal detection. Full details of the imager's subsystems are given, and experiments to image the distribution of stable free radical contrast agents in phantoms and in anesthetized rats are described. 相似文献
13.
Facchetti A Yoon MH Stern CL Hutchison GR Ratner MA Marks TJ 《Journal of the American Chemical Society》2004,126(41):13480-13501
The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) alpha,omega-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) beta,beta'-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) alpha,omega-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) beta,beta'-dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (alphanTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties. 相似文献
14.
In a gas reaction cell (GRC), installed in a high-resolution transmission electron microscope (HRTEM) (JEOL 4000EX), samples can be manipulated in an ambient atmosphere (p<50mbar). This experimental setup permits not only the observation of solid-gas reactions in situ at close to the atomic level but also the induction of structural modifications under the influence of a plasma, generated by the ionization of gas particles by an intense electron beam. Solid state reactions of non-stoichiometric niobium oxides and niobium tungsten oxides with different gases (O2, H2 and He) have been carried out inside this controlled environment transmission electron microscope (CETEM), and this has led to reaction products with novel structures which are not accessible by conventional solid state synthesis methods.Monoclinic and orthorhombic Nb(12)O(29) crystallize in block structures comprising [3x4] blocks. The oxidation of the monoclinic phase occurs via a three step mechanism: firstly, a lamellar defect of composition Nb(11)O(27) is formed. Empty rectangular channels in this defect provide the diffusion paths in the subsequent oxidation. In the second step, microdomains of the Nb(22)O(54) phase are generated as an intermediate state of the oxidation process. The structure of the final product Nb(10)O(25), which consists of [3x3] blocks and tetrahedral coordinated sites, is isostructural to PNb(9)O(25). Microdomains of this apparently metastable phase appear as a product of the Nb(22)O(54) oxidation. The oxidation reaction of Nb(12)O(29) was found to be a reversible process: the reduction of the oxidation product with H(2) results in the formation of the starting Nb(12)O(29) structure. On the other hand, the block structure of Nb(12)O(29) has been destroyed by a direct treatment of the sample with H(2) while NbO in a cubic rock salt structure is produced.This in situ technique has also been applied to niobium tungsten oxides which constitute the solid solution series Nb(8-n)W9(+n)O47 with 0< or =n< or =4. All of these phases crystallize in the threefold tetragonal tungsten bronze (TTB) superstructure of Nb(8)W(9)O(47) (n=0). In the main reaction, these phases decompose in a gas plasma (O2, H2 or He, p=20mbar) into WO(3-x), which evaporates and solidifies again near the irradiated crystallite, and (Nb,W)(24)O(64), which crystallizes in a 2a superstructure of the TTB type observed here for the first time in the system Nb-W-O. Nb(8)W(9)O(47), Nb(7)W(10)O(47) and Nb(6)W(11)O(47) always react in this way, independent of the applied gas. On the other hand, the treatment of Nb(5)W(12)O(47) (n=3) and Nb(4)W(13)O(47) (n=4) in an oxygen atmosphere often caused a different reaction: these phases have been oxidized and a heavily disordered bronze-type structure has been formed. The oxygen excess in these products is largely accommodated in segregated domains of WO(3). 相似文献
15.
The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton. 相似文献
16.
Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results. 相似文献
17.
Hai‐Jing Nie Xialing Chen Chang‐Jiang Yao Prof. Dr. Yu‐Wu Zhong Prof. Dr. Geoffrey R. Hutchison Prof. Dr. Jiannian Yao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(45):14497-14509
Electron delocalization of new mixed‐valent (MV) systems with the aid of lateral metal chelation is reported. 2,2′‐Bipyridine (bpy) derivatives with one or two appended di‐p‐anisylamino groups on the 5,5′‐positions and a coordinated [Ru(bpy)2] (bpy=2,2′‐bipyridine), [Re(CO)3Cl], or [Ir(ppy)2] (ppy=2‐phenylpyridine) component were prepared. The single‐crystal molecular structure of the bis‐amine ligand without metal chelation is presented. The electronic properties of these complexes were studied and compared by electrochemical and spectroscopic techniques and DFT/TDDFT calculations. Compounds with two di‐p‐anisylamino groups were oxidized by a chemical or electrochemical method and monitored by near‐infrared (NIR) absorption spectral changes. Marcus–Hush analysis of the resulting intervalence charge‐transfer transitions indicated that electron coupling of these mixed‐valent systems is enhanced by metal chelation and that the iridium complex has the largest coupling. TDDFT calculations were employed to interpret the NIR transitions of these MV systems. 相似文献
18.
Seth C. Rasmussen Jason C. Pickens James E. Hutchison 《Journal of heterocyclic chemistry》1997,34(1):285-288
A new synthetic route to 4-substituted-2,2′-bithiophenes has been developed utilizing 4-bromo-2,2′-bithiophene ( 1 ). Formation of the bithienyllithium adduct via halogen-metal exchange was found to be problematic and resulted in complex mixtures of products. The Grignard reagent of 1 can be obtained easily via the “entrainment” method, allowing the production of 4-substituted-2,2′-bithiophenes (where sub-stituent = octyl, hydroxyethyl, hydroxymethyl, carboxy, carbomethoxy, acetoxyethyl, and acetoxymethyl). 相似文献
19.
Maxwell Sherrod L. Culligan Brian Hutchison Jay B. Utsey Robin C. Sudowe Ralf McAlister Daniel R. 《Journal of Radioanalytical and Nuclear Chemistry》2017,311(1):439-446
The sorption and diffusion behavior of cesium was studied to support the interpretation of the ongoing in-situ experiments in the Olkiluoto test site. The distribution coefficients of cesium in the Olkiluoto pegmatitic granite, veined gneiss and their main minerals were obtained by batch sorption experiments and the diffusion of cesium was studied in rock cubes. The results were modelled with PHREEQC and Comsol Multiphysics. The distribution coefficients of cesium were largest in biotite and veined gneiss. The effective diffusion coefficients of cesium from the diffusion model were 3 × 10−13 m2 s−1 for veined gneiss and 4 × 10−13 m2 s−1 for pegmatitic granite.
相似文献20.
The more recent developments in the spectroscopy of Nuclear Magnetic Resonance on Oriented Nuclei (NMRON) are reviewed; both
theoretical and experimental advances are summarised with applications to On-Line and Off-Line determination of magnetic dipole
and electric quadrupole hyperfine parameters. Some emphasis is provided on solid state considerations with indications of
where likely enhancements in technique will lead in conventional hyperfine studies. 相似文献